3n-PTD ligand, and preparation method and application thereof
By preparing high-yield 3N-PTD ligands, the problem of low separation yields of lanthanides and actinides was solved, achieving efficient separation of lanthanides and actinides and safe processing of spent nuclear fuel, thus promoting the effective utilization of resources.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- LANZHOU UNIV
- Filing Date
- 2026-04-01
- Publication Date
- 2026-06-23
AI Technical Summary
The existing technology for preparing ligands for the separation of lanthanides and actinides has a low yield, resulting in low efficiency in the processing of spent nuclear fuel. Furthermore, the high radioactivity and toxicity of minor actinides pose a threat to the environment and health.
The 3N-PTD ligand was synthesized in one step via a click reaction, involving the reflux reaction of 3-chloropropylamine hydrochloride, sodium azide, and deionized water, followed by a click reaction with 2,6-diethynylpyridine, 3-azidopropane-1-amine, and sodium ascorbate. The 3N-PTD ligand was prepared in high yield and used for the separation and extraction of lanthanum and actinium.
This technology enables the efficient separation of lanthanum and actinium, improves the efficiency of spent nuclear fuel processing, reduces the hazards of high-level radioactive waste, and provides a safe and efficient way to utilize resources.
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Figure CN122255108A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of extraction and separation technology, specifically relating to a 3N-PTD ligand, its preparation method, and its application. Background Technology
[0002] Nuclear energy plays an increasingly important role in optimizing the energy structure and alleviating the environmental pressure caused by the consumption of fossil fuels. However, the large-scale application of nuclear energy inevitably generates a large amount of spent nuclear fuel (SNF), whose main components include recyclable nuclides such as plutonium and uranium, as well as various hazardous radioactive materials. How to safely and efficiently dispose of spent nuclear fuel has become one of the key issues restricting the sustainable development of the nuclear power industry. Currently, the PUREX process is mainly used in industry to recover and reuse plutonium and uranium from spent nuclear fuel. Although this process can effectively recover the main actinide elements, it generates a large amount of highly reactive liquid waste (HLW) during the process. This type of waste liquid has a complex composition, containing not only long-lived fission products (LLFPs) such as technetium (Tc) and iodine (I), but also minor actinide elements such as neptunium (Np), americium (Am), and curium (Cm). Among them, minor actinide elements are characterized by long half-lives, strong radioactivity, and high toxicity, posing a long-term and serious threat to the ecological environment and human health. Therefore, achieving effective separation of minor actinide elements from other nuclides is one of the core links in the harmless treatment and resource utilization of high-level radioactive waste liquid.
[0003] However, the current process for separating ligands from lanthanides and actinides suffers from low yields. Summary of the Invention
[0004] In view of this, the present invention provides a 3N-PTD ligand, its preparation method and application, and the preparation method provided by the present invention yields a high yield of the 3N-PTD ligand.
[0005] To achieve the above objectives, the present invention provides the following technical solution: This invention provides a 3N-PTD ligand having the structure shown in Formula I: Formula I.
[0006] This invention also provides a method for preparing the 3N-PTD ligand described in the above technical solution, comprising the following steps: 3-Chloropropylamine hydrochloride, sodium azide, and deionized water were mixed and refluxed to obtain 3-azidopropane-1-amine. The structural formula of the 3-azidopropane-1-amine is: ; 2,6-Diethynylpyridine, 3-azidopropane-1-amine, sodium ascorbate, and CuSO4·5H2O were dissolved and subjected to a click reaction to obtain the 3N-PTD ligand.
[0007] Preferably, the molar ratio of 3-chloropropylamine hydrochloride to sodium azide is 1:2.1~3.0; and the reflux reaction time is 15~20 h.
[0008] Preferably, the molar ratio of 2,6-diethynylpyridine to 3-azidopropane-1-amine is 1:2.1~3.0.
[0009] Preferably, the molar ratio of 2,6-diethynylpyridine, sodium ascorbate, and CuSO4·5H2O is 7.82:1.5~2.0:0.15~0.2.
[0010] Preferably, the dissolved reagent is tert-butanol and water; the click reaction temperature is 50~60℃ and the time is 1~2 h; the click reaction is carried out in a microwave reactor.
[0011] Preferably, the reflux reaction further includes cooling the reaction system to room temperature and then performing extraction, with the extracted organic phase being dried, filtered, and concentrated in sequence.
[0012] Preferably, after the click reaction, the step further includes evaporating the click reaction solution to dryness and then purifying it by chromatographic column, with the fraction obtained from the chromatographic column purification being subjected to solvent removal and drying in sequence.
[0013] The present invention also provides the application of the 3N-PTD ligand described in the above technical solution or the 3N-PTD ligand prepared by any of the above preparation methods in the separation and extraction of lanthanum and actinium.
[0014] This invention also provides a method for separating nuclear waste liquid using 3N-PTD ligands. 241 Am and 152 Eu's method includes the following steps: Extracting nuclear waste liquid using water containing an extractant, 241 Am is back-extracted to the aqueous phase; the aqueous phase containing the extractant includes HNO3, water and the extractant; the extractant is the 3N-PTD ligand described in the above technical solution or the 3N-PTD ligand prepared by any of the above preparation methods; the acidity of nitric acid in the aqueous phase containing the extractant is 0.005~0.1 M; the volume ratio of the aqueous phase containing the extractant to the nuclear waste liquid is 1:1.
[0015] This invention provides a method for preparing 3N-PTD ligands, comprising the following steps: 3-Chloropropylamine hydrochloride, sodium azide, and deionized water were mixed and refluxed to obtain 3-azidopropane-1-amine. 2,6-Diethynylpyridine, 3-azidopropane-1-amine, sodium ascorbate, and CuSO4·5H2O were dissolved and subjected to a click reaction to obtain the 3N-PTD ligand. This invention utilizes a click reaction to synthesize a water-soluble amine branch containing an alkynyl group in a one-step process, resulting in a more economical, efficient, and high-yield synthesis. Attached Figure Description
[0016] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the accompanying drawings used in the embodiments will be briefly described below.
[0017] Figure 1 The 1H NMR spectrum of 3-azidopropane-1-amine; Figure 2 The carbon NMR spectrum of 3-azidopropane-1-amine; Figure 3 The 1H NMR spectrum of the product (3N-PTD ligand) prepared in Example 1; Figure 4 The image shows the carbon NMR spectrum of the product (3N-PTD ligand) prepared in Example 1. Figure 5 The mass spectrum of 3-azidopropane-1-amine; Figure 6 The mass spectrum of the product (3N-PTD ligand) prepared in Example 1; Figure 7 High-resolution mass spectrum of the product (3N-PTD ligand) prepared in Example 1; Figure 8 The image shows the acidity test results. Figure 9 The results of the dynamic test are shown in the figure. Figure 10 The graph shows the results of the ligand concentration extraction test. Detailed Implementation
[0018] This invention provides a 3N-PTD ligand having the structure shown in Formula I: Formula I.
[0019] This invention also provides a method for preparing the 3N-PTD ligand described in the above technical solution, comprising the following steps: 3-Chloropropylamine hydrochloride, sodium azide, and deionized water were mixed and refluxed to obtain 3-azidopropane-1-amine. The structural formula of the 3-azidopropane-1-amine is: ; 2,6-Diethynylpyridine, 3-azidopropane-1-amine, sodium ascorbate, and CuSO4·5H2O were dissolved and subjected to a click reaction to obtain the 3N-PTD ligand.
[0020] In this invention, 3-chloropropylamine hydrochloride, sodium azide, and deionized water are mixed and subjected to reflux reaction to obtain 3-azidopropane-1-amine.
[0021] In one embodiment of the present invention, the molar ratio of 3-chloropropylamine hydrochloride and sodium azide can be 1:2.1~3.0, specifically 1:2.5; the reflux reaction time is 15~20 h, specifically 16 h.
[0022] In one embodiment of the present invention, the reaction system is further cooled to room temperature and then extracted after the reflux reaction. The organic phase obtained by extraction is then dried, filtered and concentrated to obtain 3-azidopropane-1-amine.
[0023] After obtaining 3-azidopropane-1-amine, the present invention dissolves 2,6-diethynylpyridine, 3-azidopropane-1-amine, sodium ascorbate, and CuSO4·5H2O, and performs a click reaction to obtain the 3N-PTD ligand.
[0024] In one embodiment of the present invention, the dissolved reagent can be tert-butanol and water, and the volume ratio of tert-butanol to water can be 3~5:1, specifically 4:1. In another embodiment of the present invention, the volume ratio of 2,6-diethynylpyridine to tert-butanol can be 7.82 mmol: 8~10 mL, specifically 7.82 mmol: 8 mL; the molar ratio of 2,6-diethynylpyridine to 3-azidopropane-1-amine can be 1:2.1~3.0, specifically 1:2.5; the molar ratio of 2,6-diethynylpyridine, sodium ascorbate, and CuSO4·5H2O can be 7.82:1.5~2.0:0.15~0.2, specifically 7.82:1.57:0.16.
[0025] In one embodiment of the present invention, the temperature of the click reaction can be 50~60℃, specifically 50℃, 55℃ or 60℃, and the time can be 1~2 h, specifically 1 h, 1.5 h or 2 h. In the present invention, the click reaction can be carried out in a microwave reactor.
[0026] In one embodiment of the present invention, after the click reaction, the reaction solution is further purified by chromatographic column filtration after evaporation to dryness. The fraction obtained from the column filtration is then subjected to solvent evaporation and drying sequentially. In another embodiment of the present invention, the mobile phase for column filtration is a mixture of dichloromethane and methanol; the volume ratio of dichloromethane to methanol in the mixture can be 90:10.
[0027] This invention also provides the application of 3N-PTD ligands in the separation and extraction of lanthanum and actinium.
[0028] This invention also provides a method for separating nuclear waste liquid using 3N-PTD ligands. 241 Am and 152 Eu's method includes the following steps: Extracting nuclear waste liquid using water containing an extractant, 241 Am is back-extracted to the aqueous phase; the aqueous phase containing the extractant includes HNO3, water and the extractant; the extractant is the 3N-PTD ligand described in the above technical solution or the 3N-PTD ligand prepared by any of the above preparation methods.
[0029] In one embodiment of the present invention, the organic phase in the nuclear waste liquid includes N,N,N′,N′-tetraoctyl-3-oxopramethylenediamide, kerosene, and n-octanol; the concentration of N,N,N′,N′-tetraoctyl-3-oxopramethylenediamide in the organic solvent can be 0.2 M; and the volume ratio of kerosene to n-octanol in the organic solvent can be 95:5.
[0030] In one embodiment of the present invention, the acidity of nitric acid in the aqueous phase containing the extractant can be 0.005~0.1 M. In another embodiment of the present invention, the concentration of 3N-PTD ligand in the aqueous phase containing the extractant can be 80 mM.
[0031] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the accompanying drawings and embodiments, but these should not be construed as limiting the scope of protection of the present invention.
[0032] Raw material specifications and sources in the examples: HNO3: Analytical grade. Deionized water: Low conductivity (18.2 MΩ).
[0033] 241 The am tracer (americium tracer) was obtained from the School of Nuclear Science and Technology, Nanhua University, with a radioactivity concentration of 34319 Bq / mL. Centrifuge tube: 10 mL. 241The activity of Am was counted using a Tri-Carb 4910 TR (Revvity) liquid scintillation counter; Eu was determined using an ICPE-9810 (SHIMADZU) inductively coupled plasma atomic emission spectrometer.
[0034] Example 1 (1) 3-Chloropropylamine hydrochloride (3.0 g, 22.61 mmol) and sodium azide (NaN3, 3.67 g, 56.53 mmol, 2.5 eq) were placed in a 100 mL round-bottom flask, and then 30 mL of deionized water was added. The reaction mixture was heated to 80 °C and stirred under reflux for 16 h. After the reaction was completed, the mixture was cooled to room temperature and 100 mL of 5 wt.% NaOH aqueous solution was added. The aqueous phase was then extracted with dichloromethane (DCM, 3 × 100 mL). The organic extracts were combined, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to give a colorless liquid product (2.2 g, yield 97%).
[0035] The structural formula of 3-azidopropane-1-amine is: ; Its 1H NMR spectrum and 1C NMR spectrum are shown below. Figures 1-2 The information from the NMR spectrum is as follows: 1 H-NMR (600 MHz, CDCl3) δ (ppm): 3.34-3.32 (m, 2H), 2.77-2.75 (m, 2H), 1.69-1.67 (m, 2H), 1.16 (s, 2H); 13 C-NMR (600 MHz, CDCl3) δ (ppm): 49.18 (1C), 39.38 (1C), 32.50 (1C); MS (ESI + ) m / z calcd. for [2M + HCl + H] + : 237.13, found: 237.1566.
[0036] Figure 5 This is the mass spectrum of 3-azidopropane-1-amine. Spectral information: Method: ESI positive mode, Chemical Formula: C3H8N4, MS (ESI) + ) m / z calcd. for [2M + HCl + H] +: 237.13, found:237.1566.
[0037] (2) In a glove box, 2,6-diethynylpyridine (1.00 g, 7.82 mmol), 3-azidopropane-1-amine (1.97 g, 19.66 mmol, 2.50 eq), sodium ascorbate (0.31 g, 1.57 mmol), and CuSO4·5H2O (0.04 g, 0.16 mmol) were added sequentially to a 20 mL microwave reaction flask. Then, 8 mL of tert-butanol and 2 mL of water were added using a syringe. The reaction flask was allowed to stand for 30 min to cool to room temperature. Next, the reaction flask was placed in a microwave reactor and reacted at 50 °C for 60 min.
[0038] After the reaction was complete, the mixture was completely evaporated to dryness, and purified by column chromatography using dichloromethane-methanol (90:10 v / v) as the mobile phase. The target component was collected and the solvent was evaporated. The resulting solid was dried under high vacuum to obtain 2.32 g of product (3N-PTD ligand), with a yield of 90% (the yield of step (2) is calculated as the actual yield of 3N-PTD ligand / theoretical yield). The purity of the ligand was 91.3 wt% (100%), and the ligand was tested by elemental analysis.
[0039] The synthetic route for 3N-PTD ligands is as follows: The proton and carbon NMR spectra of the product are shown below. Figures 3-4 The NMR information is as follows: 1 H-NMR (600 MHz, D2O) δ (ppm): 8.09-8.08 (m, 2H), 7.56-7.54 (m, 1H), 7.35-7.33 (m, 2H), 4.37-4.35 (m, 4H), 2.71-2.68 (m, 4H), 2.05-2.02 (m, 4H); 13 C-NMR (600 MHz, D2O) δ (ppm): 148.13 (2C), 146.58 (2C), 138.32 (1C), 123.60 (2C), 119.29 (2C), 48.09 (2C), 37.45 (2C), 31.29 (2C).
[0040] Figure 6The mass spectrum of the product is shown below. Spectral information: Method: ESI positive mode, Chemical Formula: C 15 H 21 N9, MS (ESI + ) m / z calcd. for [M+H] + : 328.20, found: 328.1976; MS(ESI + ) m / z calcd. for [M+Na] + : 350.18, found: 350.1800.
[0041] Figure 7 The high-resolution mass spectrum of the product is shown below. The spectral information is as follows: Method: ESI positive mode, Chemical Formula: C 15 H 21 N9, HRMS (ESI + ) m / z calcd. for [M+H] + : 328.20, found: 328.1991;HRMS (ESI + ) m / z calcd. for [M+Na] + : 350.18, found: 350.1813.
[0042] Application examples one, 241 Am tracer supported on organic phase (1) Preparation of irradiated aqueous phase Add 10 mL of 3 M HNO3 to a polypropylene centrifuge tube, then add 20 μL of HNO3. 241 Am tracer.
[0043] (2) Preparation of the organic phase of TODGA 3.521 g TODGA was dissolved in 30 mL of kerosene / n-octanol (95:5, v / v) solution to obtain an organic phase with a concentration of 0.2 MTODGA.
[0044] (3) Load Add 20 mL of the TODGA organic phase to a mixture containing water and 20 μL of... 241 Place the Am tracer in a centrifuge tube and close the tube. Then, shake the tube well for 60 minutes, centrifuge at 3000 rpm for 2 minutes, and transfer the aqueous phase to a radioactive waste bottle.
[0045] (4) Washing (to remove HNO3 dissolved in the organic phase) Add 10 mL of 0.5 M HNO3 to a centrifuge tube containing the tracer organic phase, close the centrifuge tube and shake for 15 min, centrifuge at 3000 rpm for 2 min, transfer the aqueous phase to a radioactive waste bottle, and obtain the 241Am tracer-loaded organic phase in the centrifuge tube.
[0046] II. Eu-supported organic phase (1) Preparation of irradiated aqueous phase Add 10 mL of 3 M HNO3 to a polypropylene centrifuge tube, followed by 2 mL of 1 mM Eu(NO3)3 stock solution.
[0047] (2) Preparation of the organic phase of TODGA 3.521 g TODGA was dissolved in 30 mL of kerosene / n-octanol (95:5, v / v) solution to obtain an organic phase with a concentration of 0.2 MTODGA.
[0048] (3) Load Add 20 mL of the TODGA organic phase to a centrifuge tube containing water and 2 mL of 1 mM Eu(NO3)3, and close the centrifuge tube. Then, shake the centrifuge tube well for 60 min, centrifuge at 3000 rpm for 2 min, and transfer the aqueous phase to a radioactive waste bottle.
[0049] (4) Washing Add 10 mL of 0.5 M HNO3 to the centrifuge tube containing the organic phase from step (3), close the centrifuge tube and shake for 15 min. Centrifuge at 3000 rpm for 2 min, transfer the aqueous phase to a radioactive waste bottle, and obtain the Eu-loaded organic phase in the centrifuge tube.
[0050] After washing, ICP-OES was used to further confirm that more than 99.9% of Eu was loaded in the organic phase, that is, the Eu in the organic phase was also 1 mM.
[0051] III. Stock Solution Ligand stock solution: A ligand stock solution was prepared by dissolving 573.8 mg of ligand in 10 mL of pure water, resulting in a concentration of 160 mM.
[0052] Containing 0.01 M nitric acid 241 Am(NO3)3 stock solution.
[0053] 1 mM Eu(NO3)3 stock solution.
[0054] The HNO3 stock solutions are 0.1 M and 1 M.
[0055] The stock solution of NaNO3 is 4 M.
[0056] IV: Testing (1) Preparation of acidity test solution: Aqueous phase containing 3N-PTD: The concentration of 3N-PTD ligand in the aqueous phase is 80 mM, the concentration of sodium nitrate is 0.5 M, and the acidity of nitric acid is 0.005, 0.01, 0.05, 0.10, and 0.25 M, respectively.
[0057] (2) Dynamics research.
[0058] The aqueous phase containing 3N-PTD used in the kinetic study: the concentration of 3N-PTD ligand in the aqueous phase was 80 mM, the acidity of nitric acid was 0.01 M, and the concentration of sodium nitrate was 0.5 M. Tests were conducted every 5, 10, 30, and 60 minutes.
[0059] (3) Ligand concentration extraction studies to determine the ligand concentration-partition ratio and SF Eu / Am The impact.
[0060] The aqueous phase containing 3N-PTD for ligand concentration extraction studies: the aqueous phase contained 0.01M nitric acid, 0.5M sodium nitrate, and 20, 40, 60, 80, and 100 mM ligands, respectively.
[0061] (4) Test method: Each 0.8 mL aqueous phase (aqueous phase containing 3N-PTD for acidity testing, aqueous phase containing 3N-PTD for kinetic studies, or aqueous phase containing 3N-PTD for ligand concentration extraction studies) and 0.8 mL organic phase ( 241 The Am tracer-loaded organic phase and the Eu-loaded organic phase (volume ratio 1:1) were mixed in a 10 mL centrifuge tube, vortexed for 30 min, and then centrifuged (3000 rpm, 2 min) to completely separate the two phases. Samples were then collected from both the aqueous and organic phases, and the radioactivity in different channels was counted using LSC to distinguish them. 241 The alpha radioactivity of am. This can be determined using ICP-OES. 152 The concentration of Eu. Then the count ratio in the two phases is interpreted as the extraction parameter D. Am and D Eu , and SF Eu / Am The calculation is D. Eu / D Am Compare.
[0062] (5) Test results Test results are available Figures 8-10 ,in Figure 8The results are from the acidity test. Figure 9 For the results of dynamic tests, Figure 10 The results are from the ligand concentration extraction test. Figure 8 It can be seen that the separation factor reaches its maximum value of 162 at a nitric acid concentration of 0.01 M, indicating that the optimal acidity for the ligand is 0.01 M. Furthermore, at acidities of 0.005–0.1 M, the partition ratio of metal Eu is >1 (utilizing the lipid-soluble ligand TODGA for coordination). 152 Eu is in the organic phase), while the partition ratio of metal Am is <1 (using the water-soluble extractant 3N-PTD ligand). 241 Am back-extraction in the aqueous phase indicates that ligand separation is effective in acidity ranges from 0.005 to 0.1 M.
[0063] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.
Claims
1. A 3N-PTD ligand, characterized in that, It has the structure shown in Equation I: Equation I.
2. The method for preparing the 3N-PTD ligand according to claim 1, characterized in that, Includes the following steps: 3-Chloropropylamine hydrochloride, sodium azide, and deionized water were mixed and refluxed to obtain 3-azidopropane-1-amine. The structural formula of the 3-azidopropane-1-amine is: ; 2,6-Diethynylpyridine, 3-azidopropane-1-amine, sodium ascorbate, and CuSO4·5H2O were dissolved and subjected to a click reaction to obtain the 3N-PTD ligand.
3. The preparation method according to claim 2, characterized in that, The molar ratio of 3-chloropropylamine hydrochloride to sodium azide is 1:2.1~3.0; the reflux reaction time is 15~20 h.
4. The preparation method according to claim 2, characterized in that, The molar ratio of 2,6-diethynylpyridine to 3-azidopropane-1-amine is 1:2.1~3.
0.
5. The preparation method according to claim 2, characterized in that, The molar ratio of 2,6-diethynylpyridine, sodium ascorbate, and CuSO4·5H2O is 7.82:1.5~2.0:0.15~0.
2.
6. The preparation method according to claim 2, characterized in that, The dissolved reagents are tert-butanol and water; the click reaction is carried out at a temperature of 50-60°C for 1-2 hours; and the click reaction is conducted in a microwave reactor.
7. The preparation method according to claim 3, characterized in that, The reflux reaction is followed by cooling the reaction system to room temperature and then extracting it. The extracted organic phase is then dried, filtered, and concentrated.
8. The preparation method according to claim 6, characterized in that, After the click reaction, the process further includes evaporating the click reaction solution to dryness and then purifying it by chromatographic column. The fraction obtained from the chromatographic column purification is then subjected to solvent removal and drying in sequence.
9. The application of the 3N-PTD ligand according to claim 1 or the 3N-PTD ligand prepared by any one of the preparation methods of claims 2 to 8 in the separation and extraction of lanthanum and actinium.
10. A method for separating nuclear waste liquid using 3N-PTD ligands 241 Am and 152 Eu's method includes the following steps: Extracting nuclear waste liquid using water containing an extractant, 241 Am is back-extracted to the aqueous phase; the aqueous phase containing the extractant includes HNO3, water and the extractant, wherein the extractant is the 3N-PTD ligand as described in claim 1 or the 3N-PTD ligand prepared by any one of claims 2 to 8; the acidity of nitric acid in the aqueous phase containing the extractant is 0.005 to 0.1 M; the volume ratio of the aqueous phase containing the extractant to the nuclear waste liquid is 1:1.