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CN-121975135-A - Solid adsorption material containing sulfonate anions and preparation method and application thereof

CN121975135ACN 121975135 ACN121975135 ACN 121975135ACN-121975135-A

Abstract

The invention provides a solid adsorption material containing sulfonate anions, a preparation method and application thereof, and relates to the technical field of thorium adsorption materials. The invention prepares a novel thorium solid adsorbent material by utilizing a sulfonate group-containing monomer, wherein the sulfonate group-containing monomer is N- (3-sulfopropyl) -2,4, 6-trimethylpyridinium. The thorium solid adsorbent material prepared by the invention has large specific surface area and excellent chemical stability, and simultaneously can reach adsorption saturation within 1 minute and show excellent adsorption capacity and recycling performance on thorium ions due to the strong electrostatic attraction of sulfonate anions and Th (IV) and the coordination synergistic effect of Lewis acid and alkali. Therefore, the catalyst can be used as an excellent solid adsorption material and applied to the selective adsorption separation of thorium.

Inventors

  • GAO YANAN
  • LIU HAO
  • SU XIAOFANG
  • QIAN JIAYING
  • HUANG CHENGJUN

Assignees

  • 海南大学

Dates

Publication Date
20260505
Application Date
20260130

Claims (10)

  1. 1. The solid adsorption material containing sulfonate anions is characterized by being prepared by reacting methyl monomer N- (3-sulfopropyl) -2,4, 6-trimethylpyridinium with sulfonate groups and aldehyde monomer, wherein the aldehyde monomer is selected from one or more of 1,3, 5-tri (4-formylphenyl) triazine or 2,4, 6-tri- (4-formyl-biphenyl-4-yl) -1,3, 5-triazine.
  2. 2. The sulfonate anion containing solid adsorbent material of claim 1, wherein the molar ratio of methyl monomer to aldehyde monomer is 1:1-2.
  3. 3. The method for preparing the solid adsorbent material containing sulfonate anions according to any one of claims 1 to 2, which is characterized by comprising the steps of adding an aldehyde monomer and a methyl monomer into an organic solvent, carrying out ultrasonic mixing uniformly, then adding a catalyst, freezing with liquid nitrogen, vacuumizing, sealing a tube by flame, heating for crystallization, carrying out Soxhlet extraction, washing and drying to obtain the target solid adsorbent material.
  4. 4. The method for preparing a sulfonate anion containing solid adsorption material according to claim 3, wherein the ratio of the total mass of the aldehyde monomer and the methyl monomer to the volume of the organic solvent is 60~90 mg:0.4~1.0 mL, and the ratio of the total molar amount of the aldehyde monomer and the methyl monomer to the molar amount of the catalyst is 3-6:1.
  5. 5. The method for producing a sulfonate anion containing solid adsorbent material according to claim 3, wherein the organic solvent is one or more of 1, 4-dioxane, mesitylene, n-butanol, and o-dichlorobenzene, and the catalyst is 4-dimethylaminopyridine.
  6. 6. The method for preparing the sulfonate anion containing solid adsorption material according to claim 3, wherein the ultrasonic treatment time is 8-15 min, the temperature of the heating crystallization is 120-160 ℃ and the time is 3-7 days.
  7. 7. Use of a solid adsorption material comprising sulfonate anions according to any one of claims 1 to 2 or a solid adsorption material comprising sulfonate anions obtained by the production process according to any one of claims 3 to 6 for the adsorption of thorium ions.
  8. 8. The use according to claim 7, characterized in that the solid adsorption material containing sulfonate anions is used as an adsorbent for the adsorption of thorium ions.
  9. 9. The use according to claim 8, characterized in that the pH of the solution of thorium ions is 4.0-5.0.
  10. 10. The use according to claim 8, characterized in that the saturated adsorption capacity of the solid adsorption material containing sulfonate anions to thorium ions is 1200-1290 mg g 1 The adsorption equilibrium time of the solid adsorption material containing sulfonate anions to thorium ions is 1-1.2 min.

Description

Solid adsorption material containing sulfonate anions and preparation method and application thereof Technical Field The invention relates to the technical field of thorium ion adsorption materials, in particular to a solid adsorption material containing sulfonate anions, and a preparation method and application thereof. Background With the urgent need to cope with global climate change and reduce carbon emissions, nuclear energy is becoming increasingly important as a clean, efficient and low-carbon form of energy. Compared with the traditional fossil fuel, the nuclear power generation process hardly generates greenhouse gases, has the remarkable advantages of controllable reaction, stable energy output, high energy repayment rate and the like, and is not strictly limited by geography and natural environment. However, with the large-scale development and utilization of nuclear power, the shortage problem of traditional uranium resources has prompted humans to accelerate the search for sustainable and reliable alternative energy technologies. Thorium is used as a nuclear fuel resource with great potential, the natural reserve of the thorium is 3-4 times of that of uranium, the natural reserve is higher, and the thorium is regarded as one of main candidate fuels of a future nuclear reactor (particularly a fourth generation advanced nuclear energy system such as a thorium-based molten salt reactor). However, a key challenge faced in the thorium fuel recycling process is that thorium cannot be completely burned out in a reactor, unreacted thorium, decay sub-bodies thereof, radionuclides such as coexisting rare earth elements and the like are discharged along with nuclear wastewater if improperly treated, and the serious threat is formed to soil, water sources and even the whole ecological system. Therefore, the method can capture and recycle thorium ions from complex nuclear wastewater efficiently and selectively, is not only important for environmental protection and nuclear safety, but also is a core link for realizing sustainable utilization of thorium resources and long-term healthy development of nuclear energy. At present, the main methods for separating and enriching radionuclides comprise a solvent extraction method, a precipitation method, an ion exchange method, a membrane separation method, an adsorption method and the like. Among them, the adsorption method has become one of the mainstream technologies for treating radioactive polluted water due to its simple operation, high practicality, good cost effectiveness, excellent removal performance, etc. The development of novel adsorbent materials with high adsorption capacity, excellent selectivity, good stability and easy reproducibility is the key direction of research in this field. Covalent organic framework materials (Covalent Organic Frameworks, COFs) are an emerging class of porous crystalline polymeric materials formed from organic building blocks joined by covalent bonds. COFs have the characteristics of predictable topology, extremely low density, ultra-large specific surface area and easy modification of different functional groups. The structural unit can be designed at the molecular level to regulate and optimize the frame structure and the surface property, thereby endowing the material with strong capability of efficiently removing radionuclides in a severe environment. However, in practical applications, porous materials that exhibit efficient adsorption to Th (IV) are still very rare. Disclosure of Invention In view of the above, the invention provides a solid adsorption material containing sulfonate anions, and a preparation method and application thereof. The technical scheme of the invention is realized as follows: A solid adsorption material containing sulfonate anions is prepared by reacting methyl monomer N- (3-sulfopropyl) -2,4, 6-trimethylpyridinium with sulfonate groups and aldehyde monomer, wherein the aldehyde monomer is selected from one or more of 1,3, 5-tris (4-formylphenyl) triazine or 2,4, 6-tris- (4-formylbiphenyl-4-yl) -1,3, 5-triazine. Further, the molar ratio of the methyl monomer to the aldehyde monomer is 1:1-2. The preparation process of solid adsorbing material containing sulfonate anion includes the steps of adding aldehyde monomer and methyl monomer into organic solvent, ultrasonic mixing, adding catalyst, liquid nitrogen freezing, vacuum pumping, flame sealing, heating to crystallize, soxhlet extraction to wash and drying. Further, the ratio of the total mass of the aldehyde monomer and the methyl monomer to the volume of the organic solvent is 60~90 mg:0.4~1.0 mL, and the ratio of the total molar quantity of the aldehyde monomer and the methyl monomer to the molar quantity of the catalyst is 3-6:1. Further, the organic solvent is one or more of 1, 4-dioxane, mesitylene, n-butanol and o-dichlorobenzene, and the catalyst is 4-dimethylaminopyridine. Further, the ultrasonic treatment is carried out for 8-15 min,