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CN-117019109-B - Large-scale preparation method of high-stability cesium removal adsorbent, and product and application thereof

CN117019109BCN 117019109 BCN117019109 BCN 117019109BCN-117019109-B

Abstract

The invention relates to a large-scale preparation method of a high-stability cesium removal adsorbent, a product and application thereof. The invention relates to a granular inorganic oxide or active carbon supported transition metal stabilized ferrocyanide adsorbent, which comprises a granular inorganic oxide carrier or granular active carbon carrier, a transition metal stabilized ferrocyanide layer coating the inorganic oxide or active carbon carrier, and a high polymer material layer coating the transition metal stabilized ferrocyanide layer. The adsorbent has high crush strength and low ion leaching rate. The invention also relates to a preparation method of the adsorbent and application thereof in removing radioactive isotope Cs ions and stable isotope Cs ions, and application in removing radioactive isotope Rb ions and stable isotope Rb ions.

Inventors

  • ZHAO XUAN
  • WEI JIYING
  • LI FUZHI

Assignees

  • 清华大学

Dates

Publication Date
20260505
Application Date
20180104

Claims (8)

  1. 1. A granular inorganic oxide or activated carbon supported transition metal stabilized ferrocyanide adsorbent comprises a granular inorganic oxide carrier or a granular activated carbon carrier, a transition metal stabilized ferrocyanide layer coating the inorganic oxide or activated carbon carrier, and a polymer material layer coating the transition metal stabilized ferrocyanide layer, Wherein the transition metal stabilized ferrocyanide layer coating the inorganic oxide or activated carbon support is formed by: impregnating a particulate inorganic oxide or a particulate activated carbon support in an aqueous solution of ferrocyanide at 80-100 ℃ for 2-48 hours to obtain a precursor A loaded with ferrocyanide, then mixing the precursor A with an aqueous solution of a transition metal salt and reacting in a sealed reaction vessel at a temperature of 100-150 ℃ for 2-24 hours, or The particulate inorganic oxide or the particulate activated carbon support is immersed in an aqueous solution of a transition metal salt at 80-100 ℃ for 2-48 hours to obtain a precursor B loaded with the transition metal salt, and then the precursor B is mixed with an aqueous solution of ferrocyanide and reacted in a sealed reaction kettle at a temperature of 100-150 ℃ for 2-24 hours.
  2. 2. The adsorbent of claim 1, wherein the polymeric material layer comprises sodium alginate, chitosan, polyethylene glycol having a number average molecular weight between 2000-6000, polyvinyl alcohol, sucrose, or any combination thereof.
  3. 3. The adsorbent of claim 1 or 2, having a crush strength of 2-100N/particle.
  4. 4. The adsorbent of claim 1 or 2, having such ion leaching characteristics that the turbidity of the resulting impregnation liquid is 10 mg/L or less after soaking the adsorbent at a liquid-to-solid ratio of 10 for 24 hours.
  5. 5. The adsorbent of claim 1 or 2, having such ion leaching characteristics that the electrical conductivity of the resulting liquid after soaking the adsorbent at a liquid-solid ratio of 10 for 24 hours is 15 μs/cm or less.
  6. 6. A process for preparing a particulate inorganic oxide or activated carbon supported transition metal stabilized ferrocyanide adsorbent comprising: 1) Providing a primary adsorbent; 2) Washing the primary adsorbent of step 1) with deionized water until the washing liquid has a conductivity of 25.0 mu s/cm or less and a turbidity of 30 mg/L or less; 3) Coating the washed primary adsorbent with a polymeric material in the presence of an acid or base to obtain a coated primary adsorbent, and 4) Washing the coated primary adsorbent of step 3) with deionized water until the washing liquid has a conductivity of 20.0 mu s/cm or less and a turbidity of 20 mg/L or less, Thereby obtaining the ferrocyanide adsorbent stabilized by the granular inorganic oxide or the activated carbon supported transition metal, Wherein the step of providing the primary adsorbent comprises immersing the particulate inorganic oxide or the particulate activated carbon support in an aqueous solution of ferrocyanide at 80-100 o C for 2-48 hours to obtain a precursor A loaded with ferrocyanide, then mixing the precursor A with an aqueous solution of a transition metal salt and reacting in a sealed reaction vessel at a temperature of 100-150C for 2-24 hours, or Wherein the step of providing the primary adsorbent comprises immersing the particulate inorganic oxide or the particulate activated carbon support in an aqueous solution of a transition metal salt of 80 to 100 o C for 2 to 48 hours to obtain a precursor B loaded with the transition metal salt, and then mixing the precursor B with an aqueous solution of ferrocyanide and reacting in a sealed reaction vessel at a temperature of 100 to 150C for 2 to 24 hours.
  7. 7. A particulate inorganic oxide or activated carbon supported transition metal stabilized ferrocyanide adsorbent prepared by the process of claim 6.
  8. 8. Use of a ferrocyanide adsorbent stabilized by a particulate inorganic oxide or a particulate activated carbon as claimed in any one of claims 1 to 5 or by a particulate activated carbon for adsorbing radioisotope Cs ions or adsorbing stable isotope Cs ions and/or for adsorbing radioisotope Rb ions or adsorbing stable isotope Rb ions.

Description

Large-scale preparation method of high-stability cesium removal adsorbent, and product and application thereof The application relates to a large-scale preparation method of a high-stability cesium-removing adsorbent, and a product and application thereof, which are classified application of patent application of the application, wherein the application date is 2018, 01 and 04, and the application number is 201810008565.2. Technical Field The invention relates to the field of inorganic materials, in particular to a large-scale preparation method of a cesium removal adsorbent with high stability, a product and application thereof, and the adsorbent has good adsorption performance on rubidium. Background According to the medium-long term development planning target of the Chinese nuclear power, the installed capacity of the running nuclear power reaches 5800 kilowatts by 2020, about 3000 kilowatts is built, and the national target of building the nuclear power is comprehensively realized by 2030. Facing new challenges in the development of new situations in the nuclear power industry, china is in urgent need of great development in the aspects of radioactive waste treatment, nuclear emergency technology, radioactive effluent emission standards and the like. The efficient and timely treatment of radioactive liquid is one of the important problems to be solved in the urgent need of establishing a nuclear safety deep defense system, so that development of new technology, new equipment and research and development and storage of new materials for emergency treatment of waste liquid are urgently needed, and multi-level technical guarantee for waste liquid treatment and disposal is established in a nuclear power station. The first level is the actual elimination of radionuclides during normal operation of the nuclear power plant. The technology is mainly aimed at removing radioactive wastes in the normal operation process of the nuclear power station, and realizes the waste minimization while guaranteeing the stability and effectiveness of the treatment process. The second level is that when the problems such as fuel damage occur in the power station, the emergency treatment of the waste liquid in the field is carried out in time under the conditions of wide nuclide range and various forms in the waste liquid. The technology can remove pollution in time, quickly and efficiently, and prevent radioactive substances from leaking out. The third level is the last defense line of the deep defense system, namely, under the extreme condition of over-design reference accidents, the off-site nuclear emergency treatment is rapidly started, and the influence of nuclear accidents on the environment is limited to the greatest extent. Compared with ion exchange resin, the inorganic ion adsorbent has high selectivity to main trace nuclides Cs, sr, co, ag, I and the like, can efficiently remove target nuclide ions from high-salt radioactive wastewater, can rapidly and greatly reduce the radioactivity of the waste liquid, and is little influenced by coexisting non-radioactive ions, so that the inorganic ion adsorbent has long service life and generates a small amount of solid waste. Furthermore, the large amount of radioactive elements is enriched in a small volume of solid inorganic ion exchanger, making radiation protection relatively easy. Compared with waste resin produced by adsorption, the radioactive waste produced by the inorganic adsorption technology has good thermal stability and chemical stability, strong irradiation resistance, difficult radiation decomposition or biological decomposition, convenient post treatment and disposal, and long-term safety in the long-term storage process of an underground disposal field. Further, the waste liquid deep purification device based on the inorganic adsorption technology is simple in structure, has the technical characteristics of effectiveness, strong selectivity, miniaturization, modularization and strong mobility, has low requirements on site service conditions, and is very suitable for special requirements that the components of radioactive waste liquid of a nuclear power plant are complex and the site arrangement space is limited. Based on the application characteristics of high efficiency, high speed and high selectivity of the inorganic adsorbent, the inorganic adsorption technology plays a key role in the treatment of the accident waste liquid of the nuclear power station. In the most typical case of treatment of an accident waste liquid, from the establishment of an initial radioactive waste water treatment system to the gradual perfection in the subsequent operation process, the process route of coupling of inorganic adsorption and membrane technology is always kept, the inorganic adsorption technology is adopted to selectively remove the main nuclides Cs-134 and Cs-137, the radioactivity level of the waste water is greatly reduced, the radiation protection requirement of