KR101678860B1 - Hydrogel Compositions Comprising a Magnetic Absorbent for Removing a Radioactive Element and Uses Thereof - Google Patents
Hydrogel Compositions Comprising a Magnetic Absorbent for Removing a Radioactive Element and Uses Thereof Download PDFInfo
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- KR101678860B1 KR101678860B1 KR1020150066818A KR20150066818A KR101678860B1 KR 101678860 B1 KR101678860 B1 KR 101678860B1 KR 1020150066818 A KR1020150066818 A KR 1020150066818A KR 20150066818 A KR20150066818 A KR 20150066818A KR 101678860 B1 KR101678860 B1 KR 101678860B1
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Abstract
Description
The present invention relates to a hydrogel composition comprising a magnetic adsorbent for removing radionuclides, a method for removing radionuclides using the same, and a method for reducing the amount of radionuclide-containing wastes using the same.
After the Fukushima nuclear accident, a large amount of radionuclides leaked into the environment. The radionuclides released to the outside are diffused and adsorbed by various materials such as soil, roads, and buildings due to wind and rain, and many agricultural and urban areas are contaminated with radionuclides. Among these radionuclides, radioactive cesium is known as the most dangerous radionuclides due to its long half-life (about 30 years) and high energy of gamma rays. Various methods have been applied to remove radioactive cesium from various solid surfaces contaminated with radioactive cesium. Among the above methods, the surface decontamination method using high pressure water was applied a lot, but the removal efficiency was low as 35-65%, and the water used for washing was contaminated with the radionuclide after use, . In addition, when a chemical strippable coating is used, it shows excellent radionuclide removal efficiency of 70-80%, but it has two disadvantages. First, the solvent and chelator, which are constituents of the coating material itself, use substances harmful to the human body. Moreover, since the coating material used for removing the radionuclides from the contaminated surface is itself a radioactive waste, Radioactive waste is generated.
Therefore, it is urgently required in the art to develop a new surface decontamination agent that can reduce the amount of radioactive waste generated after use, while being excellent in the removal rate of radionuclides as a surface decontamination agent and being environmentally friendly.
Throughout this specification, the patent literature is referred to and its citations are indicated. The disclosures of the cited patent documents are hereby incorporated by reference herein in their entirety to better illustrate the state of the art to which the invention pertains and the teachings of the present invention.
The present inventors have sought to develop environmentally friendly radioactive waste decontamination agents and methods. As a result, we have prepared a hydrogel solution comprising magnetic nanoparticles or clusters thereof surrounded by a hydrophilic polymer capable of binding a radionuclide binding moiety, applying the solution to a contaminating surface It has been confirmed by filming that the radionuclide can be removed from the contaminated surface by collecting the film and using it to complete the present invention by developing a method capable of removing the radionuclide from the radionuclide- .
It is therefore an object of the present invention to provide a composition for removing radionuclides.
It is another object of the present invention to provide a method for removing radionuclides in a contaminated surface.
It is yet another object of the present invention to provide a method of reducing the amount of radionuclide-containing waste.
Other objects and advantages of the present invention will become more apparent from the following detailed description of the invention, claims and drawings.
According to one aspect of the present invention, there is provided a hydrogel-free hydrogel composition comprising magnetic nanoparticles or clusters thereof surrounded by a hydrophilic polymer capable of binding a radionuclide binding moiety.
The present inventors have sought to develop environmentally friendly radioactive waste decontamination agents and methods. As a result, the present inventors have produced a hydrogel solution containing magnetic nanoparticles or clusters thereof surrounded by a hydrophilic polymer capable of bonding with a radionuclide binding moiety, applying the solution to a contaminated surface and filming the film to collect Thereby making it possible to remove the radionuclide from the contaminated surface, thereby using it to develop a method capable of removing the radionuclide from the radionuclide-containing solid matter in a short time.
Currently, the use of nuclear power is steadily increasing, and interest in its stability is increasing rapidly. Accordingly, the outflow of radioactive material causes an environmental disaster (for example, soil contamination, seawater pollution, etc.) and has a very long half-life, which poses a serious threat to the survival of mankind. Therefore, there is a urgent need for a technical or environmental method for proper treatment of radioactive waste.
The hydrogel compositions of the present invention can very efficiently and easily remove radionuclides from solids (i.e., contaminated surfaces). The hydrogel compositions of the present invention include magnetic nanoparticles or clusters thereof (i.e., magnetic adsorbents) bonded / grafted with radionuclide binding moieties.
The present invention can use magnetic nanoparticles usable in the art, specifically, super magnetic magnetic nanoparticles. For example, it may contain at least one of iron acetylacetonate, FeCl 3 .6H 2 O and FeCl 2 .4H 2 O as a precursor of magnetic nanoparticles, and may contain at least one of benzyl ether, phenyl ether, Benzyl alcohol, ethylene glycol, diethylene glycol, and triethylene glycol, and may contain at least one of hexadecanediol, sodium acetate, sodium acrylate, and urea ). ≪ / RTI > Also, the surface dispersing agent of the synthesized nanoparticles may include at least one of oleic acid, oleylamine, diethyleneamine, hexamethylene diamine, and polyethyleneimine.
The surface of the mixture is thermally decomposed for 1 hour to 12 hours under the reaction conditions of 200 ° C to 300 ° C or put into an autoclave and reacted at 100 ° C to 300 ° C for 1 hour to 24 hours (hydrothermal synthesis) (For example, Fe 3 O 4 or γ-Fe 2 O 3 ) super magnetic nanoparticles can be synthesized. The prepared super magnetic nanoparticles can be synthesized in a cluster form. For example, the superparamagnetic nanoparticles or clusters thereof that may be used in the present invention may be oleic acid coated Fe 3 O 4 , but are not limited thereto.
The average particle diameter of each of the superpowder magnetic nanoparticles can be dispersed in the radioactive contaminated liquid, and is not particularly limited. However, considering the dispersibility in an aqueous solution, a size of 1 to 50 nm is preferred. However, from the viewpoint of the self-adsorbing ability, the average particle diameter of the nanoparticles can be taken into account, even if the adsorption surface area is enlarged to 5 nm or more. From the viewpoint of enhancing the integration and magnetic separation efficiency by magnetic force, the super-magnetic nanoparticles that can be used in the composition of the present invention can form clusters, and the cluster formation can be performed by magnetic attraction It is advantageous in that it is easy to enhance the integration and the magnetic separation efficiency by increasing the speed. The size of such clusters may be in the range of 10 nm to 500 nm, preferably in the range of 25 nm to 350 nm, more preferably in the range of 50 nm to 200 nm, more preferably in the range of 50 nm to 200 nm, in view of the balance of dispersion, specific surface area, nm (see Figures 3 and 5).
Thereafter, the prepared super-magnetic nanoparticles or clusters thereof were coated with a hydrophilic polymer and then bonded with a radionuclide binding moiety (see FIG. 2). The hydrophilic polymer may be any polymer capable of binding to the radionuclide binding moiety, and specifically, poly (N-vinylpyrrolidone) (PVP), polyvinylpyrrolidone / polyvinyl alcohol, At least one member selected from the group consisting of polyvinyl acetate / polyvinyl alcohol (PVAc / PVA), alginate-acrylate, alginate-g- (polyethylene oxide-polypropylene oxide-polyethylene oxide), carboxymethyl chitin, , But is not limited thereto. In some embodiments of the present invention, the hydrophilic polymer used in the present invention is poly (N-vinylpyrrolidone) (PVP).
The radionuclide binding moiety may be varied in various ways depending on the radioactive element of interest. As used herein, the term " radioactive element-binding moiety "means a moiety capable of binding to a radionuclide by binding to a superparamagnetic nanoparticle or cluster thereof coated with a hydrophilic polymer, For example, transition metal-ferrocyanide. The transition metal includes Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Ru, Rh, Ag, Cd, Ir, W, Au and Hg. More specifically, have. The target radionuclide may be cesium-134, cesium-137, strontium-90, uranium-238, barium-133, cadmium-109, cobalt- Cobalt-60, Europium-152, Manganese-54, Sodium-22, Zinc-22, Technetium-99m, Thallium- But are not limited to, Carbon-14, Hydrogen-3, and Polonium-210.
In some embodiments of the present invention, the radionuclide binding moiety is an MFe (CN) 6 complex (M is Cu, Fe, Co, Ni or Zn) and can bind cesium-137.
Since the hydrogel composition of the present invention includes magnetic nanoparticle clusters containing a radionuclide binding moiety having a high binding force to a radionuclide, it is possible to adsorb radionuclides very easily on a solid surface, Radionuclides can be easily removed by obtaining nanoparticles or hydrogel films.
Hydrogels can be formed by chemical or physical cross-linking of various natural or homologous polymers, copolymers or oligomers in a three-dimensional, very high hydrophilic polymeric network comprising a large amount of water. Thus, the hydrogel may have various porosities, for example, micropores (e.g., diameters of about 1 nm or less), mesopores (e.g., diameters of about 1 nm to about 100 nm), or macroporous , Diameters of greater than about 100 nm). Hydrogels may also exhibit environmentally-sensitive properties such as being gelled at room temperature (15-30 DEG C), or may be environmentally unaffected, although they are liquid at low temperatures.
In some embodiments of the present invention, the water that may be used to prepare the hydrogel of the present invention may include deionized water, distilled water, and tap water.
The hydrogel of the present invention has a network structure in which polyacrylamides cross each other to form a network structure, and the polyacrylamide crosslinked by van der Waals force and alginate are physically bonded to each other to form a semi-interpenetrating polymer network, semi-IPN) structure, but the present invention is not limited thereto. That is, any hydrogel that can be used in the present invention can be used as long as it can contain magnetic nanoparticle clusters.
In some embodiments of the present invention, the hydrogel of the present invention employs a hydrophilic polymer. The hydrophilic polymer may be any hydrophilic polymer that can be used in the production of hydrogels known in the art, and specifically may include a water-soluble polymer and a natural polymer.
In some embodiments of the present invention, the hydrophilic polymer that can be used in the present invention comprises at least one water-soluble polymer, and more specifically, polyacrylamide, polyvinyl alcohol (PVA), poly (N-vinylpyrrolidone) (PEO-PPO), polyvinylpyrrolidone / polyvinyl alcohol, alginate-acrylate, polyethylene oxide-polypropylene oxide copolymer (PEO-PPO), polyvinyl pyrrolidone / polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polylysine, carboxymethylchitin, fibrin, dextran, polyethylene oxide Pluronic series), polyvinyl acetate / polyvinyl alcohol (PVAc / PVA), poly (N-isopropylacrylamide-co-ethyl methacrylate) (P (NIPAAm-co-EMA), alginate- (PEO-PPO-PEO), and mixtures thereof, and more specifically, polyalkylene oxide-polyethylene oxide (PEO-PPO-PEO) At least one water-soluble polymer selected from the group consisting of polyvinyl alcohol, polyvinyl alcohol, polyvinyl alcohol, poly (N-vinylpyrrolidone), carboxymethylchitin, fibrin, dextran, polyethylene oxide and polyvinylpyrrolidone / polyvinyl alcohol , And even more specifically at least one water-soluble polymer selected from the group consisting of polyacrylamides, polyvinyl alcohols, poly (N-vinylpyrrolidone) and polyvinylpyrrolidone / polyvinyl alcohol, Specifically, it includes polyacrylamide.
Natural polymers that can be used in the present invention include alginate, hyaluronic acid, pectin, xanthan gum, gelatin, locust bean gum, agar, glucomannan, carrageenan, gellan gum, chitosan, collagen, But is not limited to, one or more natural polymers selected from the group consisting of gum and cellulose.
In addition to the polyacrylamide / alginate mixtures, the hydrogels of the present invention may also contain other additives that may be used in the manufacture of hydrogels, such as cross-binders, initiators, accelerators, rheology modifiers, Plasticizers, and the like).
In some embodiments of the present invention, the hydrogel of the present invention has a network structure in which polyacrylamides cross each other to form a network structure, and polyacrylamide and alginate crosslinked to each other by van der Waals force are physically bonded to each other Forming an interpenetrating polymer network structure. Typically, the hydrogel is prepared by mixing the acrylamide / alginate mixture with water and then synthesizing the crosslinked polyacrylamide.
In some embodiments of the present invention, the reactive composition for making the crosslinked polyacrylamide / alginate hydrogel of the present invention comprises 1 wt% (wt%) to 15 wt% acrylamide, 1 wt% to 8 wt% Alginate and from 78% to 97% by weight of water, more specifically from 3% by weight to 12% by weight of acrylamide, from 2% by weight to 6% by weight of alginate and from 82% % Water, and most specifically from 5 wt% to 10 wt% acrylamide, from 3 wt% to 5 wt% alginate, and from 85 wt% to 91 wt% water .
The cross-linked polyacrylamides are obtained by combining acrylamide and methylene bis-acrylamide in a molar ratio of 150: 1 to 3,000: 1. The methylene bis-acrylamide functions to provide cross-linking between the acrylamide polymers, and the molar ratio can be determined in consideration of the various cross-linking densities of the hydrogel. The cross-linking may also be facilitated by the addition of an initiator such as ammonium persulfate (AMPS) and N, N, N, N'-tetramethylene ethylenediamine (TEMED).
In some embodiments of the present invention, the molar ratio of acrylamide to methylenebis-acrylamide ranges from about 150: 1 to 20,000: 1, more specifically from about 500: 1 to 9,000: 1, 1 to 3,000: 1, and even more specifically from 1,500: 1 to 2,000: 1.
Finally, the hydrogel composition of the present invention was prepared by appropriately mixing the prepared magnetic nanoparticles (or clusters thereof) with a hydrogel. In some embodiments of the invention, the composition of the present invention contains magnetic nanoparticles (or clusters thereof) in a ratio of 1: 1,000 to 10: 100 to hydrogel, more specifically from 1: 100 to 5: 100 In the ratio of magnetic nanoparticles (or clusters thereof) to hydrogel. The radionuclides that can be effectively adsorbed by the hydrogel compositions of the present invention can be determined according to the radionuclide binding moieties used, such as cesium-134, cesium-137, strontium-90, uranium-238, , Cadmium-109, cobalt-57, cobalt-60, europium-152, manganese-54, sodium-22, zinc-22, technetium-99m, thallium-204, carbon-14, tritium- -241 and more specifically cesium-137, strontium-90, uranium-238, barium-133, cadmium-109, cobalt-57, cobalt-60, europium-152, technetium- Carbon-14, tritium-3 and polonium-210, and more specifically cesium-137, strontium-90, uranium-238 and carbon-14, and most specifically cesium-137. Moreover, the method of using the hydrogel of the present invention can be used to more rapidly and effectively radionuclide on a radionuclide-contaminated surface, as it exhibits an effective radioactive cesium removal rate over 3 hours after initiating adsorption on a solid (e.g., contaminated surface) (See Figs. 8 to 10).
In some embodiments of the present invention, the hydrogel compositions of the present invention exhibit a removal rate of at least 70%, more specifically at least 80%, and more particularly at least 90%, for radionuclides : Table 1).
According to yet another aspect of the present invention, the present invention provides a method of making a radionuclide comprising: (a) applying the hydrogel composition described above to a radionuclide contaminated surface; (b) forming a magnetic adsorbent / hydrogel film at the applied site; And (c) removing the formed film. ≪ Desc /
According to still another aspect of the present invention, there is provided a method for producing a magnetic nanoparticle, comprising: (a) dissolving a magnetic nanoparticle / hydrogel film obtained according to the above-described method; And (b) separating only the magnetic adsorbent using magnetism in the dissolution solution.
Since the methods of the present invention comprise the hydrogel composition described above as an active ingredient, the description common to both is omitted in order to avoid the excessive complexity of the present specification.
As noted above, with reference to the fact that the hydrogel composition strongly bonds with the radionuclide, the methods of the present invention can be applied to a radionuclide-containing contaminating surface to effectively remove the radionuclide.
When the hydrogel composition of the present invention is used on a solid surface contaminated with a radionuclide, the adsorption reaction is carried out for a suitable time or more (for example, 3 hours or more) after applying the hydrogel composition to the contaminated surface. Thereafter, a radial nuclide can be easily and easily removed from the contaminated surface by adding a divalent metal ion (specifically, calcium ion) to form a film of the applied hydrogel composition and collecting the formed film (Note: 8).
At this time, an ionic solution containing an ammonium salt (e.g., ammonium chloride, ammonium nitrate) or trisodium nitrilotriacetate or sodium citrate is applied to the contaminated surface in advance before the hydrogel composition is applied to the solid surface contaminated with the radionuclide Upon application, desorption of radionuclides from the contaminated surface is promoted, thereby improving the efficiency of removing radionuclides using the hydrogel.
Furthermore, the method of the present invention can dissolve the magnetic nanoparticle / hydrogel film thus formed to obtain and selectively remove magnetic nanoparticles or clusters thereof bound to radionuclides, thereby dramatically reducing the amount of radionuclide-containing wastes . In the present invention, the dissolution of the magnetic nanoparticle / hydrogel film can be easily performed using a metal ion chelating agent.
Metal chelating agents that can be used in the present invention are chelating agents for divalent metal ions. When calcium ions are used for film formation, polyamino carboxylic acids can be used. For example, ethylenediaminetetraacetic acid (EDTA) acid, NTR (nitrilotriacetic acid), DTPA (diethylene triamine pentaacetic acid), HEDTA (N-hydroxyethyl-ethylenediamine-triacetic acid) and mixtures thereof.
The composition of the present invention and methods of using the same can efficiently cope with restoration of roads and building surfaces in a residential area that is heavily polluted with heavy-duty radioactive radionuclides such as Fukushima nuclear accident. In addition, among the radioactive wastes generated after use, only the magnetic adsorbent capable of collecting the target radionuclide can be selected and separated to reduce the generation of radioactive waste, thereby remarkably reducing the secondary environmental pollution caused by the waste, and saving the waste treatment cost can do. The functional materials can be used for surface decontamination of nuclear power plants and other nuclear power plants with different types of internal adsorbents.
The features and advantages of the present invention are summarized as follows:
(a) The present invention relates to a hydrogel composition comprising magnetic nanoparticles for removing radionuclides or clusters thereof, a method for removing radionuclides from a solid surface using the same, and a method for reducing the amount of radionuclide-containing wastes using the same .
(b) The hydrogel composition of the present invention contains the magnetic nanoparticles or their clusters to hydrogel solution at a mixing ratio of 1: 1,000 to 10: 100.
(c) The hydrogel composition of the present invention not only can very easily adsorb radionuclides on the solid surface, but also can easily remove radionuclides as the magnetic nanoparticles or hydrogel films are obtained in the solution.
(c) Furthermore, the amount of radionuclide-contaminated waste can be remarkably reduced by selectively obtaining only the magnetic nanoparticles or clusters thereof using a magnetic field after dissolving the hydrogel film.
(d) Therefore, the hydrogel composition of the present invention and the method of removing radionuclides using it can solve various pollutions (for example, environmental pollution such as water pollution) caused by radionuclides very efficiently and economically.
1 is a process for preparing an adsorbent / hydrogel solution for removing radionuclides in contaminated surfaces.
FIG. 2 is a method for producing a magnetic nano-adsorbent to which Cu-ferrocyanide is introduced by PVP.
3 is a transmission electron microscope (TEM) image of magnetic nanoparticles coated with oleic acid.
FIG. 4 shows X-ray diffraction (XRD) analysis results of magnetic nanoparticles coated with oleic acid.
5 is a TEM image of PVP-coated magnetic nanoparticles.
FIG. 6 shows Fourier transform infrared spectroscopy (FT-IR) spectral results of the magnetic particles coated with PVP and the magnetic adsorbent having Cu-ferrocyanide introduced therein.
Figure 7 shows FT-IR spectral results of polyacrylamide, alginate, polyacrylamide / alginate hydrogel.
FIG. 8 is a digital image after application of the hydrogel / adsorbent solution in order to remove radioactive cesium present on the surface of the cement coated with the phate and after the application.
9 is a magnetic recovery image of an adsorbent using cross-linking collapse and external magnetic field of a hydrogel / adsorbent composite material film.
FIG. 10 is an image in which the hydrogel / adsorbent composite material film is not collapsed and the hydrogel / adsorbent moves toward the outer magnet at the same time without recovering the magnetic material from the adsorbent using an external magnetic field.
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .
Example
Example 1: magnetic adsorbent / Hydrogel Preparation and Results of Solutions
The preparation of a magnetic adsorbent / hydrogel solution for the removal of radioactive cesium from contaminated surfaces is divided into three stages. The first step is to prepare a magnetic adsorbent for capturing radioactive cesium, the second step is to prepare a hydrogel polymer solution, and finally, the step of sealing the magnetic adsorbent for removing radioactive cesium into the polymer hydrogel solution. Figure 1 shows the entire synthesis process.
- Step 1: Manufacturing process and result of magnetic adsorbent
The magnetic adsorbent is synthesized in the following three steps. The magnetic adsorbent may be a magnetic adsorbent prepared in the present invention, conventional commercialized magnetic particles, and the like, but is not limited thereto. The method of coating the surface of the magnetic particles with metal-ferricyanide can also be carried out according to the method described below, and the magnetic adsorbent of the existing prior art (Registration No. 10-1429560 and Application No. 10-2015-0048602) May be used.
First, hydrophobic magnetic nanoparticles having a superparamagnetism property were prepared in a first step, and polyvinylpyrrolidone (PVP) was introduced using an emulsion method as an intermediate material for grafting Cu-ferrocyanide in two steps Finally, Cu-ferrocyanide was introduced on the surface of PVP-coated magnetic nanoparticles to prepare a new magnetic nano-adsorbent having increased degree of Cu-ferrocyanide grafting per unit particle. 2 is a schematic view of a magnetic adsorbent manufacturing process.
Specific experimental methods for producing the magnetic nanosorbent are as follows. First, iron acetylacetonate, 1,2-hexadecanediol, oleic acid, oleylamine and benzyl ether (Sigma-Aldrich, USA) were added in one step, 2 hours and 300 < 0 > C for 1 hour. After completion of the reaction, the temperature of the reactor was lowered to room temperature (15-30 ° C), ethanol was added to the resultant to obtain a precipitate, and the above procedure was repeated 2-3 times. After that, the precipitate was dried under pressure at 60 ° C. to obtain magnetic particles (OA-MNPs) coated with oleic acid and oleylamide, and chloroform was added thereto to prepare a stock solution of 75 mg / mL of magnetic nanoparticles . FIG. 3 is a TEM image of the produced magnetic particles, and FIG. 4 is an XRD result showing that the crystal structure of the magnetic particles is Fe 3 O 4 .
In order to apply Cu-ferrocyanide to the surface of the hydrophobic magnetic nanoparticles prepared in the second step, the mediator must first be grafted onto the surface of the magnetic nanoparticles. PVP polymers have a ketone (C = O) group and are known to have strong chelating bonds with transition metals such as Cu, Co, and Ni. First, 0.5 mL of a magnetic nanoparticle stock solution was added to an aqueous solution (20 mg / mL) of dodecyltrimethylammonium bromide (DTAB) (Sigma-Aldrich, USA) and stirred vigorously for 30 minutes or longer to prepare an emulsion. The temperature of the reaction was then raised to 40 ° C and the chloroform solvent in the emulsion was removed via nitrogen feed. The PVP polymer was dissolved in ethylene glycol at a concentration of 0.11 g / mL. The aqueous solution of the magnetic particles was added to the PVP solution, and the reaction was maintained at 80 ° C. for 2 hours or more in a nitrogen atmosphere. After completion of the reaction, the temperature of the reactor was lowered to room temperature, and the resultant was centrifuged to obtain a precipitate. The obtained precipitate was re-dispersed by adding ethanol again, and centrifugation was repeated three or more times to obtain PVP-coated magnetic particles (PVP-MNPs). 5 is a TEM image of PVP-coated magnetic particles.
As a final step, a magnetic nano-adsorbent grafted with a Cu-ferrocyanide complex was prepared by sequentially adding Cu ion and ferrocyanide to PVP-coated magnetic nanoparticles. The PVP-coated magnetic nanoparticles were again redispersed in water, and then CuCl 2 (Sigma-Aldrich, USA) was added to uniformly agitate for a sufficient time of 6 hours so that Cu ions could be grafted sufficiently to the surface of the particles . After 6 hours, a solid form precipitate was obtained using a magnetic field. Then, 0.25 mol / L Na 4 Fe (CN) 6 solution (Sigma-Aldrich, USA) was added and stirred for 1 hour or more. The obtained precipitate was stored under pressure drying at 60 ° C. 6 shows FT-IR results of Cu-ferrocyanide-grafted magnetic adsorbents. From the above results, it was confirmed that Cu-ferrocyanide was successfully introduced.
-
(Sigma-Aldrich, USA), 0.004251 wt% N, N'-methylenebisacrylamide (Sigma-Aldrich, , USA), 0.006967 wt% Ammonium persulfate (Sigma-Aldrich, USA) and 0.015295 wt% tetramethylethylenediamine (Sigma-Aldrich, USA) were added. In the reaction for preparing the polyacrylamide, acrylamide, N, N'-methylenebisacrylamide, ammonium persulfate and tetramethylethylenediamine may be used as monomers, cross-linkers, initiators and It was used as an accelerator. The reaction mixture was stirred for 30 minutes or longer to make a homogeneous mixture. Thereafter, the mixture was maintained at the reaction initiation temperature of 50 DEG C for 4 hours to induce the polymerization reaction of the acrylamide, and the crosslinked polyacrylamide crosslinked with N, N'-methylenebisacrylamide as a crosslinking agent To prepare a hydrogel solution in which sodium alginate and polyacrylamide were mixed with each other. The temperature of the product was then lowered to room temperature and then the unreacted material was removed. It was confirmed by FT-IR analysis that it was well synthesized into a solution composed of alginate and polyacrylamide (FIG. 7). Finally, a hydrogel / adsorbent solution was prepared by adding a magnetic nano-adsorbent having a weight of 1/100 or 5/100 of the initial total weight of alginate and acrylamide to the hydrogel solution.
Example 2: magnetic adsorbent / Hydrogel Process of removing radioactive nuclides from contaminated surfaces using solution
The process of removing radioactive cesium from contaminated surfaces using the prepared adsorbent / hydrogel solution is divided into three stages. First, the step of applying the adsorbent / hydrogel solution prepared on the contaminated surface, the step of forming the applied adsorbent / hydrogel film by adding Ca 2 + ion to the contaminated surface secondly, and the step of capturing the radioactive cesium And removing a contaminated surface remover film (FIG. 8).
More specifically, the cement surface was painted with a radial cesium solution on a cement surface (diameter of 4 cm in diameter), and then dried naturally for 24 hours or more to contaminate the surface of the cement with radioactive cesium. A 3 g hydrogel / adsorbent composite material was then applied to the contaminated surface and left for more than 3 hours to allow the radioactive cesium to adsorb to the composite material. Then, 1.2 mL of a 0.2 mol / L Ca 2 + solution was added to the viscous hydrogel / adsorbent composite material to form a hydrogel / adsorbent film. The formed film could be easily removed from the cement. Table 1 shows the results of removal of radioactive cesium from the surface of the cement coated with paint contaminated with radioactive cesium.
(absorbent:
Alginate
/
Acrylamide
)
DF
= A
0
/
A
f
R = [(A
0
-
A
f
) / A
0
]
Decontamination Coefficient of Hydrogel / Adsorbent Composites for Removal of Radioactive Cesium on Paint - Coated Cement Surface.
Example 4: magnetic adsorbent / Hydrogel Magnetic Separation Process of Magnetic Adsorbent Collecting Radionuclides
The method of reducing the volume of radioactive waste by magnetic separation of only the magnetic adsorbent collecting radioactive cesium in the adsorbent / hydrogel film after use can be roughly divided into two steps. First, the adsorbent / hydrogel film was added to the EDTA (Sigma-Aldrich, USA) solution to dissolve the hydrogel film. Secondly, only the magnetic adsorbent was magnetically separated from the hydrogel solution dissolved using the external magnet (FIG. 9).
The adsorbent / hydrogel film was placed in a 0.2 mol / L EDTA aqueous solution, and EDTA induced chelating bonding of Ca-alginate with Ca for a sufficient time. The magnetic adsorbent could then be recovered by placing a magnet on one side of the beaker containing the aqueous solution. FIG. 9 is a digital image showing the results of the experiment described above. The cross-linking of the Ca-alginate in the hydrogel / adsorbent film is broken by the EDTA aqueous solution of 0.2 mol / L and the magnetic nanosorbent located in the hydrogel is released, It was confirmed that the aqueous solution turned to a dark black color, which is the color of the magnetic adsorbent. Thereafter, the magnetic nano - adsorbents were separated by one side of the magnet and the EDTA aqueous solution was clarified again by the external magnet. That is, the polyacrylamide and alginate present in the aqueous solution of EDTA can be treated as general wastes, and only the magnetic adsorbent separated separately by the magnet can be treated with radioactive waste. As a result, the radioactive waste of hydrogel / adsorbent composite material It is possible to drastically reduce the amount (Fig. 9). On the other hand, as shown in Fig. 10, the cross-linking of the Ca-alginate in the hydrogel was not collapsed in the ordinary aqueous solution without EDTA, so that the magnetic recovery of the adsorbent was impossible.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. It will be obvious. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.
Claims (14)
(b) coating the hydrophobic magnetic nanoparticles with poly (N-vinylpyrrolidone) (PVP) or polyvinylpyrrolidone / polyvinyl alcohol by an emulsion method to obtain a cluster of coated magnetic nanoparticles ;
(c) grafting the coated cluster with an MFe (CN) 6 complex to obtain a magnetic nanosorbent; And
(d) mixing the magnetic nanosorbent and the hydrogel to obtain a composition;
≪ / RTI > wherein the method comprises the steps of:
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107374662A (en) * | 2017-07-31 | 2017-11-24 | 沈阳东软医疗系统有限公司 | A kind of radioactive source prepares and correlation technique, radioactive source and PET system |
| KR20190051439A (en) | 2017-11-07 | 2019-05-15 | 한국원자력연구원 | Hydrogel bead of removing radionuclide and method for manufacturing the same |
| WO2020060171A1 (en) * | 2018-09-18 | 2020-03-26 | 한국원자력연구원 | Method for separating fine particles in soil using cationic magnetic nanoparticles |
| KR20200032600A (en) * | 2018-09-18 | 2020-03-26 | 한국원자력연구원 | Method for separating fine particles in soil using cationic magnetic nanoparticles |
| KR20210028448A (en) * | 2019-09-04 | 2021-03-12 | 한국원자력연구원 | Method and apparatus for separating fine particles in contaminated soil |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013186020A (en) * | 2012-03-09 | 2013-09-19 | Mitsubishi Paper Mills Ltd | Adsorbent |
| KR20150050251A (en) * | 2013-10-31 | 2015-05-08 | 한국원자력연구원 | Absorbent/hydrogel, manufacturing method for the same, and removing method for radioactive substance in using the absorbent/hydrogel |
-
2015
- 2015-05-13 KR KR1020150066818A patent/KR101678860B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013186020A (en) * | 2012-03-09 | 2013-09-19 | Mitsubishi Paper Mills Ltd | Adsorbent |
| KR20150050251A (en) * | 2013-10-31 | 2015-05-08 | 한국원자력연구원 | Absorbent/hydrogel, manufacturing method for the same, and removing method for radioactive substance in using the absorbent/hydrogel |
Non-Patent Citations (1)
| Title |
|---|
| Sumitra Datta 외 2인, 3 Biotech.(2013) 3권, 1-9쪽* * |
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| WO2020060171A1 (en) * | 2018-09-18 | 2020-03-26 | 한국원자력연구원 | Method for separating fine particles in soil using cationic magnetic nanoparticles |
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| KR102258599B1 (en) * | 2019-09-04 | 2021-05-31 | 한국원자력연구원 | Method and apparatus for separating fine particles in contaminated soil |
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| CN114203330A (en) * | 2021-12-13 | 2022-03-18 | 中国核动力研究设计院 | Ultrathin nickel-63 radiation source and preparation method and application thereof |
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