A novel molybdenum-99 adsorption material and a preparation method thereof

Abstract

The application belongs to the technical field of radiochemistry, and particularly relates to a novel molybdenum-99 adsorption material and a preparation method thereof. A metal composite adsorption material is obtained through the steps of washing, filtering, drying and calcining, by taking a zirconium-containing compound and lye as starting materials and introducing ionic liquid in the preparation process to assist synthesis. 99 Mo- 99m Tc generator.

Description

Technical Field

[0001] This invention belongs to the field of radiochemistry technology, specifically relating to a novel molybdenum-99 adsorbent material and its preparation method. Background Technology

[0002] 99m Tc is the most widely used radioactive isotope in nuclear medicine, among which 99 Mo is used in the preparation of radioisotopes. 99m The parent compound of Tc has a half-life of 66 hours. To avoid the large amount of radioactive waste generated by the fission reaction of low / high enriched uranium under neutron irradiation, a neutron activation method can be used. 98 Mo(n,γ) 99 Mo nuclei reaction generates 99 Mo. Although this method is simple to operate and produces less waste, it generates... 99 Mo activity was low, and a large amount of unconverted molecules were present. 98 Mo is present. Therefore, in clinical applications, it is necessary to use medications that target Mo. 99 Mo is used as a chromatography column material with high adsorption capacity to prepare 99 Mo- 99m Tc generator, to obtain sufficient quantity 99m Tc. In addition, gel type 99 Mo- 99m The Tc generator also needs to be... 99 Mo is a chromatography column material with high adsorption capacity to ensure sufficient adsorption. 99m Tc solution 99 The Mo content meets the usage requirements, extending the service life of the generator.

[0003] According to reports 99 Mo- 99m Alumina is commonly used as the adsorbent in Tc generators, but its adsorption capacity is low, only 2–20 mg / g. This means it cannot produce a sufficient concentration of radioactivity. 99m Tc, on the other hand, the size of the chromatography column would be very large, leading to a significant increase in cost. Patent (CN 109701482 B) discloses a fission-type technetium [ 99m The preparation process of γ-alumina adsorbent for Tc generators is described, with the maximum exchange capacity of γ-alumina containing oxidant for molybdenum being 183.71 (mg Mo / g γ-Al2O3) in the examples. Patent application (CN 114898909 A) discloses a low specific activity molybdenum technetium generator and a method for obtaining Tc-99m products and recovering and enriching metallic molybdenum. In the examples, the filling material is macroporous / mesoporous γ-type alumina, with a maximum static adsorption capacity of 250 mg / g for metallic molybdenum ions. Patent (CN 111485123 B) discloses a method for separating molybdenum ions from a large amount of low specific activity Mo solution.99m Tc generator, wherein the resin filled in the chromatographic separation column is resin A derived from cross-linking with polyethylene glycol as the backbone or resin B derived from cross-linking with N,N-dimethyl acrylamide and polyethylene glycol acrylamide copolymerization, and the purification column is an acidic cation exchange column and an acidic Al2O3 column, but no adsorption capacity is mentioned. In the above patent method, part of the adsorption material is reported, but in order to further improve the low specific activity 99 Mo utilization rate, it is still necessary to study 99 Mo has high adsorption capacity, and the related content does not pay attention to the radiation resistance of the adsorption material itself. SUMMARY

[0004] The purpose of the present application is to solve the above problems, by combining ionic liquid assisted synthesis of metal composite materials, further improve the adsorption capacity of molybdenum-99. Suitable for adsorbing nuclide molybdenum-99. According to this method, metal composite materials with high adsorption performance and radiation resistance to molybdenum-99 can be prepared, which can be used to prepare 99 Mo- 99m Tc generator, in order to obtain a 99m Tc solution that meets the use requirements.

[0005] To this end, the first aspect of the present application provides a preparation method of a new molybdenum-99 adsorption material, which comprises:

[0006] Step 1: add alkali solution to a fully dissolved zirconium-containing compound solution, adjust the pH to 9-13, then add ionic liquid, stir vigorously, and obtain a gel solution after sufficient reaction; this step uses ionic liquid to assist the crystallization process of metal composite materials;

[0007] Step 2: washing, drying, calcining, grinding, and optionally sieving to obtain the adsorption material;

[0008] The ionic liquid is one or more of 1-butyl-1-methylpyrrolidine bis(trifluoromethylsulfonyl) amide, 1-butyl-1-methylpyrrolidine bis(trifluoromethylsulfonyl) imide, 1-butyl-1-methylpyrrolidine bis(trifluoromethylsulfonyl) imide, and methyltrioctylammonium chloride.

[0009] The ionic liquid is preferably one or more of 1-butyl-1-methylpyrrolidine bis(trifluoromethylsulfonyl) imide and methyltrioctylammonium chloride.

[0010] The ionic liquid can be used as a green alternative to traditional organic solvents, which can help reduce the aging of sols during synthesis, alleviate the shrinkage problem during gel drying, and assist the synthesis of zirconium oxide adsorbent materials to prevent the reduction of specific surface area of the adsorbent materials and thus affect the adsorption capacity. The adsorption capacity of the adsorbent material obtained by the above method for molybdenum-99 is ≥ 290 mg / g.

[0011] As a preferred solution, in the preparation method of the new molybdenum-99 adsorbent material, the zirconium-containing compound is one or more of zirconium oxychloride and zirconium nitrate, and more preferably zirconium oxychloride.

[0012] As a preferred solution, in the preparation method of the new molybdenum-99 adsorbent material, in step 1, the ionic liquid is 0.1%-99.9% of the mass of the zirconium-containing compound, and preferably 0.3%-10%.

[0013] As a preferred solution, in the preparation method of the new molybdenum-99 adsorbent material, in step 1, the zirconium-containing compound solution is obtained by mixing the zirconium-containing compound with water, optionally adding a dispersing agent, and stirring vigorously to fully mix and dissolve the zirconium-containing compound; the dispersing agent is one or more of anhydrous ethanol and polyethylene glycol.

[0014] As a preferred solution, in the preparation method of the new molybdenum-99 adsorbent material, in step 1, the alkali solution is one or more of ammonia and sodium hydroxide; preferably, the alkali solution is added dropwise.

[0015] As a preferred solution, in the preparation method of the new molybdenum-99 adsorbent material, in step 1, the reaction time is 20-28h.

[0016] As a preferred solution, in the preparation method of the new molybdenum-99 adsorbent material, in step 2, the drying temperature is 20℃-300℃, and the operation time is 5min-60h, and preferably the operation time is 3-9h.

[0017] As a preferred solution, in the preparation method of the new molybdenum-99 adsorbent material, in step 2, the calcination temperature is 500℃-1000℃, and the operation time is 5min-60h, and preferably the operation time is 3-9h.

[0018] As a preferred solution, in the preparation method of the new molybdenum-99 adsorbent material, in step 2, the washing includes repeatedly washing by suction filtration multiple times; the washing preferably uses one or more of distilled water and anhydrous ethanol.

[0019] According to the present application, in a specific embodiment, in the preparation method of the new molybdenum-99 adsorbent material, after sieving, the particle size of the adsorbent material is 100-200 mesh.

[0020] The second aspect of the present application provides a new molybdenum-99 adsorption material prepared by the preparation method described above.

[0021] Compared with the prior art, the present application at least includes the following beneficial effects:

[0022] The present application prepares a new molybdenum-99 adsorption material, which has a molybdenum-99 adsorption capacity greater than 290 mg / g and good radiation resistance, and can be used to prepare a molybdenum-99 generator. 99 Mo- 99m Tc generator.

[0023] The above description is only a summary of the technical solutions of the present application, in order to more clearly understand the technical means of the present application, and to be implemented according to the content of the specification, and in order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the following specific embodiments of the present application are described. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 The new molybdenum-99 adsorption material prepared in Example 1 of the present application. DETAILED DESCRIPTION

[0025] In the following description, a large number of specific details are given in order to provide a more thorough understanding of the technical solutions provided by the present application. However, it is obvious to those skilled in the art that the technical solutions provided by the present application can be implemented without one or more of these details.

[0026] In the embodiments of the present application, the ionic liquid is derived from Aladdin Biochem Technology Co., Ltd.

[0027] In the embodiments, the specific conditions are not specified. The reagents or instruments used are not specified by the manufacturer, and are all conventional products that can be purchased on the market.

[0028] Example 1

[0029] 6.45 g of zirconium oxychloride octahydrate was weighed and dissolved in 100 mL of water, and kept at room temperature to fully dissolve. After adding 10 mL of anhydrous ethanol, it was stirred vigorously, and after 0.5 h, ammonia water was added to adjust the pH to 9. After 0.5 h, 1 mol·L -1NaOH solution was added until pH=13, and the mixture was stirred vigorously. Then, 0.5 mL of methyltrioctylammonium chloride was added, and the mixture was stirred vigorously again until the reaction was complete, allowing it to react for 24 h. 20 mL of anhydrous ethanol and 600 mL of distilled water were added separately, and the gel solution was washed repeatedly by vacuum filtration. The washed gel filter cake was then placed in a 100℃ oven for drying. After 6 h, it was removed and placed in a muffle furnace for calcination at 600℃ for 5 h. After cooling, it was removed, milled, and sieved to obtain a 100-200 mesh adsorbent material sample. Figure 1 By measuring the concentration of molybdenum ions before and after adsorption, and calculating the adsorption capacity (see Formula 1), the adsorption capacity of the adsorption material sample is 354 mg / g.

[0030] (Formula 1)

[0031] in:

[0032] q: Adsorption capacity (unit: mg / g or g / g)

[0033] Co: Initial concentration of the adsorbate (unit: mg / L or g / L)

[0034] Ce: Concentration at adsorption equilibrium (unit: mg / L or g / L)

[0035] V: Solution volume (unit: L)

[0036] W: Mass of adsorbent (in g)

[0037] Example 2

[0038] Weigh 12.89 g of zirconium oxychloride octahydrate and dissolve it in 100 mL of water, maintaining room temperature to allow it to dissolve completely. After 0.5 h, add 1 mol·L⁻¹ solution dropwise. -1 The pH of the NaOH solution was adjusted to 13, and the mixture was stirred vigorously. 1 mL of methyltrioctylammonium chloride was added, and the mixture was stirred vigorously again until the reaction was complete, which was allowed to proceed for 24 h. Then, 20 mL of anhydrous ethanol and 600 mL of distilled water were added, and the gel solution was washed repeatedly by vacuum filtration. The washed gel filter cake was then placed in a 100℃ oven for drying. After 6 h, it was removed and placed in a muffle furnace for calcination at 500℃ for 2 h. After cooling, it was removed, milled, and sieved to obtain a 100-200 mesh adsorbent material sample. The adsorption capacity was calculated (see Formula 1) by measuring the concentration of molybdenum ions before and after adsorption, and the adsorption capacity was determined to be 297 mg / g.

[0039] Comparative Example 1

[0040] The only difference from Example 1 is that no ionic liquid was added after adjusting the pH, and the mixture was stirred vigorously.

[0041] Take 6.45 g of zirconium oxychloride octahydrate and dissolve it in 100 mL of water, keeping the room temperature, and make it fully dissolved. After adding 10 mL of anhydrous ethanol, stir it vigorously, and after 0.5 h, add ammonia water dropwise to adjust the pH to 9. After 0.5 h, add 1 mol / L NaOH solution to the reaction solution until the pH is 13, and stir it vigorously. After making it fully react for 24 h, wash the gel solution by repeatedly suction-filtering with 20 mL of anhydrous ethanol and 600 mL of distilled water. Then, place the washed gel filter cake in a 100℃ oven to dry. After 6 h, take it out and place it in a muffle furnace to calcine at 600℃ for 5 h. Then, take it out after it cools down, grind it, sieve it to obtain an adsorbent material sample of 100 mesh-200 mesh, and calculate the adsorption capacity of the adsorbent material sample by measuring the concentration of molybdenum ions before and after adsorption (see Formula 1), which is 57 mg / g. -1

[0042] Comparative Example 2

[0043] The difference from Example 2 is only that no ionic liquid is added after adjusting the pH, and it is stirred vigorously.

[0044] Take 12.89 g of zirconium oxychloride octahydrate and dissolve it in 100 mL of water, keeping the room temperature, and make it fully dissolved. After 0.5 h, add 1 mol / L NaOH solution dropwise to adjust the pH to 13, and stir it vigorously. After making it fully react for 24 h, wash the gel solution by repeatedly suction-filtering with 20 mL of anhydrous ethanol and 600 mL of distilled water. Then, place the washed gel filter cake in a 100℃ oven to dry. After 6 h, take it out and place it in a muffle furnace to calcine at 500℃ for 2 h. Then, take it out after it cools down, grind it, sieve it to obtain an adsorbent material sample of 100 mesh-200 mesh, and calculate the adsorption capacity of the adsorbent material sample by measuring the concentration of molybdenum ions before and after adsorption (see Formula 1), which is 104 mg / g. -1

[0045] Example 3

[0046] The difference from Example 1 is only that the ionic liquid is replaced by 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide.

[0047] Calculate the adsorption capacity of the adsorbent material sample by measuring the concentration of molybdenum ions before and after adsorption (see Formula 1), which is 301 mg / g.

[0048] Example 4

[0049] ​​The difference from Example 2 is that the ionic liquid is replaced by 1-butyl-1-methylpyrrolidine bis(trifluoromethylsulfonyl)imide.

[0050] The adsorption capacity of the sample of the adsorption material is 304 mg / g by measuring the concentration of molybdenum ions before and after adsorption and calculating the adsorption capacity (see Formula 1).

[0051] The above merely describes the preferred embodiments of the present application, and is not used to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a novel molybdenum-99 adsorbent material, characterized by, The preparation method comprises: Step 1: adding a lye to a well-dissolved zirconium-containing compound solution, adjusting the pH to 9-13, then adding an ionic liquid, stirring vigorously, and obtaining a gel solution after sufficient reaction; Step 2: washing, drying, calcining, grinding, and optionally sieving to obtain the adsorbent material; The ionic liquid is one or more of 1-butyl-1-methylpyrrolidine bis(trifluoromethylsulfonyl) imide and methyltrioctylammonium chloride; The zirconium-containing compound is zirconium oxychloride.

2. The method of claim 1, wherein the novel molybdenum-99 adsorbent material is prepared by the steps of: In step 1, the lye is one or more of ammonia and sodium hydroxide; optionally, in step 1, the lye is added dropwise.

3. The method of claim 1, wherein the novel molybdenum-99 adsorbent material is prepared by the steps of: In step 1, the ionic liquid is 0.1%-99.9% of the mass of the zirconium-containing compound.

4. The method of claim 3, wherein the novel molybdenum-99 adsorbent material is prepared by the steps of: In step 1, the ionic liquid is 0.3%-10% of the mass of the zirconium-containing compound.

5. The preparation method of the novel molybdenum-99 adsorbent material according to claim 1, characterized in that, In step 1, the well-dissolved zirconium-containing compound solution is obtained by mixing the zirconium-containing compound with water and optionally adding a dispersing agent, and stirring vigorously to fully mix and dissolve; optionally, the dispersing agent is one or more of anhydrous ethanol and polyethylene glycol; In step 2, the washing comprises repeatedly filtering and washing multiple times; optionally, the washing uses one or more of distilled water and anhydrous ethanol.

6. The preparation method of the novel molybdenum-99 adsorbent material according to claim 1, characterized in that, In step 1, the sufficient reaction time is 20-28h; In step 2, the drying temperature is 20℃-300℃, and the operation time is 5min-60h; In step 2, the calcination temperature is 500℃-1000℃, and the operation time is 5min-60h.

7. The preparation method of the novel molybdenum-99 adsorbent material according to claim 1, characterized in that, After sieving, the particle size of the adsorbent material is 100-200 mesh.

8. A novel molybdenum-99 adsorbent material characterized by, The novel molybdenum-99 adsorbent material is prepared by the preparation method of any one of claims 1-7.

9. The novel molybdenum-99 adsorbent material of claim 8, wherein, The adsorption capacity of the adsorbent material for molybdenum-99 is ≥290mg / g.

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