Preparation method and application of porous rhenium imprinted composite material
By synthesizing porous rhenium-imprinted composite materials through an ionic liquid mixing system, the problem of low rhenium separation efficiency in existing technologies has been solved, enabling efficient extraction of high-purity ammonium perrhenate and reducing production costs.
Patent Information
- Application Number
- CN202511697291.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-19
- Publication Date
- 2026-02-03
AI Technical Summary
Existing technologies are insufficient to efficiently and economically separate trace amounts of valuable rhenium from molybdenum and other impurities with similar chemical properties, which affects rhenium recovery rates and production costs.
Porous rhenium-imprinted composite materials were synthesized using nano-regions of an ionic liquid mixing system as soft templates. By adding substances such as N-vinylimidazole and 4-chloromethylstyrene to an aqueous solution containing rhenium ionic liquid, porous rhenium-imprinted composite materials with mesopores and micropores were prepared.
The prepared porous rhenium-imprinted composite material has high activity and can efficiently extract ammonium perrhenate with a purity of over 99.999%, avoiding the drawbacks of the hard template method. It is also low in cost and easy to use.
Smart Images
Figure CN121446459A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of hydrometallurgy, and particularly relates to a preparation method and application of a porous rhenium imprint composite material. BACKGROUND
[0002] Rhenium is known as "aviation engine bone powder". About 80% of the global rhenium is used for producing aviation engines, which has important significance in military strategy. Rhenium, known as "the core of aerospace", is a rare metal rarer than rare earth, and is an important strategic metal mineral resource. In order to ensure the safety of key raw materials in the fields of aviation, aerospace and military, strive for technological leadership and ensure long-term development, it is necessary to carry out scientific research and technical development of rhenium, and to do well in the strategic reserve of rhenium resources.
[0003] The core difficulty of rhenium extraction is how to efficiently and economically separate trace and precious rhenium from molybdenum and other impurities with similar chemical properties. Whether it is rhenium-molybdenum separation and phase state control in solvent extraction, or elution efficiency in ion exchange, it is directly related to the recovery rate of rhenium and production cost. At present, in view of these difficulties, researches are mainly concentrated in the development of higher selective extractants and resins, the optimization of existing process (such as controlling extraction conditions to prevent third phase), and the exploration of extraction-ion exchange combined process.
[0004] At present, the demand for high-purity metals at home and abroad is increasing, and the requirement for purity is extremely strict. The current market extraction rhenium method still has room for further improvement, therefore, it is urgent to design and develop a porous rhenium imprint composite material which can efficiently extract rhenium. SUMMARY
[0005] In view of the above technical problems, the application provides a preparation method of a porous rhenium imprint composite material, which uses a nano microzone of an ionic liquid mixed system as a soft template to synthesize the porous rhenium imprint composite material, avoiding various disadvantages of etching of a hard template method. The prepared porous rhenium imprint composite material has mesopores and micropores at the same time, and the hierarchical porous rhenium imprint composite material has the advantages of large specific surface area, adjustable pore size and designable pore environment, so that it exhibits very high activity in rhenium extraction.
[0006] To achieve the above purpose, the application adopts the following technical scheme:
[0007] The preparation method of the porous rhenium imprinting composite material is as follows: firstly, porous silica is synthesized in an ionic liquid mixed system, the porous silica is dispersed in a rhenium-containing ionic liquid aqueous solution, then N-vinylimidazole and 4-chloromethylstyrene are added, and azobisisobutyronitrile is added, and the mixture is heated and stirred at 50-70 DEG C for 10-12 h; after the reaction is completed, a dilute hydrochloric acid solution is used to wash away the perrhenate ions used for imprinting and other reactants which are not polymerized and remain on the surface, and the porous rhenium imprinting composite material is obtained after drying.
[0008] Further, in the preparation method of the porous rhenium imprinting composite material, the rhenium-containing ionic liquid aqueous solution is [C4mim][BF4] / H2O / NH4ReO4.
[0009] Further, in the rhenium-containing ionic liquid aqueous solution, the ratio of [C4mim][BF4] to H2O is 6-8:2-4 by weight fraction, and the concentration of NH4ReO4 is 20 g / L.
[0010] Further, in the preparation method of the porous rhenium imprinting composite material, the ratio of N-vinylimidazole to 4-chloromethylstyrene is 1:0.9-1.1 by weight fraction.
[0011] Further, in the preparation method of the porous rhenium imprinting composite material, the amount of azobisisobutyronitrile is 1-3% of the total mass of N-vinylimidazole and 4-chloromethylstyrene.
[0012] Further, in the preparation method of the porous rhenium imprinting composite material, the mass concentration of the dilute hydrochloric acid solution is 3-6%.
[0013] Further, in the preparation method of the porous rhenium imprinting composite material, the preparation method of the porous silica is as follows: 10 parts of an ionic liquid mixed system and 2 parts of TEOS are mixed, the mixture is stirred at 80 DEG C and 600 rpm for 30 minutes, then the temperature is lowered to 25 DEG C to form a porous gel and stabilize for 48 hours until the TEOS is completely hydrolyzed, the obtained precipitate is washed with water for 3 times to obtain the porous silica.
[0014] Further, in the preparation method of the porous silica, the ionic liquid mixed system is [C8mim]Br / H2O / NaCl system.
[0015] Preferably, in the ionic liquid mixed system, the ratio of [C8mim]Br:H2O:NaCl is 6-8:1-3:0.5-2 by weight fraction.
[0016] The porous rhenium imprinting composite material prepared by the preparation method described in any one of the above is applied to the extraction and preparation of ammonium perrhenate.
[0017] The beneficial effects of the present application are:
[0018] 1、The porous rhenium imprinted composite material prepared by the present application has the advantages of convenient transportation and storage, low cost, simple use and high rhenium extraction efficiency.
[0019] 2、The porous rhenium imprinted composite material is synthesized by using the nano microzone of the ionic liquid mixed system as a soft template, which avoids various drawbacks of etching by a hard template method.
[0020] 3、The porous rhenium imprinted composite material of the present application is a composite material with a porous structure, and has mesopores and micropores at the same time. These hierarchical porous rhenium imprinted composite materials have the advantages of large specific surface area, adjustable pore size and designable pore environment, so that they exhibit very high activity in rhenium extraction. When the material is applied to the extraction and preparation of ammonium rhenate, the purity of the ammonium rhenate product can reach 99.999% or above. BRIEF DESCRIPTION OF DRAWINGS
[0021] Figure 1 It is a TEM image of the porous rhenium imprinted composite material of Example 1.
[0022] Figure 2 It is a TEM image of the porous rhenium imprinted composite material of Example 2.
[0023] Figure 3 It is a TEM image of the porous rhenium imprinted composite material of Example 3.
[0024] Figure 4 It is a BET image of the porous rhenium imprinted composite material of Example 1. DETAILED DESCRIPTION
[0025] It should be noted that the following examples are only used to illustrate the technical solutions described in the present application and do not limit the technical solutions described in the present application, therefore, although the present application has been described in detail with reference to the following examples, those skilled in the art should understand that the present application can still be modified or replaced by equivalents; and all solutions and improvements that do not deviate from the spirit and technical scope of the present application should be covered in the scope of the claims of the present application.
[0026] Example 1
[0027] 1) Preparation of porous silica
[0028] 10 parts of the ionic liquid mixture ([C8mim]Br / H2O / NaCl) and 2 parts of tetraethyl orthosilicate (TEOS) were mixed, the ionic liquid mixture contained 75 wt% of ionic liquid [C8mim]Br, 20 wt% of H2O and 5 wt% of NaCl, the mixture was stirred at 80°C for 30 minutes (600 rpm), and then cooled to 25°C to form a porous gel and stabilized for 48 hours until the TEOS was completely hydrolyzed. The obtained precipitate was repeatedly washed with water for 3 times to obtain porous silica, which was ready for use.
[0029] 2) Preparation of porous rhenium imprinted composite material
[0030] 10 parts of porous silica were put into 100 parts of 20 g / L ammonium perrhenate ionic liquid aqueous solution ([C4mim][BF4] / H2O / NH4ReO4), which contained 70 wt% of [C4mim][BF4] and 30 wt% of H2O, and stirred and dispersed. Then 4 parts of N-vinylimidazole and 3.85 parts of 4-chloromethylstyrene were added, and after mixing for 30 min, 0.2 parts of azobisisobutyronitrile was added, and stirred in a 70°C water bath for 12 h. After the reaction was completed, 5% hydrochloric acid solution was used to wash away the perrhenate ions used for imprinting, and at the same time, other reactants that were not polymerized and remained on the surface were washed away, until no rhenium element was detected in the washing liquid, and finally deionized water was used for washing 3 times, and dried at 50°C to constant weight, to obtain a porous rhenium imprinted composite material.
[0031] 3) Performance test
[0032] The obtained porous rhenium imprinted composite material was applied to rhenium extraction from copper smelting waste acid, with high selectivity and a yield of up to 98.36%, and the purity of ammonium rhenate product was as high as 99.99946%.
[0033] Example 2
[0034] 1) Preparation of porous silica
[0035] 10 parts of the ionic liquid mixture ([C8mim]Br / H2O / NaCl) and 2 parts of tetraethyl orthosilicate (TEOS) were mixed, the ionic liquid mixture contained 75 wt% of ionic liquid [C8mim]Br, 20 wt% of H2O and 5 wt% of NaCl, the mixture was stirred at 80°C for 30 minutes (600 rpm), and then cooled to 25°C to form a porous gel and stabilized for 48 hours until the TEOS was completely hydrolyzed. The obtained precipitate was repeatedly washed with water for 3 times to obtain porous silica, which was ready for use.
[0036] 2) Preparation of porous rhenium imprinted composite material
[0037] 10 parts of porous silica was put into 100 parts of 20 g / L aqueous solution of ammonium perrhenate ionic liquid ([C4mim][BF4] / H2O / NH4ReO4), the aqueous solution of ammonium perrhenate ionic liquid contained 75 wt% [C4mim][BF4] and 25 wt% H2O, and was dispersed by stirring. Then 4 parts of N-vinylimidazole and 4 parts of 4-chloromethylstyrene were added, and after mixing for 30 min, 0.2 parts of azobisisobutyronitrile was added, and stirring was carried out at 70°C water bath for 12 h. After the reaction was completed, 4% hydrochloric acid solution was used to wash away the perrhenate ions used for imprinting, and at the same time, other reactants that were not polymerized and remained on the surface were washed away, until no rhenium element was detected in the washing liquid, and finally deionized water was used for washing 3 times, and was placed at 50°C for drying to constant weight, to obtain a porous rhenium imprinting composite material.
[0038] 3) Performance test
[0039] The obtained porous rhenium imprinting composite material was applied to rhenium extraction from copper smelting waste acid, and the selectivity was high, and the yield could reach 98.49%, and the purity of ammonium rhenate product was as high as 99.99932%.
[0040] Example 3
[0041] 1) Preparation of porous silica
[0042] 10 parts of ionic liquid mixture system ([C8mim]Br / H2O / NaCl) and 2 parts of tetraethyl orthosilicate (TEOS) were mixed, the ionic liquid mixture system contained 80 wt% ionic liquid [C8mim]Br, 10 wt% H2O and 10 wt% NaCl, the mixture was stirred at 80°C for 30 min (600 rpm), and then cooled to 25°C to form a porous gel and stabilized for 48 h until the TEOS was completely hydrolyzed. The obtained precipitate was repeatedly washed with water for 3 times to obtain porous silica, which was used for standby.
[0043] 2) Preparation of porous rhenium imprinting composite material
[0044] 10 parts of porous silica was put into 100 parts of 20 g / L ammonium perrhenate ionic liquid aqueous solution ([C4mim][BF4] / H2O / NH4ReO4), the ammonium perrhenate ionic liquid aqueous solution contained 80 wt% [C4mim][BF4] and 20 wt% H2O, and was dispersed by stirring. Then 4 parts of N-vinylimidazole and 3.9 parts of 4-chloromethylstyrene were added, 0.2 parts of azobisisobutyronitrile was added after mixing for 30 min, and stirring was carried out at 70°C water bath for 12 h. After the reaction was completed, 5% hydrochloric acid solution was used to wash away the perrhenate ions used for imprinting, and at the same time, other reactants that were not polymerized and remained on the surface were washed away, until no rhenium element was detected in the washing liquid, finally deionized water was used for washing 3 times, and was dried at 50°C to constant weight, to obtain a porous rhenium imprinting composite material.
[0045] 3) Performance test
[0046] The obtained porous rhenium imprinting composite material was applied to rhenium extraction from copper smelting waste acid, and the selectivity was high, the yield could reach 98.78%, and the purity of ammonium rhenate product was as high as 99.99918%.
[0047] Figures 1-3 The TEM images of the porous rhenium imprinting composite materials prepared in Examples 1-3, respectively, from the figure it can be seen that the porous rhenium imprinting composite materials all have porous structure, which benefits from the microstructure of the ionic liquid mixed system, Figure 4 The BET image of the porous rhenium imprinting composite material of Example 1, from the figure it can be seen that the porous rhenium imprinting composite material has both mesopores and micropores, which well proves that the synthesized material is a hierarchical pore structure.
Claims
1. A method for preparing a porous rhenium-imprinted composite material, characterized in that, The preparation method is as follows: First, porous silica is synthesized in an ionic liquid mixture system. The porous silica is dispersed in an aqueous solution containing rhenium ionic liquid. Then, N-vinylimidazolium and 4-chloromethylstyrene are added, along with azobisisobutyronitrile. The mixture is heated and stirred at 50-70°C for 10-12 h. After the reaction is completed, the perrhenate ions used for imprinting are washed away with dilute hydrochloric acid solution. At the same time, other unpolymerized reactants remaining on the surface are washed away. The mixture is then dried to obtain a porous rhenium imprinted composite material.
2. The preparation method according to claim 1, characterized in that, The porous silica is prepared as follows: 10 parts of ionic liquid mixture system and 2 parts of TEOS are mixed. The mixture is stirred at 80°C and 600 rpm for 30 minutes. Then it is cooled to 25°C to form a porous gel and stabilized for 48 hours until TEOS is completely hydrolyzed. The precipitate is washed with water 3 times to obtain porous silica.
3. The preparation method according to claim 2, characterized in that, The ionic liquid mixture system is the [C8mim]Br / H2O / NaCl system.
4. The preparation method according to claim 3, characterized in that, In the ionic liquid mixture system, the ratio of [C8mim]Br:H2O:NaCl by weight is 6-8:1-3:0.5-2.
5. The preparation method according to claim 1, characterized in that, The rhenium-containing ion-containing aqueous solution is [C4mim][BF4] / H2O / NH4ReO4.
6. The preparation method according to claim 5, characterized in that, In the rhenium-containing ionic liquid aqueous solution, the ratio of [C4mim][BF4]:H2O by weight is 6-8:2-4, and the concentration of NH4ReO4 is 20 g / L.
7. The preparation method according to claim 1, characterized in that, The ratio of N-vinylimidazole to 4-chloromethylstyrene by weight is 1:0.9-1.
1.
8. The preparation method according to claim 1, characterized in that, The amount of azobisisobutyronitrile used is 1-3% of the total mass of N-vinylimidazolium and 4-chloromethylstyrene.
9. The preparation method according to claim 1, characterized in that, The mass concentration of the dilute hydrochloric acid solution is 3-6%.
10. The application of the porous rhenium-imprinted composite material prepared by the preparation method according to any one of claims 1-9 in the extraction and preparation of ammonium perrylate.