Method for connecting amido podand molecule to solid-phase material and application of amido podand molecule
By linking amide ether molecules onto mesoporous silica-based porous materials, modified solid-phase materials were prepared, solving the adsorption problem of Eu(III) in high-level radioactive waste liquid. This achieved efficient adsorption and easy material recovery, avoiding the generation of a third phase, and has good potential for industrial application.
Patent Information
- Application Number
- CN202511003772.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-21
- Publication Date
- 2025-11-07
AI Technical Summary
Existing technologies are difficult to effectively treat radioactive minor actinides, such as Eu(III), in high-level radioactive waste liquids, and the extractant is prone to generating a third phase during use, which affects separation efficiency and material utilization.
A modified solid-phase material is prepared by attaching amide ether molecules to mesoporous silica-based porous materials. The reaction of silane coupling agent and acyl chloride forms Si-O bonds, fixing the amide ether molecules at a suitable pore size, thereby modifying the material and avoiding the formation of a third phase.
It improves the adsorption effect and recycling rate of materials, simplifies the process, reduces solid waste, and has good prospects for industrial application.
Smart Images
Figure CN120900587A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of radioactive waste treatment, in particular to a method for connecting amide pod ether molecules to solid phase materials and application. BACKGROUND
[0002] Nuclear energy has developed rapidly due to its own advantages such as cleanliness, high energy density, and less waste and recycling. However, the spent fuel reprocessing work is facing increasingly severe challenges, and high-level liquid waste (HLLW) is one of the main waste produced in the spent fuel wet reprocessing process. These difficult-to-treat nuclear waste, i.e. high-level liquid waste (HLLW) and other radioactive waste, contains super-uranium elements and a large amount of fission products (FPs) such as long half-life radionuclides (trivalent minor actinide elements, Am and Cm, etc.).
[0003] Because Eu has similar chemical properties to Am and Cm and other radioactive minor actinide elements, Eu is considered to be able to replace Am and Cm and other radioactive minor actinide elements for experiments to simulate the chemical behavior of other elements. Eu often exists in the form of Eu(III) in solution, so Eu(III) is mostly studied in experiments.
[0004] Amide pod ether extractants are a kind of extractants proposed in recent years, and this kind of extractants has excellent extraction performance for trivalent actinide and lanthanide elements, and has good application prospect in the separation process of high-level liquid waste actinide elements. SUMMARY
[0005] To solve the above technical problems, the present application provides a method for connecting amide pod ether molecules to mesoporous silica-based porous materials to produce an adsorbent material. The method has the characteristics of easy recovery, good adsorption effect, and difficulty in generating a third phase. Moreover, the method can separate solid waste generated during the synthesis of pod ether from the required material, thereby improving the utilization rate.
[0006] The present application provides a method for connecting amide pod ether molecules to solid phase materials, comprising the following steps:
[0007] (1) Disperse the silane coupling agent in toluene solvent to obtain a silane solution with a concentration of 6-11%, and add triethylamine to the silane solution;
[0008] (2) Under ice bath conditions, add an acyl chloride solution with a concentration of 1-4% to the above solution, and after the acyl chloride solution is completely added, perform a synthesis reaction under room temperature condensation reflux stirring; and sequentially filter and rotary evaporate the product after synthesis to obtain amide pod ether;
[0009] (3) the solid phase material, amide pod ether, triethylamine are mixed according to the mass volume ratio of 1g: 0.8-3mL: 7-15mL, and then the mixture is stirred and refluxed for a period of time, and then the reaction product is filtered, washed and dried in sequence to obtain the modified solid phase material.
[0010] Further, the experimental system in steps (1), (2) and (3) is kept in anhydrous environment.
[0011] Further, in step (1), the silane coupling agent is one of 3-[2-(2-aminoethylamino) ethylamino] propyl-trimethoxysilane, N-aminoethyl-γ-propylamino trimethoxysilane and 3-aminopropyl triethoxysilane.
[0012] Further, in step (1), the molar ratio of triethylamine to acyl chloride is 2-3:1, and the reaction temperature of step (1) is controlled below 10℃.
[0013] Further, in step (2), the ice bath reaction time is 1-2h, the acyl chloride solution is added dropwise by using a constant pressure funnel, and the room temperature reaction time is 12-16h.
[0014] Further, in step (2), the filtrate is reserved for rotary evaporation to obtain a yellow viscous liquid, the rotary evaporation temperature is 97℃, and the pressure is-0.08MPa.
[0015] Further, in step (3), the solid phase material includes microporous material and mesoporous silica-based porous material, the solid phase material is pre-activated, the activation temperature is 150℃, and the activation time is 2-3h, and the reaction solvent is toluene.
[0016] Further, in step (3), the stirring speed is 100-130r / min, the stirring temperature is 50-120℃, the stirring time is 24-26h, the washing is performed by using toluene for multiple times, and the drying temperature is 40℃, and the drying time is 2-4h.
[0017] The application further provides a modified solid phase material prepared by a method of connecting an amide pod ether molecule to a solid phase material.
[0018] The application further provides an application of the modified solid phase material, and the solid phase material is applied to adsorption of Eu(III).
[0019] The application has the following beneficial effects:
[0020] The method of the present application first synthesizes an amide pod ether by using silane, so that the amide pod ether has Si-O bond and can be connected with solid phase material; then the solid phase material is modified by using the amide pod ether, and the modified solid phase material is connected with chloroform by using silane, so that the amide pod ether molecules are fixed on the proper pore size; the present application has the characteristics of simple process, easy-to-obtain material, etc., and compared with the current method, the present application can separate the solid waste generated in the process of synthesizing pod ether (the reaction of silane and chloroform) from the target material, and improve the utilization rate. The solid phase material adsorbent prepared by the present application has the advantages of easy recovery, good adsorption effect and no easy generation of third phase, and has good industrial application prospect. BRIEF DESCRIPTION OF DRAWINGS
[0021] Figure 1 The infrared spectrum of the MCM-41 modified in Example 1 of the present application. DETAILED DESCRIPTION
[0022] The present application will be further described in detail below in combination with specific embodiments, and the examples given are only for illustrating the present application, but not for limiting the scope of the present application.
[0023] In the following examples, the experimental methods are conventional methods, unless otherwise specified.
[0024] In the following examples, the materials, reagents, etc. used are commercially available, unless otherwise specified.
[0025] A method for connecting an amide pod ether molecule to solid phase material, first synthesizes an amide pod ether, and then modifies the solid phase material with the amide pod ether to fix it on the solid phase material. Specifically:
[0026] (1) Synthesis of amide pod ether
[0027] In anhydrous environment, the temperature is controlled below 10℃, the silane coupling agent, toluene and triethylamine are mixed and stirred, when the temperature drops to about 0℃, the acyl chloride solution is added to the above solution, and the ice bath is stirred for 1-2h, and then the normal temperature reaction is carried out for 12h; the product is subjected to suction filtration to obtain the filtrate; the filtrate is subjected to rotary evaporation to remove toluene, triethylamine and acyl chloride, and a yellow viscous liquid is obtained.
[0028] (2) Modification of solid phase material
[0029] The solid phase material is vacuum dried and activated at 150℃ for 2h; in anhydrous environment, the solid phase material, the synthesized amide pod ether and triethylamine are mixed according to the mass volume ratio of 1g: 0.8-3ml: 7-15ml, the solvent is toluene, and the condensation reflux reaction is carried out at 50-120℃ for 24-26h; the reaction is subjected to suction filtration, and the solid is obtained, which is washed with toluene for multiple times and then dried at 40℃ for 2h;
[0030] The concentration of the silane solution in the method for synthesizing the amide gourd ether is 6-11%.
[0031] The acyl chloride solution is added dropwise in the method for synthesizing the amide gourd ether, the solvent of the acyl chloride solution is toluene, and the concentration of the acyl chloride solution is 1-4%.
[0032] The silane coupling agent in the method for synthesizing the amide gourd ether is 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane, N-aminoethyl-γ-propylaminotrimethoxysilane or 3-aminopropyltriethoxysilane.
[0033] The product is filtered in the method for synthesizing the amide gourd ether, the filtrate is taken for rotary evaporation to remove toluene, triethylamine and DGA-Cl, and the amide gourd ether is retained according to the boiling point of the material. The rotary evaporation is performed by vacuum distillation at a temperature of 97°C and a pressure of-0.08 MPa.
[0034] The concentration of the amide gourd ether in the method for modifying the solid phase material is 0.8-3%.
[0035] The stirring speed in the method for modifying the solid phase material is 100-130 r / min.
[0036] Example 1
[0037] (1) Synthesis of amide gourd ether
[0038] In an anhydrous environment, 7 ml of N-aminoethyl-γ-propylaminotrimethoxysilane, 45 mL of toluene and 15 mL of triethylamine are placed in a three-necked flask and a magnetic stirrer is installed; 2 mL of 2,2’oxydiacyl chloride (DGA-Cl) is measured in a 250 mL constant pressure funnel containing 70 mL of toluene; a thermometer is placed in the side hole of the three-necked flask, and the constant pressure funnel is placed in the middle; the three-necked flask is placed in an ice bath, and when the temperature of the solution in the container drops to about 0°C, the plug of the constant pressure funnel is opened, and 2,2’oxydiacyl chloride (DGA-Cl) is allowed to react with N-aminoethyl-γ-propylaminotrimethoxysilane for 1 h; the temperature during the reaction needs to be controlled below 10°C, and after the solution in the constant pressure funnel is added dropwise, the reaction can be carried out at room temperature, and the reaction time is 12 h; the product is filtered, and the filtrate is taken; the filtrate is subjected to rotary evaporation to remove toluene, triethylamine and DGA-Cl, and a yellow viscous liquid is obtained.
[0039] (2) Modification of MCM-41
[0040] 1 g of MCM-41 was placed in a three-necked flask and dried under vacuum at 150 °C for 2 h. Under anhydrous conditions, 100 mL of toluene was added to a 250 mL three-necked flask, a magnetic stir bar was placed, and the activated MCM-41 powder was dispersed into the toluene. A condenser was inserted through the center hole, and glass stoppers were inserted into the other two holes. 0.8 mL of DGA-N-aminoethyl-γ-propylaminotrimethoxysilane (amide ether) and 1.2 mL of triethylamine were added to the three-necked flask. The mixture was refluxed at 50 °C for 24 h. The reactants were filtered, the solid was collected, washed several times with toluene, and dried at 40 °C for 2 h.
[0041] from Figure 1 As can be seen, compared with the initial infrared absorption peak of MCM-41, two additional characteristic peaks appear around 1650-1400, corresponding to the infrared absorption peaks of the -C=O- group of acyl chloride (1680-1630 cm⁻¹). -1 The absorption peak of -NH- on silane (1650-1550 cm⁻¹) is similar to that of silane. -1 The modification of MCM-41 was successful.
[0042] (3) The modified MCM-41 was used to adsorb Eu(III), and the adsorption capacity of the material for Eu(III) reached 200 mg / g.
[0043] Example 2
[0044] (1) Synthesis of amide podyl ether
[0045] The synthesis method is the same as that in Example 1.
[0046] (2) Modification of microporous materials
[0047] 1 g of microporous zeolite was placed in a three-necked flask and dried and activated under vacuum at 150 °C for 2 h. Under anhydrous conditions, 100 mL of toluene was added to a 250 mL three-necked flask, a magnetic stir bar was placed, and the activated MCM-41 powder was dispersed into the toluene. A condenser was inserted through the middle hole, and glass stoppers were inserted into the other two holes. 0.8 mL of DGA-N-aminoethyl-γ-propylaminotrimethoxysilane (amide ether) and 1.2 mL of triethylamine were added to the three-necked flask. The mixture was refluxed at 120 °C for 24 h. The reactants were filtered, the solid was collected, washed several times with toluene, and dried at 40 °C for 2 h. The modified microporous material was then used to adsorb Eu(III).
[0048] Comparative Example 1
[0049] Synthesis of amide podyl ethers
[0050] In anhydrous environment, 7 mL N-aminoethyl-gamma-propylaminotrimethoxysilane and 45 mL toluene were placed in a three-necked flask and equipped with a magnetic stirrer; 2 mL DGA-Cl was measured in a 250 mL constant pressure funnel containing 70 mL toluene; a thermometer was placed in the side hole of the three-necked flask, and the constant pressure funnel was placed in the middle; the three-necked flask was placed in an ice bath, and when the temperature of the solution in the container dropped to about 0°C, the plug of the constant pressure funnel was opened, and DGA-Cl was allowed to react with N-aminoethyl-gamma-propylaminotrimethoxysilane for 1 h; the temperature during the reaction should be controlled below 10°C, and after the solution in the constant pressure funnel was added dropwise, the reaction could be carried out at room temperature, and the reaction time was 12 h; the product was suction filtered, and the filtrate was obtained; the filtrate was subjected to rotary evaporation to remove toluene and DGA-Cl, and a light yellow liquid was obtained.
[0051] As can be seen from the final amide pod ether sample, when triethylamine is not added, the obtained sample is a light yellow liquid, which is quite different from the yellow viscous liquid of Example 1.
[0052] Comparative Example 2
[0053] Synthesis of amide pod ether
[0054] 7 mL N-aminoethyl-gamma-propylaminotrimethoxysilane and 45 mL toluene were placed in a three-necked flask and equipped with a magnetic stirrer; 2 mL DGA-Cl was measured in a 250 mL constant pressure funnel containing 70 mL toluene; a thermometer was placed in the side hole of the three-necked flask, and the constant pressure funnel was placed in the middle; the three-necked flask was placed in an ice bath, and when the temperature of the solution in the container dropped to about 0°C, the plug of the constant pressure funnel was opened, and DGA-Cl was allowed to react with N-aminoethyl-gamma-propylaminotrimethoxysilane for 1 h; the temperature during the reaction should be controlled below 10°C, and after the solution in the constant pressure funnel was added dropwise, the reaction could be carried out at room temperature, and the reaction time was 12 h; at this time, a white gel was obtained;
[0055] In the case of not ensuring a sealed and anhydrous environment, after the acyl chloride solution was stirred for a period of time, the solution became a white gel.
[0056] The above description of the disclosed embodiments is merely intended to enable those skilled in the art to implement or use the present application. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to the embodiments shown herein but will be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A method of attaching an amide pod molecule to a solid phase material, characterized by, The method comprises the following steps: (1) dispersing silane coupling agent in toluene solvent to obtain a silane solution with a concentration of 6-11%, and adding triethylamine into the silane solution; (2) adding an acyl chloride solution with a concentration of 1-4% into the solution under ice bath condition, and performing synthesis reaction under condensation reflux stirring at room temperature after the acyl chloride solution is completely added dropwise; and sequentially filtering and rotary evaporating the product after synthesis to obtain an amide pod ether; (3) condensation reflux stirring the solid phase material, the amide pod ether and triethylamine according to a mass volume ratio of 1g:0.8-3mL:7-15mL, and sequentially performing suction filtration, washing and drying on the reaction product to obtain a modified solid phase material.
2. The method of claim 1, wherein the amide pod molecule is attached to the mesoporous silica-based porous material by, The experimental system of steps (1), (2) and (3) is kept in anhydrous environment.
3. The method of claim 1, wherein the amide pod molecule is attached to the mesoporous silica-based porous material by, In step (1), the silane coupling agent is one of 3-[2-(2-aminoethylamino) ethylamino] propyl-trimethoxysilane, N-aminoethyl-gamma-propylamino trimethoxysilane and 3-aminopropyl triethoxysilane.
4. The method of claim 1, wherein the amide pod molecule is attached to the mesoporous silica-based porous material by, In step (1), the molar ratio of triethylamine to acyl chloride is 2-3:1, and the reaction temperature of step (1) is controlled below 10℃.
5. The method of claim 1, wherein the amide pod molecule is attached to the mesoporous silica-based porous material by a covalent bond. In step (2), the ice bath reaction time is 1-2h, the acyl chloride solution is added dropwise by using a constant pressure funnel, and the room temperature reaction time is 12-16h.
6. The method of claim 1, wherein the amide pod molecule is attached to the mesoporous silica-based porous material by, In step (2), the filtrate is reserved for rotary evaporation to obtain a yellow viscous liquid, the rotary evaporation temperature is 97℃, and the pressure is-0.08MPa.
7. The method of claim 1, wherein the amide pod molecule is attached to the mesoporous silica-based porous material by a covalent bond. In step (3), the solid phase material includes microporous material and mesoporous silica-based porous material, the solid phase material is pre-activated, the activation temperature is 150℃, and the activation time is 2-3h, and the reaction solvent is toluene.
8. The method of claim 1, wherein the amide pod molecule is attached to the mesoporous silica-based porous material by, In step (3), the stirring speed is 100-130r / min, the stirring temperature is 50-120℃, the stirring time is 24-26h, the washing is performed by using toluene for multiple times, and the drying temperature is 40℃, and the drying time is 2-4h.
9. A modified solid phase material prepared by a method of connecting the amide pod ether molecule of claim 1 to a solid phase material.
10. Use of the modified solid phase material according to claim 9, characterized in that The solid phase material is applied to adsorption of Eu(III).