DSC-BTrzPhen ligand, preparation method and application thereof, and method for separating lanthanide and actinide from waste liquid

Abstract

The application provides a DSC-BTrzPhen ligand and a preparation method and application thereof, and a method for separating lanthanide elements and actinide elements from waste liquid, and belongs to the technical field of extraction separation. The application starts from the design of a ligand molecular structure, develops a new DSC-BTrzPhen ligand by designing the structure of the ligand, and ensures high distribution ratio for Eu, and meanwhile, the introduction of the water-soluble ligand also ensures efficient stripping for Am, and the lanthanide-actinide separation factor SF of the DSC-BTrzPhen ligand is up to 440, and the separation effect is good. Eu / Am In addition, the water-solubility and extraction kinetics of the ligand are good, the water-solubility is extremely good, and equilibrium can be reached in 15 minutes. The ligand provides a new effective method for spent fuel reprocessing, and provides important support for sustainable development of nuclear energy, scientific treatment and safe management of existing radioactive waste.

Description

Technical Field

[0001] This invention relates to the field of extraction and separation technology, and in particular to a DSC-BTrzPhen ligand, its preparation method and application, and a method for separating lanthanides and actinides from waste liquid. Background Technology

[0002] The separation of lanthanides and actinides is crucial for the safe management of nuclear waste and the sustainable development of nuclear energy. Due to the chemical complexity of these elements, the separation process is challenging.

[0003] Methods for separating lanthanides and actinides include physical and chemical methods. Physical methods include high-speed countercurrent chromatography (HSCCC) and methods based on graphene oxide ion-sieving membranes. HSCCC is a novel separation method that combines the advantages of liquid-liquid extraction and partition chromatography, requiring no solid support and showing potential in radiochemistry. Graphene oxide ion-sieving membrane methods utilize the layered structure of graphene oxide nanosheets and adjustable nanoscale interlayer channels to separate lanthanides and actinides. Chemical methods include ion-exchange chromatography and liquid-liquid extraction. Ion-exchange chromatography separates lanthanides and actinides by utilizing the different adsorption capacities of lanthanides and actinides on ion-exchange resins. Liquid-liquid extraction separates lanthanides and actinides by selecting appropriate extractants to transfer them from one solvent to another. However, liquid-liquid extraction suffers from low separation factors and poor separation efficiency. Summary of the Invention

[0004] In view of this, the object of the present invention is to provide a DSC-BTrzPhen ligand, its preparation method and application, and a method for separating lanthanides and actinides from waste liquid. The separation factor SF of the DSC-BTrzPhen ligand of the present invention for lanthanum and actinides is... Eu / Am High efficiency and good separation effect.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] This invention provides a DSC-BTrzPhen ligand having the structure shown in Formula I:

[0007]

[0008] This invention also provides a method for preparing the DSC-BTrzPhen ligand described in the above technical solution, comprising the following steps:

[0009] A first oxidation reaction was carried out by mixing 2,9-dimethyl-1,10-o-phenanthroline, an organic solvent, and an oxidant to obtain 2,9-dialdehyde-1,10-o-phenanthroline.

[0010] The 2,9-dialdehyde-1,10-o-phenanthroline, K2CO3, Ohira-Bestmann reagent and organic solvent were mixed and subjected to a Sefert-Gilbert carbon-raising reaction to obtain 2,9-dieethynyl-1,10-o-phenanthroline.

[0011] A first nucleophilic substitution reaction was carried out by mixing 1,4-cyclohexanediol, pyridine, p-toluenesulfonyl chloride and an organic solvent to give 1-hydroxy-4-toluenesulfonylcyclohexane;

[0012] The 1-hydroxy-4-toluenesulfonylcyclohexane, potassium thioacetate, and an organic solvent were mixed to carry out a second nucleophilic substitution reaction to obtain S-(4-hydroxycyclohexyl)ethyl sulfate.

[0013] S-(4-hydroxycyclohexyl) ethyl sulfate, triphenylphosphine, diethyl azodicarbonate, diphenylphosphine azide and an organic solvent were mixed and subjected to phototelephoto reaction to obtain S-(4-azido-cyclohexyl) ethyl sulfate;

[0014] The S-(4-azido-cyclohexyl)ethyl sulfate, acetic acid, and hydrogen peroxide were mixed to carry out a second oxidation reaction. Then, the pH of the resulting oxidation product was adjusted to neutral with an inorganic alkaline substance to obtain 1-azido-4-sulfonate sodium-cyclohexane. The inorganic alkaline substance contained sodium ions.

[0015] The 2,9-diethynyl-1,10-o-phenanthroline, sodium 1-azido-4-sulfonate-cyclohexane, sodium ascorbate, diisopropylethylamine, Cu(II)-TBTA solution and solvent were mixed to carry out a copper-catalyzed azide-alkyne cycloaddition reaction to obtain the DSC-BTrzPhen ligand.

[0016] Preferably, the oxidant includes selenium dioxide.

[0017] Preferably, the Seifert-Gilbert carburization reaction is carried out under a protective atmosphere, and the Seifert-Gilbert carburization reaction takes 1 to 5 hours.

[0018] Preferably, the copper-catalyzed azide-alkyne cycloaddition reaction is carried out in a protective atmosphere for 70-80 hours.

[0019] This invention also provides the application of the DSC-BTrzPhen ligand described in the above technical solution in the separation of lanthanides and actinides.

[0020] This invention also provides a method for separating lanthanides and actinides from waste liquid, comprising the following steps:

[0021] The waste liquid is mixed with an extractant for solvent extraction, wherein the extractant is the DSC-BTrzPhen ligand as described in claim 1, and the waste liquid contains lanthanide and actinide elements.

[0022] Preferably, the lanthanide elements include europium, and the actinide elements include americium.

[0023] Preferably, the acidity of the waste liquid is 0.001 to 4 M.

[0024] Preferably, the concentration of DSC-BTrzPhen ligand in the system during solvent extraction is 2.5–40 mM.

[0025] This invention provides a DSC-BTrzPhen ligand having the structure shown in Formula I. Compared with the prior art, the advantages of this invention are as follows:

[0026] The ligand of this invention ensures both a high partition ratio for Eu and efficient back-extraction of Am, with a separation factor of SF. Eu / Am With a high efficiency of 440, the separation effect is excellent. Furthermore, the ligand exhibits good water solubility and extraction kinetics, reaching equilibrium within 15 minutes. This ligand not only provides a new and effective method for spent fuel reprocessing but also offers crucial support for the sustainable development of nuclear energy and the scientific treatment and safe management of existing radioactive waste.

[0027] This invention also provides a method for preparing the DSC-BTrzPhen ligand described in the above technical solution. The preparation method of this invention is simple, efficient, inexpensive, and easy to industrialize. Attached Figure Description

[0028] Figure 1 The reaction principle diagram for preparing the DSC-BTrzPhen ligand is shown in the example.

[0029] Figure 2 The acidity test curve for DSC-BTrzPhen;

[0030] Figure 3 Extraction curves for ligand concentrations of DSC-BTrzPhen;

[0031] Figure 4 The kinetic test curves for the DSC-BTrzPhen are shown. Detailed Implementation

[0032] This invention provides a DSC-BTrzPhen ligand having the structure shown in Formula I:

[0033]

[0034] This invention also provides a method for preparing the DSC-BTrzPhen ligand described in the above technical solution, comprising the following steps:

[0035] A first oxidation reaction was carried out by mixing 2,9-dimethyl-1,10-o-phenanthroline, an organic solvent, and an oxidant to obtain 2,9-dialdehyde-1,10-o-phenanthroline.

[0036] The 2,9-dialdehyde-1,10-o-phenanthroline, K2CO3, Ohira-Bestmann reagent and organic solvent were mixed and subjected to a Sefert-Gilbert carbon-raising reaction to obtain 2,9-dieethynyl-1,10-o-phenanthroline.

[0037] A first nucleophilic substitution reaction was carried out by mixing 1,4-cyclohexanediol, pyridine, p-toluenesulfonyl chloride and an organic solvent to give 1-hydroxy-4-toluenesulfonylcyclohexane;

[0038] The 1-hydroxy-4-toluenesulfonylcyclohexane, potassium thioacetate, and an organic solvent were mixed to carry out a second nucleophilic substitution reaction to obtain S-(4-hydroxycyclohexyl)ethyl sulfate.

[0039] S-(4-hydroxycyclohexyl) ethyl sulfate, triphenylphosphine, diethyl azodicarbonate, diphenylphosphine azide and an organic solvent were mixed and subjected to phototelephoto reaction to obtain S-(4-azido-cyclohexyl) ethyl sulfate;

[0040] The S-(4-azido-cyclohexyl)ethyl sulfate, acetic acid, and hydrogen peroxide were mixed to carry out a second oxidation reaction. Then, the pH of the resulting oxidation product was adjusted to neutral with an inorganic alkaline substance to obtain 1-azido-4-sulfonate sodium-cyclohexane. The inorganic alkaline substance contained sodium ions.

[0041] The 2,9-diethynyl-1,10-o-phenanthroline, sodium 1-azido-4-sulfonate-cyclohexane, sodium ascorbate, diisopropylethylamine, Cu(II)-TBTA solution and solvent were mixed to carry out a copper-catalyzed azide-alkyne cycloaddition reaction to obtain the DSC-BTrzPhen ligand.

[0042] Unless otherwise specified, all raw materials used in this invention are commercially available products in the field.

[0043] In this invention, 2,9-dimethyl-1,10-o-phenanthroline, an organic solvent, and an oxidant are mixed to carry out a first oxidation reaction to obtain 2,9-dialdehyde-1,10-o-phenanthroline.

[0044] In this invention, the oxidant preferably includes selenium dioxide, which is preferably used in the form of a selenium dioxide solution. The solvent of the selenium dioxide solution is preferably 1,4-dioxane and water, the volume ratio of 1,4-dioxane and water is preferably 120:3.4, and the amount ratio of selenium dioxide to water is preferably 5.59 g:3.4 mL.

[0045] In this invention, the organic solvent for the first oxidation reaction is preferably 1,4-dioxane.

[0046] In this invention, the molar ratio of 2,9-dimethyl-1,10-o-phenanthroline to the oxidant is preferably 24.01:50.42.

[0047] In this invention, the first oxidation reaction is preferably carried out under reflux conditions, and the time is preferably 0.5 to 2 hours.

[0048] In a specific embodiment of the present invention, selenium dioxide is preferably weighed into a double-necked round-bottom flask, a magnetic stir bar is added, and then 1,4-dioxane and water are added to the flask containing selenium dioxide. 2,9-dimethyl-1,10-o-phenanthroline is weighed into a heart-shaped flask, and 1,4-dioxane is added to the heart-shaped flask to completely dissolve it. The round-bottom flask containing the selenium dioxide solution is mounted on an oil bath, and a reflux condenser is mounted on the top neck. The side neck is covered with a rubber stopper. The oil bath is heated to 110°C for reflux. The 2,9-dimethyl-1,10-o-phenanthroline solution is transferred to a reaction flask through a conduit to carry out the first oxidation reaction.

[0049] After the first oxidation reaction begins, preferably during reflux for 30 min, a filtration system is prepared using a Büchner funnel and a 2 cm thick layer of diatomaceous earth. Before filtration, hot 1,4-dioxane is poured onto the diatomaceous earth and heated. The hot reaction mixture is then filtered while still hot. Some product will remain on the diatomaceous earth pad after filtration. The remaining crystals are washed with a mixture of hot 1,4-dioxane and chloroform / methanol (chloroform and methanol volume ratio 1:1). The resulting filtrate is evaporated to obtain the initial product. The initial product is dissolved in a chloroform / methanol mixture (volume ratio 1:1) and adsorbed onto silica. The crude product is purified by chromatography to obtain the 2,9-dialdehyde-1,10-o-phenanthroline.

[0050] In this invention, the mobile phase for chromatographic purification preferably comprises dichloromethane and methanol, and the volume ratio of dichloromethane to methanol in the mobile phase is preferably 9:1.

[0051] After obtaining 2,9-dialdehyde-1,10-o-phenanthroline, the present invention mixes the 2,9-dialdehyde-1,10-o-phenanthroline, K2CO3, Ohira-Bestmann reagent and organic solvent to carry out a Sefert-Gilbert carbon-raising reaction to obtain 2,9-dieethynyl-1,10-o-phenanthroline.

[0052] In this invention, the Seifert-Gilbert carbonization reaction is preferably carried out under a protective atmosphere, preferably nitrogen, and the reaction time is preferably 1 to 5 hours, specifically 1, 2, 3, 4 or 5 hours, with room temperature being the preferred temperature.

[0053] In this invention, the Ohira-Bestmann reagent is preferably dimethyl (1-diazo-2-oxopropyl)phosphonate.

[0054] In this invention, the molar ratio of 2,9-dialdehyde-1,10-o-phenanthroline to the Ohira-Bestmann reagent is preferably 12.7:26.67.

[0055] In this invention, the molar ratio of 2,9-dialdehyde-1,10-o-phenanthroline to K2CO3 is preferably 12.7:38.1.

[0056] In this invention, the organic solvent is preferably dry methanol.

[0057] In a specific embodiment of the present invention, preferably 2,9-dialdehyde-1,10-o-phenanthroline and K2CO3 are added to a two-necked round-bottom flask equipped with a magnetic stir bar, a rubber stopper, and a N2 supply, and dry methanol is added. Then, the Ohira-Bestmann reagent is dissolved in dry methanol and added to the reaction flask to carry out the Sefert-Gilbert carbonization reaction.

[0058] After the Sefert-Gilbert carbonization reaction is completed, the obtained solution is preferably diluted with chloroform, then washed twice with saturated NaHCO3 aqueous solution, then washed twice with brine, and then dried with anhydrous MgSO4. The solution is then evaporated using a rotary evaporator, and then purified by chromatography using a mixed solution of chloroform:ethyl acetate:methanol:triethylamine in a volume ratio of 80:14:6:0.1 as the mobile phase to obtain the 2,9-dieethynyl-1,10-o-phenanthroline.

[0059] In this invention, 1,4-cyclohexanediol, pyridine, p-toluenesulfonyl chloride and an organic solvent are mixed to carry out a first nucleophilic substitution reaction to obtain 1-hydroxy-4-toluenesulfonylcyclohexane.

[0060] In this invention, the temperature of the first nucleophilic substitution reaction is preferably 0°C, and the time is preferably 12 to 16 hours, specifically 12, 14 or 16 hours.

[0061] In this invention, the preferred ratio of 1,4-cyclohexanediol to pyridine is 2.0 g: 10 mL.

[0062] In this invention, the molar ratio of 1,4-cyclohexanediol to p-toluenesulfonyl chloride is preferably 17:16.92 mL.

[0063] In this invention, the organic solvent for the first nucleophilic substitution reaction is preferably dichloromethane.

[0064] In a specific embodiment of the present invention, preferably, a dichloromethane solution of p-toluenesulfonyl chloride is added to a pyridine solution of 1,4-cyclohexanediol at 0°C, and the mixture is stirred at room temperature to carry out the first nucleophilic substitution reaction.

[0065] After the first nucleophilic substitution reaction is completed, water is preferably added to separate the layers. Then, the aqueous layer is back-extracted with ethyl acetate, and the organic layer is washed with water and brine in sequence. The resulting organic phase is concentrated to obtain a pure yellow oily product, which is the 1-hydroxy-4-toluenesulfonylcyclohexane.

[0066] After obtaining 1-hydroxy-4-toluenesulfonylcyclohexane, the present invention mixes the 1-hydroxy-4-toluenesulfonylcyclohexane, potassium thioacetate and an organic solvent to carry out a second nucleophilic substitution reaction to obtain S-(4-hydroxycyclohexyl)ethyl sulfate.

[0067] In this invention, the molar ratio of 1-hydroxy-4-toluenesulfonylcyclohexane to potassium thioacetate is preferably 26.55:53.10.

[0068] In this invention, the organic solvent for the second nucleophilic substitution reaction is preferably N,N-dimethylformamide (DMF).

[0069] In this invention, the preferred ratio of 1-hydroxy-4-toluenesulfonylcyclohexane to organic solvent is 26.55 mmol: 80 mL.

[0070] In this invention, the temperature of the second nucleophilic substitution reaction is preferably 40-60°C, specifically 40, 50 or 60°C, and the time is preferably 20-28h, specifically 20, 24 or 28h.

[0071] In a specific embodiment of the present invention, preferably 1-hydroxy-4-toluenesulfonylcyclohexane and potassium thioacetate are weighed into a round-bottom flask, DMF is added, and then the second nucleophilic substitution reaction is carried out.

[0072] After the second nucleophilic substitution reaction is completed, the present invention preferably evaporates the resulting reaction mixture to remove DMF, then adds pure water, extracts the aqueous solution with dichloromethane, then dries the resulting organic phase with anhydrous MgSO4 and evaporates it, and then purifies it by chromatography to obtain the S-(4-hydroxycyclohexyl)ethyl sulfate.

[0073] In this invention, the mobile phase used in the chromatographic method is a methanol-dichloromethane solution, wherein the volume percentage of methanol in the methanol-dichloromethane solution is 5%.

[0074] After obtaining S-(4-hydroxycyclohexyl)ethyl sulfate, the present invention mixes the S-(4-hydroxycyclohexyl)ethyl sulfate, triphenylphosphine (PPh3), diethyl azodicarbonate (DEADcat), diphenylphosphine azide (DPPA) and an organic solvent to carry out a photoelongation reaction to obtain S-(4-azido-cyclohexyl)ethyl sulfate.

[0075] In this invention, the molar ratio of S-(4-hydroxycyclohexyl)ethyl sulfate to triphenylphosphine is preferably 15.18:22.77.

[0076] In this invention, the molar ratio of S-(4-hydroxycyclohexyl)ethyl sulfate to diethyl azodicarbonate is preferably 15.18:22.77.

[0077] In this invention, the molar ratio of S-(4-hydroxycyclohexyl)ethyl sulfate and diphenylphosphoazide is preferably 15.18:22.77.

[0078] In this invention, the organic solvent for the photoelongation reaction is preferably tetrahydrofuran (THF).

[0079] In this invention, the temperature of the photoelongation reaction is preferably -10°C, and the time is preferably 12 to 18 hours, specifically 12, 14, 16 or 18 hours.

[0080] In a specific embodiment of the present invention, diethyl azodicarbonate is added to a solution of S-(4-hydroxycyclohexyl) ethyl sulfate and triphenylphosphine cooled (preferably -10°C) and stirred in THF. After 5 min, a solution of diphenylphosphine azide in THF is added. The resulting reaction mixture is stirred at -10°C for 6 h and then stirred overnight at room temperature to carry out the photoelongation reaction.

[0081] After the photoelectrophoresis reaction is completed, the present invention preferably dilutes the reaction mixture with dichloromethane, then washes it with pure water, extracts the aqueous layer with dichloromethane, adds anhydrous MgSO4 to the obtained organic phase, dries and evaporates it, and then purifies it by column chromatography to obtain the S-(4-azido-cyclohexyl)ethyl sulfate.

[0082] In this invention, the mobile phase used for column chromatography purification is preferably a methanol-dichloromethane solution, and the volume percentage of methanol in the methanol-dichloromethane solution is preferably 5%.

[0083] After obtaining S-(4-azido-cyclohexyl)ethyl sulfate, the present invention mixes the S-(4-azido-cyclohexyl)ethyl sulfate, acetic acid and hydrogen peroxide to carry out a second oxidation reaction, and then adjusts the pH of the resulting oxidation product to neutral with an inorganic alkaline substance to obtain 1-azido-4-sulfonate sodium-cyclohexane; the inorganic alkaline substance contains sodium ions.

[0084] In this invention, the inorganic alkaline substance is preferably a saturated NaHCO3 solution.

[0085] In this invention, the preferred ratio of S-(4-azido-cyclohexyl)ethyl sulfate, acetic acid, and hydrogen peroxide is 1.71 g: 20 mL: 20 mL.

[0086] In this invention, the temperature of the second oxidation reaction is preferably room temperature, and the time is preferably 12 to 16 hours, specifically 12, 14 or 16 hours.

[0087] In a specific embodiment of the present invention, S-(4-azido-cyclohexyl)ethyl sulfate was placed in a flask, acetic acid and hydrogen peroxide were added, and then the reaction mixture was stirred overnight at room temperature to carry out the second oxidation reaction.

[0088] After the second oxidation reaction is completed, the present invention preferably evaporates the reaction mixture to remove acetic acid and hydrogen peroxide.

[0089] In this invention, pure water is added to the obtained second oxidation reaction product, the pH of the water is adjusted to 7 using a saturated NaHCO3 solution, the aqueous phase is washed with dichloromethane, and then evaporated to obtain 1-azido-4-sulfonate sodium-cyclohexane.

[0090] After obtaining 2,9-diethynyl-1,10-o-phenanthroline and sodium 1-azido-4-sulfonate-cyclohexane, the present invention mixes the 2,9-diethynyl-1,10-o-phenanthroline, sodium 1-azido-4-sulfonate-cyclohexane, sodium ascorbate, diisopropylethylamine (DIPEA), Cu(II)-TBTA solution and solvent to carry out a copper-catalyzed azide-alkyne cycloaddition reaction (CuAAC) to obtain the DSC-BTrzPhen ligand.

[0091] In this invention, the molar ratio of 2,9-diethynyl-1,10-o-phenanthroline and sodium 1-azido-4-sulfonate-cyclohexane is preferably 1.26:2.78.

[0092] In this invention, the molar ratio of 2,9-diethynyl-1,10-o-phenanthroline and sodium ascorbate is preferably 1.26:2.78.

[0093] In this invention, the molar ratio of 2,9-dieethynyl-1,10-o-phenanthroline to diisopropylethylamine is preferably 1.26:9.16.

[0094] In this invention, the preferred ratio of 2,9-diethynyl-1,10-o-phenanthroline to Cu(II)-TBTA solution is 1.26 mmol: 2.9 mL, and the molar percentage of Cu(II) in the Cu(II)-TBTA solution is 2.3%.

[0095] In this invention, the copper-catalyzed azide-alkyne cycloaddition reaction is preferably carried out in a protective atmosphere, preferably nitrogen, and the time is preferably 70-80 h, specifically 70, 72, 74, 76, 78 or 80 h.

[0096] In this invention, the solvent for the copper-catalyzed azide-alkyne cycloaddition reaction preferably includes degassed dichloromethane and degassed pure water.

[0097] In a specific embodiment of the present invention, the 2,9-diethynyl-1,10-o-phenanthroline, sodium 1-azido-4-sulfonate-cyclohexane, sodium ascorbate, and a stirring rod are loaded into a Schlenk tube, which is connected to a Schlenk line. The tube is evacuated and refilled with nitrogen three times, and kept under nitrogen. Then, degassed dichloromethane and degassed pure water are added. Next, diisopropylethylamine is added to the Schlenk tube, and finally, Cu(II)-TBTA solution is added dropwise to carry out the copper-catalyzed azide-alkyne cycloaddition reaction.

[0098] In a specific embodiment of the present invention, the Cu(II)-TBTA solution is preferably prepared by a method comprising the following steps: mixing 65 mg TBTA (tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine, CAS No.: 510758-28-8) and 30 mg CuSO4·5H2O in 11.8 mL of degassed water / DMSO solvent, wherein the volume ratio of water to DMSO in the degassed water / DMSO solvent is 1:1.

[0099] In this invention, the Cu content in the Cu(II)-TBTA solution is preferably 2.3 mol%.

[0100] In this invention, TBTA is an auxiliary ligand used in copper-catalyzed click chemistry reactions. It is typically used to promote the stabilization of copper (I) ions to enhance the efficiency and selectivity of copper-catalyzed azide-alkyne cycloaddition reactions (click reactions). TBTA forms a complex with copper ions and can act as a solvator for copper in click reactions, reducing the activation energy of the reaction and promoting its progress. The aim is to improve the rate and yield of click reactions and ensure high chemoselectivity.

[0101] After the copper-catalyzed azide-alkyne cycloaddition reaction is completed, the reaction mixture is preferably centrifuged to remove the dichloromethane layer. Then, the aqueous layer is evaporated using a rotary evaporator. The resulting yellow initial product is redissolved in a mixture of water and methanol (the volume ratio of water to methanol in the mixture is 2:1). The resulting mixture is stirred overnight for recrystallization. After recrystallization, the mixture is filtered and the solid is washed with acetone. Then, using water as the mobile phase and methanol volume concentration gradually increased from 0% to 50%, reversed-phase chromatography is performed on C-18 silica gel for purification. The purified material is then vacuum dried to obtain the DSC-BTrzPhen ligand.

[0102] This invention also provides the application of the DSC-BTrzPhen ligand described in the above technical solution in the separation of lanthanides and actinides.

[0103] This invention also provides a method for separating lanthanides and actinides from waste liquid, comprising the following steps:

[0104] The waste liquid is mixed with an extractant for solvent extraction. The extractant is the DSC-BTrzPhen ligand described in the above technical solution. The waste liquid contains lanthanides and actinides.

[0105] In this invention, the waste liquid is preferably a high-level radioactive waste liquid, which refers to waste liquid with a radioactivity greater than 3.7 × 10⁻⁶. 10 The radioactive waste liquid of Bq / L is preferably derived from the raffinate phase of the co-decontamination cycle section of a spent fuel reprocessing plant, and the acidity of the high-level radioactive waste liquid is preferably 3-4M.

[0106] In this invention, the lanthanide elements include europium (Eu), and the actinide elements include americium (Am).

[0107] In this invention, the acidity of the waste liquid is preferably 0.001 to 4 M, specifically 0.001, 0.005, 0.01, 0.05, 0.10, 0.25, 0.5, 0.75, 1.0, 1.25, 1.5, 3, or 4 M. This invention preferably uses nitric acid to adjust the acidity of the waste liquid.

[0108] In this invention, the concentration of DSC-BTrzPhen ligand in the system during solvent extraction is 2.5 to 40 mM, specifically 2.5, 5, 10, 20, 25, 30 or 40 mM.

[0109] In this invention, the solvent extraction temperature is preferably room temperature, and the extraction time is preferably 5 to 60 minutes, specifically 5, 10, 15, 30, 45 or 60 minutes.

[0110] In this invention, the solvent extraction is preferably carried out under stirring conditions, and the stirring speed is preferably 3000 rpm.

[0111] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0112] Figure 1 This is a schematic diagram illustrating the principle of preparing DSC-BTrzPhen ligands according to an embodiment of the present invention.

[0113] Example 1

[0114] 1.1(a): 2,9-dialdehyde-1,10-o-phenanthroline

[0115]

[0116] Weigh 5.59 g of selenium dioxide (50.42 mmol) into a 250 mL double-necked round-bottom flask. Add a suitable magnetic stir bar. Then add 120 mL of 1,4-dioxane and 3.4 mL of water to the flask containing selenium dioxide. Simultaneously, weigh 5 g of 2,9-dimethyl-1,10-o-phenanthroline (24.01 mmol) into a 250 mL heart-shaped flask, and add 100 mL of 1,4-dioxane to the heart-shaped flask until completely dissolved. Attach the round-bottom flask containing the selenium dioxide solution to an oil bath and attach a reflux condenser to the top neck. Cover the side neck with a rubber stopper and heat the oil bath to 110 °C for reflux. After reflux, transfer the 2,9-dimethyl-1,10-o-phenanthroline solution to the reaction flask using a tubing. Reflux the reaction mixture for 30 min. During reflux for 30 min, a filtration system was prepared using a large Büchner funnel and a 2 cm thick layer of diatomaceous earth. Before filtration, 200 mL of hot 1,4-dioxane was poured onto the diatomaceous earth and heated. The hot reaction mixture was filtered while still hot. Some product remained on the diatomaceous earth pad after filtration. The remaining crystals were washed with hot 1,4-dioxane and a chloroform / methanol mixture (chloroform to methanol volume ratio 1:1). The resulting filtrate was evaporated to give the primary product. The primary product was dissolved in 300 mL of a chloroform / methanol mixture (volume ratio 1:1), adsorbed onto 50 g of silica, and purified by chromatography (mobile phase: dichloromethane / methanol volume ratio = 9:1) to give 4.54 g of a pale yellow powder (yield 80%).

[0117] 1 H-NMR(CDCl3)δ10.55(s,2H),8.51-8.48(d,J=8.2Hz,2H),8.38-8.36(d,J=8.2Hz,2H),8.04(s,2H); 13C- NMR(CDCl3)δ193.48(2C),152.78(2C),146.05(2C),138.08(2C),131.75(2C),129.18(2C),120.59(2C).

[0118] 1.2(b): 2,9-Diethynyl-1,10-o-phenanthroline

[0119]

[0120] 3.0 g (12.7 mmol) of 2,9-dialdehyde-1,10-o-phenanthroline and 5.27 g (38.1 mmol) of K₂CO₃ were added to a two-necked round-bottom flask (500 mL) equipped with a magnetic stir bar, a rubber stopper, and a nitrogen supply, followed by 150 mL of dry methanol. Then, 5.04 mL of dimethyl 1-diazo-2-oxopropyl phosphonate (Ohira-Bestmann reagent, 26.67 mmol) was dissolved in 100 mL of dry methanol and added to the reaction flask. The reaction was stirred at room temperature for 3 h. After 3 h, the solution was diluted with chloroform (500 mL), washed twice with 200 mL of saturated NaHCO₃ aqueous solution, and then twice with 100 mL of brine. The organic solution was then dried over anhydrous MgSO₄ and evaporated using a rotary evaporator. Using a mixed solution of chloroform:ethyl acetate:methanol:triethylamine in a volume ratio of 80:14:6:0.1 as the mobile phase, the solution was purified by chromatography to give 1.36 g of a pale yellow solid (yield 47%).

[0121] 1 H-NMR(CDCl3)δ8.20-8.18(d,J=8.2Hz,2H),7.78-7.76(d,J=8.3Hz,4H),3.29(t,2H); 13 C-NMR(CDCl3)δ145.67(2C),142.90(2C),136.44-136.17(2C),128.27(2C),127.21(2C),126.91(2C),83.71-83.5(2C),78.71-78.13(2C); MS(APCI + )m / z calcd.for[M+H] + :229.08found:229.2,calcd.for[M+Na] + :251.06found:251.1.

[0122] 1.3(c): 1-Hydroxy-4-toluenesulfonylcyclohexane

[0123]

[0124] A solution of p-toluenesulfonyl chloride (3.257 g, 16.92 mmol) in 10 mL of dichloromethane was added to a solution of 1,4-cyclohexanediol (2.0 g, 17.0 mmol) in pyridine (10 mL) at 0 °C for 1 h. The mixture was stirred overnight at room temperature to carry out a nucleophilic substitution reaction. After overnight incubation, water was added, and the layers were separated. The aqueous layer was back-extracted with ethyl acetate, and the organic layer was washed with water (100 mL) and brine (100 mL). The organic phase was concentrated to give 3.78 g of a pure yellow oily product (yield 82%).

[0125] 1 H NMR (400MHz, CDCl3) δ (ppm): 7.70-7.69 (d, J = 4.9Hz, 2H), 7.24 (s, 2H), 4.49-4. 40(d,J=37.4Hz,1H),3.59(s,1H),2.35(s,3H),1.81-1.43(m,8H),1.27(s,1H); 13 C NMR (400MHz, CDCl3) δ (ppm): 144.89 (1C), 134.59 (1C), 130.13 (2C), 127.81 (2C), 80.85 (1C), 79.52 (1C), 30.24 (2C), 28.51 (2C), 21.89 (1C); MS (ESI + )m / z calcd.for[M+Na] + :293.08,found:293.0912.

[0126] 1.4(d): S-(4-hydroxycyclohexyl)ethyl sulfate

[0127]

[0128] 7.25 g (26.55 mmol) of 1-hydroxy-4-toluenesulfonylcyclohexane and 6.19 g (53.10 mmol) of potassium thioacetate were weighed into a 250 mL round-bottom flask, and 80 mL of DMF was added. The mixture was then reacted at 50 °C for 24 h. After 24 h, the reaction mixture was evaporated completely to remove the DMF. 100 mL of pure water was added, and the aqueous solution was extracted with dichloromethane (3 × 100 mL). The organic phase was dried over anhydrous MgSO4 and evaporated. The raw material was purified by chromatography using a methanol-dichloromethane solution (5% methanol by volume) as the mobile phase, yielding 3.01 g of product (65% yield).

[0129] 1 H NMR (400MHz, CDCl3) δ (ppm): 3.56 (s, 1H), 3.30 (s, 1H), 2.90-2.82 (d, J = 48.0Hz, 1H), 2.23 (s, 3H), 1.97-1.83 (m, 4H), 1.38-1.33 (m, 4H); 13 C NMR (400MHz, CDCl3) δ (ppm): 195.60 (1C), 66.69 (1C), 41.30 (1C), 33.14 (2C), 30.59 (1C), 25.63 (2C); MS (ESI +)m / z calcd.for[M+Na] + :197.06,found:197.0707.

[0130] 1.5: (e)S-(4-azidocyclohexyl)ethyl sulfate

[0131]

[0132] Add 3.78 mL of diethyl azodicarbonate (4.18 g, 22.77 mmol) to a solution of S-(4-hydroxycyclohexyl) ethyl sulfate (2.7 g, 15.18 mmol) and triphenylphosphine (6.034 g, 22.77 mmol) in THF (82 mL) under cooling (-10 °C) and stirring. After 5 min, slowly add 5.06 mL of a solution of diphenylphosphine azide (6.46 g, 22.77 mmol) in THF (82 mL). The reaction mixture was stirred at -10 °C for 6 h and then stirred overnight at room temperature. After overnight, the reaction mixture was diluted with dichloromethane (100 mL) and then washed with 100 mL of pure water. The aqueous layer was extracted with 100 mL of dichloromethane. Anhydrous MgSO4 was added to the organic phase for drying and evaporation. The product was purified by column chromatography using a methanol-dichloromethane solution as the mobile phase (the volume percentage of methanol in the methanol-dichloromethane solution was 5%) to obtain 2.27 g of product (yield 75%).

[0133] 1 H NMR (400MHz, CDCl3) δ (ppm): 3.61 (s, 1H), 3.39-3.33 (m, 1H), 2.31-2.30 (d, J = 3.8Hz, 3H), 2.08-1.39 (m, 8H); 13 C NMR (400MHz, CDCl3) δ (ppm): 195.83 (1C), 67.40 (1C), 41.08 (1C), 32.47 (2C), 30.90 (1C), 28.33 (2C); MS (ESI + )m / zcalcd.for[2M+H] + :407.23,found:409.3577.

[0134] 1.6: (f)1-Sodium 1-azido-4-sulfonate-cyclohexane

[0135]

[0136] S-(4-azidocyclohexyl)ethyl sulfate (1.71 g, 8.41 mmol) was placed in a 100 mL flask, and 20 mL of acetic acid and 20 mL of hydrogen peroxide were added. The reaction mixture was then stirred overnight at room temperature. The next day, the reaction mixture was evaporated completely to remove the acetic acid and hydrogen peroxide. 100 mL of pure water was added to the flask, and the pH of the water was adjusted to 7 using a saturated NaHCO3 solution. The aqueous phase was then washed with dichloromethane (3 × 100 mL) and evaporated to give 1.57 g of product (yield 82%).

[0137] 1 H NMR(400MHz,D2O)δ(ppm):4.01(s,1H),3.48-3.40(m,1H),2.85-2.78(m,2H),2.24-2.12(m, 4H),2.00-1.97(d,J=11.1Hz,4H),1.72-1.68(m,4H),1.61-1.51(m,2H),1.46-1.36(m,2H); 13 C NMR (400MHz, D2O) δ (ppm): 62.79 (1C), 58.23 (1C), 57.79 (1C), 56.44 (1C), 31.50 (2C), 28.44 (2C), 26.16 (2C), 22.03 (2C); MS (ESI + )m / z calcd.for[M+Na] + :254.06,found:254.1700;MS(ESI + m / zcalcd.for[M+H] + :232.07, found:232.1875; FT-IR(KBr disc):ν max 3559(s),2525(m),2175(m),1646(s),1566(s),1372(s),1260(m),804(w),567(m).

[0138] 1.7: (g)DSC-BTrzPhen

[0139]

[0140] 2,9-Diethynyl-1,10-o-phenanthroline (288 mg, 1.26 mmol), sodium 1-azido-4-sulfonate-cyclohexane (0.73 mg, 2.78 mmol), 489 mg (2.78 mmol) sodium ascorbate, and a stir bar were placed into a 250 mL Schlenk tube. The Schlenk tube was connected to a Schlenk line. The tube was evacuated and refilled three times with nitrogen, and maintained under nitrogen atmosphere. Then, 30.5 mL of degassed dichloromethane and 28.5 mL of degassed pure water were added. Then, 1.6 mL (9.16 mmol) of diisopropylethylamine was added to a Schlenk tube, followed by dropwise addition of 2.9 mL (2.3 mol%) of Cu(II)-TBTA solution (prepared by mixing 65 mg TBTA and 30 mg CuSO4·5H2O in 11.8 mL of degassed water / DMSO solvent, with a water to DMSO volume ratio of 1:1). The reaction mixture was stirred at room temperature under an inert gas atmosphere for 72 h. After 72 h, the reaction mixture was centrifuged to remove the dichloromethane layer, and the aqueous layer was evaporated using a rotary evaporator. The yellow initial product was redissolved in a mixture of 10 mL water and 5 mL methanol. The mixture was then stirred overnight for recrystallization. After recrystallization, the mixture was filtered and the solid was washed with acetone. The purified material was purified by reversed-phase chromatography on C-18 silica gel using water as the mobile phase and methanol volume percentage gradually increased from 0% to 50%. The purified material was then dried under vacuum. The product was 0.78g (yield 84%).

[0141] ElementalAnalysis calcd.for:C,49.26;H,4.13;N,16.41;Na,6.74;O,14.06;S,9.39,Found:C,48.27;H,5.17;N,15.41; 1 H NMR (400MHz, D2O) δ (ppm): 8.02-7.91 (d, J = 43.9Hz, 2H), 7.19 (s, 2H), 6.79-6.75 (d, J = 15. 0Hz, 4H), 4.33-4.14 (d, J=16.3Hz, 2H), 3.02-2.84 (d, J=72.3Hz, 2H), 2.28-1.62 (m, 16H); 13 C NMR(400MHz,D2O)δ(ppm):151.76(2C),144.57(2C),143.20(2C),131.84(2C),128.88(2C),1 23.99(2C),121.75(2C),119.25(2C),60.56(2C),56.78(2C),31.87(4C),24.69(4C);MS(ESI- )m / z calcd.for[M-Na] - :659.15,found:659.1454;MS(ESI - )m / z calcd.for[M-2Na] 2- :318.08,found:318.0780;MS(ESI - )m / z calcd.for[M-2Na+H] - :637.17,found:637.1624;MS(ESI + )m / z calcd.for[M+Na] + :683.14,found:683.1416;MS(ESI + )m / z calcd.for[M-2Na+3H] + :639.18,found:639.1762;MS(ESI + )m / z calcd.for[M-Na+2H] + :661.16,found:661.1588; HRMS(ESI + m / zcalcd.for[M+Na] + :705.13,found:705.1268.

[0142] 2. Solvent Extraction Test

[0143] 2.1 Stock solution

[0144] All organic phases for solvent extraction experiments were prepared using the tracer-supported organic phase (TLOP) scheme.

[0145] A ligand stock solution was prepared by dissolving 318 mg of the ligand in 10 mL of pure water, resulting in a concentration of 40 mM.

[0146] 241Am(NO3)3 stock solution containing 0.01M nitric acid.

[0147] A 152 / 154 Eu(NO3)3 stock solution containing 0.01M nitric acid.

[0148] The HNO3 stock solutions are 0.1M and 1M.

[0149] The stock solution of NaNO3 is 4M.

[0150] 2.2 Tracer-supported organic phase (TLOP) scheme

[0151] I. Preparation of Irradiated Aqueous Phase

[0152] Prepare 100 mL of 3M HNO3 in a clean conical flask, and add 10 mL of 3M HNO3 to a polypropylene centrifuge tube. Add 20 μL of 241Am tracer and 20 μL of 152 / 154Eu to the centrifuge tube.

[0153] II. Preparation of TODGA

[0154] 0.2M TODGA (N,N,N′,N′-tetraoctyl-3-oxopramidine) organic phase: Dissolve 3.521 g TODGA in 30 mL of kerosene / n-octanol (95:5, v / v) solution.

[0155] III. Load

[0156] Add 20 mL of the organic phase to a centrifuge tube containing water, 20 μL of 241Am tracer, and 20 μL of 152 / 154Eu phase, and close the centrifuge tube appropriately. Then, mount the centrifuge tube on a vibrating sieve and vibrate for 60 min. Afterward, centrifuge at 3000 rpm for 2 min and carefully transfer the aqueous phase to a radioactive waste bottle.

[0157] IV. Washing (removing HNO3 dissolved in the organic phase)

[0158] Add 10 mL of 0.5 M HNO3 to the centrifuge tube containing the organic phase of the tracer, close the centrifuge tube and shake for 15 min. Centrifuge at 3000 rpm for 2 min, and carefully transfer the aqueous phase to a radioactive waste bottle.

[0159] Then, an organic phase sample was taken for LSC to measure the initial 241Am and 152 / 154Eu counts.

[0160] Prepared TLOPs should be safely stored in a refrigerator to minimize solvent evaporation and maintain the same counting ratio over many days. Use 1 mL of organic phase for each sample tube.

[0161] 2.3 Three types of tests:

[0162] 2.3.1 Acidity test to determine the effect of nitric acid concentration on the partition ratio and SF. Eu / Am The impact.

[0163] For the ligand DSC-BTrzPhen, acidity studies were conducted at nitric acid concentrations of 0.001, 0.005, 0.01, 0.05, 0.10, and 0.25 M. The standard concentration of the ligand was 10 mM sodium nitrate.

[0164] 2.3.2 Kinetic studies were conducted to determine the kinetics of the extraction process.

[0165] The aqueous phase contained a constant concentration of ligand (10 mM) and 1.0 M sodium nitrate and 0.01 M nitric acid, and was tested every 5, 10, 15, 30, 45 and 60 min.

[0166] 2.3.3 Ligand concentration extraction studies were conducted to determine the ligand concentration-partition ratio and SF. Eu / Am The impact.

[0167] The ligand DSC-BTrzPhen was tested at concentrations of 2.5, 5, 10, 15, and 25 mM. The acidity was constant at 0.01 M nitric acid, and the sodium nitrate concentration was 1 M. 2.3.4

[0169] Mix 1 mL of aqueous phase and 1 mL of organic phase in a PP vial, vortex (standard 60 min), and then centrifuge (3000 rpm, 2 min) to completely separate the two phases. Samples from both the aqueous and organic phases are then collected, and the radioactivity in different channels is counted using LSC to distinguish between alpha radioactivity of 241Am and beta radioactivity of 152Eu / 154Eu. To ensure data accuracy, measurements are performed on each sample for at least 5 min. The count ratios in the two phases are then interpreted as extraction parameter D. Am and D Eu , and SF Eu / Am The calculation is D. Eu / D Am Compare.

[0170] 2.4 Solvent Extraction Results

[0171] Figure 2 The acidity test curve for DSC-BTrzPhen is shown. Figure 3 The extraction curves for DSC-BTrzPhen ligand concentration are shown. Figure 4 The kinetic test curves for DSC-BTrzPhen show that the optimal acidity for DSC-BTrzPhen is 0.001–0.01 M, resulting in good separation performance. SF Eu / Am The temperature ranges from 360 to 440°C, and the equilibration time is good, less than 15 minutes.

[0172] In summary, this invention has developed a novel DSC-BTrzPhen ligand by designing its structure. This ligand ensures both a high partition ratio for Eu and efficient back-extraction of Am, thanks to the introduction of this water-soluble ligand. The lanthanum-actinium separation factor (SF) of the DSC-BTrzPhen ligand is [not specified in the original text]. Eu / AmAbove 400, the separation effect is good. Furthermore, the ligand exhibits good water solubility and extraction kinetics; its water solubility is excellent, reaching equilibrium within 15 minutes. This invention's ligand not only provides a new and effective method for spent fuel reprocessing but also offers crucial support for the sustainable development of nuclear energy and the scientific treatment and safe management of existing radioactive waste.

[0173] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A DSC-BTrzPhen ligand, characterized in that, It has the structure shown in Equation I:

2. The method for preparing the DSC-BTrzPhen ligand according to claim 1, characterized in that, Includes the following steps: 2,9-Dimethyl-1,10-o-phenanthroline, an organic solvent, and an oxidant were mixed and subjected to a first oxidation reaction to obtain 2,9-dialdehyde-1,10-o-phenanthroline. The 2,9-dialdehyde-1,10-o-phenanthroline, K2CO3, Ohira-Bestmann reagent and organic solvent were mixed and subjected to a Sefert-Gilbert carbon-raising reaction to obtain 2,9-dieethynyl-1,10-o-phenanthroline. A first nucleophilic substitution reaction was carried out by mixing 1,4-cyclohexanediol, pyridine, p-toluenesulfonyl chloride and an organic solvent to give 1-hydroxy-4-toluenesulfonylcyclohexane; The 1-hydroxy-4-toluenesulfonylcyclohexane, potassium thioacetate, and an organic solvent were mixed to carry out a second nucleophilic substitution reaction to obtain S-(4-hydroxycyclohexyl)ethyl sulfate. S-(4-hydroxycyclohexyl) ethyl sulfate, triphenylphosphine, diethyl azodicarbonate, diphenylphosphine azide and an organic solvent were mixed and subjected to phototelephoto reaction to obtain S-(4-azido-cyclohexyl) ethyl sulfate; The S-(4-azido-cyclohexyl)ethyl sulfate, acetic acid, and hydrogen peroxide were mixed to carry out a second oxidation reaction. Then, the pH of the resulting oxidation product was adjusted to neutral with an inorganic alkaline substance to obtain 1-azido-4-sulfonate sodium-cyclohexane. The inorganic alkaline substance contained sodium ions. The 2,9-diethynyl-1,10-o-phenanthroline, sodium 1-azido-4-sulfonate-cyclohexane, sodium ascorbate, diisopropylethylamine, Cu(II)-TBTA solution and solvent were mixed to carry out a copper-catalyzed azide-alkyne cycloaddition reaction to obtain the DSC-BTrzPhen ligand.

3. The preparation method according to claim 2, characterized in that, The oxidant includes selenium dioxide.

4. The preparation method according to claim 2, characterized in that, The Seifert-Gilbert carburization reaction is carried out under a protective atmosphere, and the reaction time is 1 to 5 hours.

5. The preparation method according to claim 2, characterized in that, The copper-catalyzed azide-alkyne cycloaddition reaction was carried out under a protective atmosphere for 70–80 h.

6. The application of the DSC-BTrzPhen ligand as described in claim 1 in the separation of lanthanides and actinides.

7. A method for separating lanthanides and actinides from waste liquid, characterized in that, Includes the following steps: The waste liquid is mixed with an extractant for solvent extraction, wherein the extractant is the DSC-BTrzPhen ligand as described in claim 1, and the waste liquid contains lanthanides and actinides.

8. The method according to claim 7, characterized in that, The lanthanides include europium, and the actinides include americium.

9. The method according to claim 7, characterized in that, The acidity of the waste liquid is 0.001 to 4 M.

10. The method according to claim 7, characterized in that, The concentration of DSC-BTrzPhen ligand in the system during solvent extraction is 2.5–40 mM.

Images