DSC-BTrzPhen ligand, preparation method and application thereof, and method for separating lanthanides and actinides from waste liquid

Abstract

The invention provides a DSC-BTrzPhen ligand, 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. Starting from the molecular structure design of the ligand, the novel DSC-BTrzPhen ligand is developed by designing the structure of the ligand, the ligand ensures the high distribution ratio of Eu, meanwhile, the introduction of the water-soluble ligand also ensures the efficient reverse extraction of Am, the lanthanum actinide separation factor SFEu / Am of the DSC-BTrzPhen ligand reaches up to 440, and the separation effect is good. In addition, the ligand is good in water solubility and extraction kinetics, the water solubility is extremely good, and balance can be achieved within 15 min. The ligand provided by the invention not only provides a new effective method for spent fuel post-treatment, but also provides important support for sustainable development of nuclear energy and scientific treatment and safe management of existing radioactive wastes.

Description

Technical Field

[0001] The invention relates to the technical field of extraction and separation, in particular to a DSC-BTrzPhen ligand and a preparation method and application thereof, and a method for separating lanthanide elements and actinide elements from waste liquid. Background Art

[0002] The separation of lanthanides and actinides is very important in 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 methods and chemical methods. Physical methods include high-speed countercurrent chromatography (HSCCC) and methods based on graphene oxide ion sieving membranes, wherein: HCCCC is a new type of separation method that combines the advantages of liquid-liquid extraction and partition chromatography, does not require a solid carrier, and shows potential in the field of radiochemistry, and methods based on graphene oxide ion sieving membranes utilize the layered structure of graphene oxide nanosheets and adjustable nanoscale interlayer channels to achieve the separation of lanthanides and actinides. Chemical methods include ion exchange chromatography and liquid-liquid extraction, wherein ion exchange chromatography utilizes the different adsorption capacities of lanthanides and actinides on ion exchange resins for separation, and liquid-liquid extraction achieves separation by selecting appropriate extractants to transfer lanthanides and actinides from one solvent to another. The liquid-liquid extraction method in the related art has the problems of low separation factor and poor separation effect. Summary of the invention

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

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

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

[0007]

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

[0009] Mixing 2,9-dimethyl-1,10-phenanthroline, an organic solvent and an oxidant to perform a first oxidation reaction to obtain 2,9-dialdehyde-1,10-phenanthroline;

[0010] The 2,9-diacetyl-1,10-phenanthroline, K2CO3, Ohira-Bestmann reagent and organic solvent are mixed to perform a Seyfert-Gilbert carbon addition reaction to obtain 2,9-diethynyl-1,10-phenanthroline;

[0011] 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;

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

[0013] The S-(4-hydroxycyclohexyl)ethyl sulfate, triphenylphosphine, diethyl azodicarboxylate, diphenylphosphoryl azide and an organic solvent are mixed to perform a Mitsunobu reaction to obtain S-(4-azido-cyclohexyl)ethyl sulfate;

[0014] The S-(4-azido-cyclohexyl) ethylsulfate, acetic acid and hydrogen peroxide are mixed for a second oxidation reaction, and then the pH value of the obtained oxidation product is adjusted to be neutral with an inorganic alkaline substance to obtain 1-azido-4-sodium sulfonate-cyclohexane; the inorganic alkaline substance contains sodium ions;

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

[0016] Preferably, the oxidizing agent comprises selenium dioxide.

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

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

[0019] The present invention also provides the use of the DSC-BTrzPhen ligand described in the above technical solution in separating lanthanides and actinides.

[0020] The present 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 according to claim 1, and the waste liquid contains lanthanides and actinides.

[0022] Preferably, the lanthanide element includes europium, and the actinide element includes americium.

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

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

[0025] The present invention provides a DSC-BTrzPhen ligand having a structure shown in Formula I. Compared with the prior art, the present invention has the following beneficial effects:

[0026] The ligand of the present invention not only ensures a high distribution ratio for Eu, but also the introduction of the water-soluble ligand also ensures efficient stripping of Am, with a separation factor SF Eu / Am As high as 440, the separation effect is excellent. In addition, the ligand has good water solubility and extraction kinetics, and equilibrium can be reached within 15 minutes. This ligand not only provides a new and effective method for spent fuel reprocessing, but also provides important support for the sustainable development of nuclear energy, the scientific treatment and safe management of existing radioactive waste.

[0027] The present invention also provides a method for preparing the DSC-BTrzPhen ligand described in the above technical solution. The preparation method of the present invention is simple and efficient in synthesis, low in price, and easy for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The reaction principle diagram of the preparation of DSC-BTrzPhen ligand in the embodiment;

[0029] Figure 2 is the acidity test curve of DSC-BTrzPhen;

[0030] Figure 3 is the ligand concentration extraction curve of DSC-BTrzPhen;

[0031] Figure 4 This is the kinetic test curve of DSC-BTrzPhen. DETAILED DESCRIPTION

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

[0033]

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

[0035] Mixing 2,9-dimethyl-1,10-phenanthroline, an organic solvent and an oxidant to perform a first oxidation reaction to obtain 2,9-dialdehyde-1,10-phenanthroline;

[0036] The 2,9-diacetyl-1,10-phenanthroline, K2CO3, Ohira-Bestmann reagent and organic solvent are mixed to perform a Seyfert-Gilbert carbon addition reaction to obtain 2,9-diethynyl-1,10-phenanthroline;

[0037] 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;

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

[0039] The S-(4-hydroxycyclohexyl)ethyl sulfate, triphenylphosphine, diethyl azodicarboxylate, diphenylphosphoryl azide and an organic solvent are mixed to perform a Mitsunobu reaction to obtain S-(4-azido-cyclohexyl)ethyl sulfate;

[0040] The S-(4-azido-cyclohexyl) ethylsulfate, acetic acid and hydrogen peroxide are mixed for a second oxidation reaction, and then the pH value of the obtained oxidation product is adjusted to be neutral with an inorganic alkaline substance to obtain 1-azido-4-sodium sulfonate-cyclohexane; the inorganic alkaline substance contains sodium ions;

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

[0042] In the present invention, unless otherwise specified, the raw materials used are all commercially available products in the art.

[0043] The invention mixes 2,9-dimethyl-1,10-phenanthroline, an organic solvent and an oxidant to carry out a first oxidation reaction to obtain 2,9-dialdehyde-1,10-phenanthroline.

[0044] In the present invention, the oxidant preferably includes selenium dioxide, and the selenium dioxide 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 dosage ratio of selenium dioxide to water is preferably 5.59g:3.4mL.

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

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

[0047] In the present 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 magnet is added, and then 1,4-dioxane and water are added to the flask containing selenium dioxide, 2,9-dimethyl-1,10-phenanthroline is weighed into a heart-shaped flask, 1,4-dioxane is added to the heart-shaped flask to completely dissolve it, the round-bottom flask containing the selenium dioxide solution is installed on an oil bath, and a reflux condenser is installed on the top neck, the side neck is covered with a rubber stopper, the oil bath is heated to 110° C. and refluxed, and the 2,9-dimethyl-1,10-phenanthroline solution is transferred to the reaction flask with a catheter to carry out the first oxidation reaction.

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

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

[0051] After obtaining 2,9-diacetyl-1,10-phenanthroline, the present invention mixes the 2,9-diacetyl-1,10-phenanthroline, K2CO3, Ohira-Bestmann reagent and an organic solvent to carry out a Seyfert-Gilbert carbon addition reaction to obtain 2,9-diethynyl-1,10-phenanthroline.

[0052] In the present invention, the Seyfert-Gilbert carburizing reaction is preferably carried out under a protective atmosphere, and the protective atmosphere is preferably nitrogen. The time of the Seyfert-Gilbert carburizing reaction is preferably 1 to 5 hours, specifically 1, 2, 3, 4 or 5 hours, and the temperature is preferably room temperature.

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

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

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

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

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

[0058] After the Seyfert-Gilbert carbon addition reaction is completed, the resulting solution is preferably diluted with chloroform, then washed twice with a saturated NaHCO3 aqueous solution, then washed twice with brine, and then the organic solution is dried over anhydrous MgSO4, and then evaporated using a rotary evaporator, and then chromatographically purified using a mixed solution of chloroform: ethyl acetate: methanol: triethylamine in a volume ratio of 80:14:6:0.1 as a mobile phase to obtain the 2,9-diethynyl-1,10-phenanthroline.

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

[0060] In the present 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 the present invention, the usage ratio of 1,4-cyclohexanediol to pyridine is preferably 2.0 g:10 mL.

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

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

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

[0065] After the first nucleophilic substitution reaction is completed, the present invention preferably adds water, separates the layers, then back-extracts the aqueous layer with ethyl acetate, washes the organic layer with water and brine in sequence, and concentrates the obtained organic phase to obtain a pure yellow oily product, namely 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 the present invention, the molar ratio of 1-hydroxy-4-toluenesulfonylcyclohexane to potassium thioacetate is preferably 26.55:53.10.

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

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

[0070] In the present 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 20-28 h, specifically 20, 24 or 28 h.

[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, and then dries the resulting organic phase with anhydrous MgSO4 and evaporates, and then purifies by chromatography to obtain the S-(4-hydroxycyclohexyl) ethyl sulfate.

[0073] In the present invention, the mobile phase used in the chromatography is a methanol-dichloromethane solution, and 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 azodicarboxylate (DEADcat), diphenylphosphoryl azide (DPPA) and an organic solvent to perform a Mitsunobu reaction to obtain S-(4-azido-cyclohexyl) ethyl sulfate.

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

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

[0077] In the present invention, the molar ratio of S-(4-hydroxycyclohexyl) ethyl sulfate to diphenylphosphoryl azide is preferably 15.18:22.77.

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

[0079] In the present invention, the temperature of the Mitsunobu 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 azodicarboxylate is added to a solution of S-(4-hydroxycyclohexyl)ethylsulfate and triphenylphosphine in THF which is cooled (preferably -10°C) and stirred. After 5 minutes, a solution of diphenylphosphoryl azide in THF is added, and the resulting reaction mixture is stirred at -10°C for 6 hours and continued to stir overnight at room temperature to carry out the Mitsunobu reaction.

[0081] After the Mitsunobu reaction is completed, the present invention preferably dilutes the reaction mixture with dichloromethane, then washes 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 the present invention, the mobile phase for column chromatography purification is preferably a dichloromethane solution of methanol, and the volume percentage of methanol in the dichloromethane solution of methanol 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 uses an inorganic alkaline substance to adjust the pH value of the obtained oxidation product to be neutral, thereby obtaining 1-azido-4-sodium sulfonate-cyclohexane; the inorganic alkaline substance contains sodium ions.

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

[0085] In the present invention, the usage ratio of S-(4-azido-cyclohexyl)ethylsulfate, acetic acid and hydrogen peroxide is preferably 1.71 g:20 mL:20 mL.

[0086] In the present 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)ethylsulfate is placed in a flask, acetic acid and hydrogen peroxide are added, and then the reaction mixture is stirred at room temperature overnight to perform 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] The present invention preferably adds pure water to the obtained second oxidation reaction product, uses saturated NaHCO3 solution to adjust the pH value of the water to 7, then washes the aqueous phase with dichloromethane, and then evaporates to obtain 1-azido-4-sodium sulfonate-cyclohexane.

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

[0091] In the present invention, the molar ratio of 2,9-diethynyl-1,10-phenanthroline to sodium 1-azide-4-sulfonate-cyclohexane is preferably 1.26:2.78.

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

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

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

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

[0096] In the present 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-phenanthroline, 1-azido-4-sodium sulfonate-cyclohexane, sodium ascorbate and a stirring bar are loaded into a Schlenk tube, which is connected to a Schlenk line, evacuated and refilled with nitrogen three times, and kept under nitrogen, and then degassed dichloromethane and degassed pure water are added, and then 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: 65 mg TBTA (tri[(1-benzyl-1H-1,2.3-triazol-4-yl)methyl]amine, CAS No.: 510758-28-8) and 30 mg CuSO4·5H2O are mixed 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 the present invention, the content of Cu in the Cu(II)-TBTA solution is preferably 2.3 mol%.

[0100] In the present invention, the TBTA is an auxiliary ligand used in copper-catalyzed click chemistry reactions, which is generally 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 be used as a solvating agent for copper in the click reaction, thereby reducing the activation energy of the reaction and promoting the reaction, aiming to increase the rate and yield of the click reaction and ensure a high degree of chemical selectivity.

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

[0102] The present invention also provides the use of the DSC-BTrzPhen ligand described in the above technical solution in separating lanthanides and actinides.

[0103] The present 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, wherein the extractant is the DSC-BTrzPhen ligand described in the above technical solution, and the waste liquid contains lanthanide elements and actinide elements.

[0105] In the present invention, the waste liquid is preferably high-level waste liquid, which refers to waste liquid with a radioactivity greater than 3.7×10 10 The radioactive waste liquid of 100 Bq / L is preferably derived from the raffinate water phase of the co-decontamination circulation section of the spent fuel reprocessing plant, and the acidity of the high-level waste liquid is preferably 3-4M.

[0106] In the present invention, the lanthanide element includes europium (Eu), and the actinide element includes americium (Am).

[0107] In the present 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. In the present invention, nitric acid is preferably used to adjust the acidity of the waste liquid.

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

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

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

[0111] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

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

[0113] Example 1

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

[0115]

[0116] Weigh 5.59g of selenium dioxide (50.42mmol) into a 250mL double-necked round-bottom flask. Add a suitable magnet. Then add 120mL of 1,4-dioxane and 3.4mL of water to the flask containing selenium dioxide. At the same time, weigh 5g of 2,9-dimethyl-1,10-phenanthroline (24.01mmol) into a 250mL heart-shaped flask, and add 100mL of 1,4-dioxane to the heart-shaped flask to completely dissolve it. Install the round-bottom flask containing the selenium dioxide solution on an oil bath, and install a reflux condenser on the top neck. Cover the side neck with a rubber stopper and heat the oil bath to reflux at 110°C. After the solution refluxes, transfer the 2,9-dimethyl-1,10-phenanthroline solution to the reaction flask using a catheter. Reflux the reaction mixture for 30min. During reflux for 30 min, prepare the filtration system with a large Buchner funnel and a 2 cm thick diatomaceous earth layer. Before filtering, heat 200 mL of hot 1,4-dioxane on the diatomaceous earth. Filter the hot reaction mixture while it is hot. Some product will still remain on the diatomaceous earth pad after filtration. Wash the remaining crystals with hot 1,4-dioxane and a chloroform / methanol mixture (chloroform to methanol volume ratio 1:1 in the chloroform / methanol mixture). The filtrate obtained is evaporated to obtain the initial product. The initial product is dissolved in 300 mL of chloroform / methanol mixture (volume ratio 1:1), adsorbed on 50 g of silica, and the crude product is purified by chromatography (mobile phase: dichloromethane / methanol volume ratio = 9:1) to obtain 4.54 g of light 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-phenanthroline

[0119]

[0120] 3.0 g (12.7 mmol) 2,9-dialdehyde-1,10-phenanthroline and 5.27 g (38.1 mmol) K2CO3 were added to a two-necked round-bottom flask (500 mL) equipped with a magnetic stirring bar, a rubber stopper seal and a N2 supply, and 150 mL dry methanol was added. Then 5.04 mL (1-diazo-2-oxypropyl) dimethyl phosphonate (Ohira-Bestmann reagent, 26.67 mmol) was dissolved in dry methanol (100 mL) 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 saturated NaHCO3 aqueous solution, and then washed twice with 100 mL brine. The organic solution was then dried with anhydrous MgSO4 and evaporated using a rotary evaporator. The product was purified by chromatography using a mixed solution of chloroform:ethyl acetate:methanol:triethylamine=80:14:6:0.1 by volume as the mobile phase to obtain 1.36 g (yield 47%) of a light yellow solid.

[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] To a solution of 1,4-cyclohexanediol (2.0 g, 17.0 mmol) in pyridine (10 mL) at 0°C for 1 h, a solution of p-toluenesulfonyl chloride (3.257 g, 16.92 mmol) in 10 mL of dichloromethane was added. The mixture was stirred at room temperature overnight for nucleophilic substitution reaction. After overnight, 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). After the organic phase was concentrated, 3.78 g of pure yellow oily product was obtained (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] Weigh 7.25g (26.55mmol) of 1-hydroxy-4-tosylcyclohexane and 6.19g of potassium thioacetate (53.10mmol) in a 250mL round-bottom flask, add 80mL of DMF, and then react at 50°C for 24h. After 24h, fully evaporate the reaction mixture to remove DMF. Add 100mL of pure water, extract the aqueous solution with dichloromethane (3×100mL), and dry the organic phase with anhydrous MgSO4 and evaporate. Purify the raw material by chromatography, with the mobile phase being a dichloromethane solution of methanol (the volume percentage of methanol in the dichloromethane solution of methanol is 5%), and obtain 3.01g of product (yield 65%).

[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-azido-cyclohexyl) ethyl sulfate

[0131]

[0132] To a solution of S-(4-hydroxycyclohexyl) ethylsulfate (2.7 g, 15.18 mmol) and triphenylphosphine (6.034 g, 22.77 mmol) in THF (82 mL) cooled (-10 ° C) and stirred, 3.78 mL of diethyl azodicarboxylate (4.18 g, 22.77 mmol) was added. After 5 min, 5.06 mL of a solution of diphenylphosphoryl azide (6.46 g, 22.77 mmol) in THF (82 mL) was slowly added. The reaction mixture was stirred at -10 ° C for 6 h, and stirring was continued at room temperature overnight. After overnight, the reaction mixture was diluted with dichloromethane (100 mL), and the mixture was 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 and dried and evaporated. The product was purified by column chromatography using a mobile phase of methanol in dichloromethane (the volume percentage of methanol in the methanol in dichloromethane was 5%) to obtain 2.27 g of the 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) Sodium 1-azido-4-sulfonate-cyclohexane

[0135]

[0136] S-(4-azido-cyclohexyl) ethylsulfate (1.71 g, 8.41 mmol) was placed in a 100 mL flask, 20 mL of acetic acid and 20 mL of hydrogen peroxide were added, and the reaction mixture was stirred at room temperature overnight. The next day, the reaction mixture was fully evaporated to remove acetic acid and hydrogen peroxide. 100 mL of pure water was added to the flask, and the pH value 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-phenanthroline (288 mg, 1.26 mmol), 1-azido-4-sodium sulfonate-cyclohexane (0.73 mg, 2.78 mmol), 489 mg (2.78 mmol) sodium ascorbate and a stirring rod were loaded into a Schlenk tube (250 mL). The Schlenk tube was connected to the Schlenk line. It was evacuated and refilled three times with nitrogen and kept under nitrogen. 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 the Schlenk tube, and finally 2.9 mL (2.3 mol%) of Cu(II)-TBTA solution (prepared as follows: 65 mg TBTA and 30 mg CuSO4·5H2O were mixed in 11.8 mL of degassed water / DMSO solvent, and the volume ratio of water to DMSO in the degassed water / DMSO solvent was 1:1) was added dropwise, and the reaction mixture was stirred at room temperature under inert gas for 72 h. After 72 h, the reaction mixture was centrifuged to remove the dichloromethane layer, and the water layer was evaporated using a rotary evaporator. The yellow primary product was redissolved in a mixture of 10 mL of water and 5 mL of methanol. Next, the mixture was stirred overnight for recrystallization. After recrystallization, the mixture was filtered and the solid was washed with acetone. Reverse phase chromatography was performed on C-18 silica gel with water as the mobile phase and the volume percentage of methanol gradually increased from 0% to 50%. The purified material was dried in vacuo. The product was 0.78 g (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] The organic phases for all solvent extraction experiments were prepared using the tracer loaded organic phase (TLOP)-protocol.

[0145] Ligand stock solution was prepared by dissolving 318 mg of ligand in 10 mL of pure water to give a concentration of 40 mM.

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

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

[0148] HNO3 stock solutions were 0.1M and 1M.

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

[0150] 2.2 Tracer-loaded organic phase (TLOP) - Scheme

[0151] 1. Preparation of irradiated aqueous phase

[0152] Prepare 100 mL of 3M HNO3 into 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] 2. Preparation of TODGA

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

[0155] 3. Load

[0156] 20 mL of organic phase was added to the centrifuge tube containing water and 20 μL of 241Am tracer and 20 μL of 152 / 154Eu phase, and the centrifuge tube was properly closed. The centrifuge tube was then mounted on an orbital shaker and vibrated for 60 min. Afterwards, it was centrifuged at 3000 rpm for 2 min, and the aqueous phase was carefully transferred to a radioactive waste bottle.

[0157] 4. 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, a sample of the organic phase was taken for LSC to measure the initial 241Am and 152 / 154Eu counts.

[0160] The prepared TLOP should be stored safely in a refrigerator to minimize solvent evaporation and maintain the same count ratio over many days. For each sample tube, use 1 mL of organic phase.

[0161] 2.3 Three types of tests:

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

[0163] For the ligand DSC-BTrzPhen, acidity studies were performed at 0.001, 0.005, 0.01, 0.05, 0.10, and 0.25 M nitric acid, and the standard concentration of the ligand was 10 mM, 1 M sodium nitrate.

[0164] 2.3.2 Kinetic studies 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 the test was performed at intervals of 5, 10, 15, 30, 45 and 60 min.

[0166] 2.3.3 Ligand concentration extraction studies to determine the effect of ligand concentration on partition ratio and SF Eu / Am 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] Each 1 mL of aqueous phase and 1 mL of organic phase were mixed in a PP vial, shaken using a vortex oscillator (standard 60 min), and then centrifuged (3000 rpm, 2 min) to completely separate the two phases. Samples from the aqueous and organic phases were then collected, and the radioactivity in different channels was counted using LSC, which could distinguish the α radioactivity of 241Am and the β radioactivity of 152Eu / 154Eu. To ensure the accuracy of the data, each sample was measured for at least 5 min. The count ratios in the two phases were then interpreted as the extraction parameters D Am and D Eu , while SF Eu / Am Then calculate D Eu / D Am Compare.

[0170] 2.4 Solvent extraction results

[0171] Figure 2 is the acidity test curve of DSC-BTrzPhen, Figure 3 is the DSC-BTrzPhen ligand concentration extraction curve, Figure 4 The kinetic test curve of DSC-BTrzPhen shows that the best acidity for DSC-BTrzPhen is 0.001-0.01M, and the separation effect is good. Eu / Am The temperature is 360-440, and the equilibrium time is good, less than 15 minutes.

[0172] In summary, the present invention develops a new DSC-BTrzPhen ligand by designing the structure of the ligand. The ligand not only ensures a high distribution ratio for Eu, but also the introduction of the water-soluble ligand also ensures efficient stripping of Am. The lanthanum-actinium separation factor SF of the DSC-BTrzPhen ligand is Eu / AmAbove 400, the separation effect is good. In addition, the ligand has good water solubility and extraction kinetics, and the water solubility is excellent, and equilibrium can be reached in 15 minutes. The ligand of the present invention not only provides a new and effective method for spent fuel reprocessing, but also provides important support for the sustainable development of nuclear energy, the scientific treatment and safe management of existing radioactive waste.

[0173] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

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

2. The method for preparing the DSC-BTrzPhen ligand according to claim 1, characterized in that: The following steps are involved: Mixing 2,9-dimethyl-1,10-phenanthroline, an organic solvent and an oxidant to perform a first oxidation reaction to obtain 2,9-dialdehyde-1,10-phenanthroline; The 2,9-diacetyl-1,10-phenanthroline, K2CO3, Ohira-Bestmann reagent and organic solvent are mixed to perform a Seyfert-Gilbert carbon addition reaction to obtain 2,9-diethynyl-1,10-phenanthroline; 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; The 1-hydroxy-4-toluenesulfonylcyclohexane, potassium thioacetate and an organic solvent are mixed to carry out a second nucleophilic substitution reaction to obtain S-(4-hydroxycyclohexyl)ethyl sulfate; The S-(4-hydroxycyclohexyl)ethyl sulfate, triphenylphosphine, diethyl azodicarboxylate, diphenylphosphoryl azide and an organic solvent are mixed to perform a Mitsunobu reaction to obtain S-(4-azido-cyclohexyl)ethyl sulfate; The S-(4-azido-cyclohexyl) ethylsulfate, acetic acid and hydrogen peroxide are mixed for a second oxidation reaction, and then the pH value of the obtained oxidation product is adjusted to be neutral with an inorganic alkaline substance to obtain 1-azido-4-sodium sulfonate-cyclohexane; the inorganic alkaline substance contains sodium ions; The 2,9-diethynyl-1,10-phenanthroline, 1-azido-4-sodium sulfonate-cyclohexane, sodium ascorbate, diisopropylethylamine, Cu(II)-TBTA solution and solvent are mixed to carry out copper-catalyzed azide-alkyne cycloaddition reaction to obtain the DSC-BTrzPhen ligand.

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

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

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

6. Use of the DSC-BTrzPhen ligand according to claim 1 in separation of lanthanides and actinides.

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

8. The method according to claim 7, characterized in that The lanthanide elements include europium, and the actinide elements include americium.

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

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

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