KR101658475B1 - Method for preparing magnetic absorbent - Google Patents
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- KR101658475B1 KR101658475B1 KR1020150048602A KR20150048602A KR101658475B1 KR 101658475 B1 KR101658475 B1 KR 101658475B1 KR 1020150048602 A KR1020150048602 A KR 1020150048602A KR 20150048602 A KR20150048602 A KR 20150048602A KR 101658475 B1 KR101658475 B1 KR 101658475B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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Abstract
The present invention relates to a method for producing a magnetic adsorbent comprising forming a transition metal-ferrocyanide complex on the surface of a superpowder-like nanoparticle.
Description
The present invention relates to a method for producing a magnetic adsorbent comprising forming a transition metal-ferrocyanide complex on the surface of a superpowder-like nanoparticle.
As the industry develops, the severity of environmental pollution is increasing day by day. In particular, as an energy source required for various industries, nuclear power generation is widely used in various economical aspects such as facility investment costs, and the efficiency of the radioactive waste treatment generated in nuclear power plants and research institutes related to nuclear power depends on the efficiency of radioactive nuclides. The development of selective adsorbents that can be exchanged is urgently required, and researches on this are being actively carried out.
In recent years, the Fukushima Daiichi Nuclear Power Plant accident caused by the Pacific Ocean earthquake in the Tohoku region, centered on the Pacific Ocean Sanriku area, has become a major barrier to the recovery work, especially in high concentrations of radioactive pollutants. For example, the half-life of radioactive Cs-137 contained in the radioactive contaminated liquid of Fukushima Nuclear Power Plant is 30.1 years, and the radioactive contamination liquid of Fukushima Nuclear Power Plant is present in large quantities, which is very serious. Among the radioactive contaminated nuclides, Cs-137 has a long half-life, accumulates in food chains, fish muscle tissues of animals, and is reported to increase the probability of liver cancer, kidney cancer and bladder cancer by entering the body. Therefore, it is necessary to develop a technology capable of rapidly and effectively decontaminating Cs-137, which has a half-life in the event of a serious accident.
The main nuclear species, cesium, was adsorbed using zeolite as a means of decontaminating water environments contaminated with radioactive materials such as pools, rivers, rivers, lakes and wetlands due to Fukushima nuclear accident. However, And the secondary waste was generated in a large amount due to the high concentration treatment. Therefore, it is required to develop a highly efficient adsorbent capable of removing radionuclides that are rarely present in pools, rivers, rivers, lakes, wetlands, etc. after accidents in which radioactive materials leach out. Development of processing technology is required.
Studies have been carried out to decontaminate cesium by using Cs-137 and metal-ferrocyanide with high adsorption power for the decontamination of radioactive cesium as mentioned above. Among them, researches on the decontamination of liquid radioactive waste Cs-137 has been actively researched. In the precipitation method using metal ferrocyanide, a process for recovering and removing precipitates after adsorption of cesium is indispensable, and magnetic adsorbents are in the spotlight.
As a prior art related to the present invention, magnetic adsorbents having transition metal-ferrocyanide capable of adsorbing radioactive cesium to a recoverable magnetic particle have been conventionally existed. However, in these cases, there is a problem in that the transition metal-ferrocyanide And a high molecular weight material such as a silane coupling agent must be used as an intermediary material. Therefore, if it is possible to directly synthesize the transition metal-ferrocyanide on the surface of magnetic particles without an intermediate material, it is possible to provide a magnetic adsorbent having a better process, cost and adsorption efficiency, .
It is an object of the present invention to provide a method for producing a magnetic adsorbent comprising forming a transition metal-ferrocyanide complex on the surface of a superpowder-like nanoparticle.
It is still another object of the present invention to provide a magnetic adsorbent obtained through the above production method, particularly a magnetic adsorbent for cesium adsorption.
In order to remove radioactive cesium in the radioactive material with high efficiency, the magnetic adsorbent may be prepared by directly bonding a transition metal-ferricyanide complex capable of adsorbing radioactive cesium to the surface of magnetic nanoparticles having superparamagnetism The objective of the present invention is to develop a magnetic adsorbent of high efficiency capable of recovering strong magnetic force based on magnetic nanoparticle clusters as well as being easy to recover by a magnetic field.
The method comprising in order to attain the object, an aspect of the invention is preparing a precursor solution comprising (i) MFe 2 O 4 superparamagnetic nanoparticle; (ii) preparing an aqueous solution of an alkali metal salt of hexacyanoferrate (III) or an alkali metal salt of hexacyanoferrate (II); (iii) preparing a reaction solution by mixing the precursor solution, the aqueous hexacyanoferrate (III) alkali metal salt solution or the aqueous hexacyanoferrate (II) alkali metal salt solution; And (iv) adjusting the pH of the reaction solution to 0.5 to 3 to form an AMFe (CN) 6 or MFe (CN) 6 complex on the surface of the superpowder nanoparticles, wherein A is an alkali metal, Wherein M is Fe, Co, Ni, Cu or Zn.
The method may further comprise adjusting the pH of the precursor solution of step (i), the aqueous solution of step (ii), or both to 0.5 to 3.
The hexacyano iron (III) aqueous acid alkali metal salt or hexacyano iron (II) acid aqueous solution of alkali metal salt of step (ii) may be a K 4 Fe (CN) 6 aqueous solution or K 3 Fe (CN) 6 aqueous solution have.
The MFe 2 O 4 superparamagnetic nanoparticles can form clusters.
The clusters may be 10-1000 nm in size.
In step (iv), the pH of the precursor solution may be adjusted to 1.5 to 2.5. The pH adjustment of step (iv) may be accomplished by the addition of hydrochloric acid.
The MFe2O 4 superparamagnetic nanoparticles can be prepared by hydrothermal synthesis.
The hydrothermal synthesis may be performed using a mixture comprising FeCl 3 .6H 2 O.
The mixture may further comprise XCl 2 .4H 2 O, and X may be Co, Ni, Cu or Zn.
Another aspect of the present invention provides a magnetic adsorbent produced by the method of the present invention described above.
The magnetic adsorbent may be for adsorbing radioactive cesium.
Hereinafter, the present invention will be described in more detail.
Further comprising: an aspect of the invention is preparing a precursor solution comprising (i) MFe 2 O 4 superparamagnetic nanoparticle; (ii) preparing an aqueous solution of an alkali metal salt of hexacyanoferrate (III) or an alkali metal salt of hexacyanoferrate (II); (iii) preparing a reaction solution by mixing the precursor solution, the aqueous hexacyanoferrate (III) alkali metal salt solution or the aqueous hexacyanoferrate (II) alkali metal salt solution; And (iv) adjusting the pH of the reaction solution to 0.5 to 3 to form an AMFe (CN) 6 or MFe (CN) 6 complex on the surface of the superpowder nanoparticles, wherein A is an alkali metal, Wherein M is Fe, Co, Ni, Cu or Zn.
In the step of preparing a precursor solution containing the magnetic nanoparticles MFe 2 O 4 portrait of step (i), M may be Fe, Co, Ni, Cu, Cr, Mn or Zn. That is, the precursor solution is prepared by mixing superfine magnetic nanoparticles Fe 3 O 4 , CoFe 2 O 4 , NiFe 2 O 4 , CuFe 2 O 4 , CrFe 2 O 4 , MnFe 2 O 4 Or ZnFe 2 O 4 . If the radioactive material to be adsorbed is cesium, it may be particularly effective that M is Fe, Co, Ni, Cu or Zn.
The method of preparing the super-magnetic nanoparticles is not particularly limited, and any known method may be used without limitation, and those commercially available as commercial products may be used.
Method of manufacturing a superparamagnetic nanoparticles as described above is not particularly limited, as an example, the MFe2O 4 superparamagnetic nanoparticles can be prepared by hydrothermal synthesis.
The hydrothermal synthesis may be performed using a mixture comprising FeCl 3 .6H 2 O, wherein the mixture further comprises XCl 2 .4H 2 O, wherein X is Co, Ni, Cu, Cr, Mn or Zn .
In one embodiment, the mixture may comprise at least one of FeCl 3 .6H 2 O, FeCl 2 .4H 2 O, iron acetylacetonate as precursors of magnetic particles, and ethylene glycol , Diethylene glycol, and triethylene glycol, and may contain at least one of sodium acetate, sodium acrylate, and urea as a reducing agent. (Fe 3 O 4 or γ-Fe 2 O 3) super-magnetic nanoparticles can be synthesized by hydrothermal synthesis by reacting the mixture in an autoclave apparatus at 100 ° C. to 300 ° C. for 2 to 48 hours have. These super magnetic nanoparticles can be synthesized in cluster form.
In a further embodiment, the mixture is a precursor of the magnetic particles XCl 2 · 4H 2 O including (X = Co, Ni, Cu, Cr, Mn or Zn) and, FeCl 3 · 6H 2 O,
In the method for producing a magnetic adsorbent of the present invention, in step (ii) and step (iii), an aqueous solution of an alkali metal hexacyanoferrate (III) or an aqueous solution of an alkali metal hexacyanoferrate (II) And a reaction solution is prepared. The alkali metal salt of hexacyanoferrate (III) or the alkali metal salt of hexacyanoferrate (II) may be in the form of A 4 Fe (CN) 6 or A 3 Fe (CN) 6 , May be a metal element. To preferably from the hexacyano iron (III) acid and alkali metal salt or hexacyano iron (II) acid alkali metal salt is K 4 Fe (CN) 6 or K 3 Fe (CN) 6, or Na 4 Fe (CN) 6 Or Na 3 Fe (CN) 6 , more preferably K 4 Fe (CN) 6 or K 3 Fe (CN) 6 . This step serves to provide the ferrocyanide (hexacyanoferrate) moiety of the transition metal-ferricyanide complex which is the adsorption-active material of the magnetic adsorbent provided in the present invention.
In the method for producing a magnetic adsorbent of the present invention, the step (iii) may include a step of forming a KMFe (CN) 6 or MFe (CN) 6 complex on the surface of the superpowder nanoparticles by adjusting the pH of the precursor solution to 0.5 to 3 .
That is, the method for producing a magnetic adsorbent according to the present invention is a method for producing a magnetic adsorbent , which comprises forming a supercritical nano particle (for example, Fe 3 O 4 , CoFe 2 O 4 , NiFe 2 O 4 , CuFe 2 O 4 , CrFe 2 O 4 , MnFe 2 O 4 Or ZnFe 2 O 4 ) is dispersed in a solution-strong acidic condition, Fe, Co, Ni, Cu, Cr, Mn or Zn ions are dissolved and formed from the surface of the superpowder nanoparticles, When reacted with the provided ferrocyanide, various transition metal-ferrocyanides are synthesized and attached directly to the surface of the nanoparticles.
The method for producing a magnetic adsorbent of the present invention is characterized in that a super-magnetic nano-particle (core) on which a magnetic adsorbent is based and an intermediate for the conjugation of the two substances between the transition metal- There is an advantage that the manufacturing process is simplified since the transition metal-ferrocyanide is directly adhered to the superpowder magnetic nanoparticles without a substance (for example, a silane coupling agent). In addition, since there is no intermediate substance, the adsorption amount per g of the finally obtained magnetic adsorbent is increased, so that the efficiency of the magnetic adsorbent as a final product can be maximized.
In addition, the method of producing a magnetic adsorbent of the present invention is not limited to attaching the pre-synthesized transition metal-ferrocyanide to the surface of magnetic particles, but also to form a transition metal-ferricyanide in situ on the surface of the supercritical nano- Ferrocyanide can be adhered while being directly synthesized, the amount of transition metal-ferrocyanide, which is an effective adsorption material, can be easily controlled, and when the components are controlled so as to contain various transition metals as superpowder nanoparticles, It also has the advantage of being able to produce magnetic adsorbents for cesium removal where the transition metal-ferrocyanide is attached to the surface.
In step (iv), the pH of the precursor solution may be adjusted to 1.5 to 2.5, because the step (iv) is for dispersing the super-pure magnetic nanoparticle precursor solution in a solution-strong acid condition. More preferably, the pH can be adjusted to about 2. The pH of step (iv) may be adjusted by adding a strong acid such as hydrochloric acid, sulfuric acid, nitric acid or the like, but the present invention is not limited thereto. Preferably, the pH can be adjusted by adding hydrochloric acid.
In one embodiment, the MFe 2 O 4 superparamagnetic nanoparticles of step (i) can form clusters. The cluster may be between 10 nm and 1000 nm in size.
The magnetic adsorbent provided in the present invention can act as a dispersed phase based on single super magnetic nanoparticles. However, when the super magnetic nanoparticles form clusters, the magnetic adsorbent has a higher magnetic property, . Since the magnetic adsorbent based on the magnetic nanoparticle clusters based on the superparamagnetic particles effectively adsorbs / removes only radioactive cesium from the radioactive contaminated liquid such as pools, rivers, and rivers contaminated with radioactive cesium, the magnetic core can be used even when the magnetic field is relatively weak due to high magnetic properties. It can be easily recovered.
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 of the radioactive contaminated liquid, it is preferably 1 to 50 nm in size. However, from the viewpoint of the self-adsorbing ability, the average particle diameter of the nanoparticles can be considered to be not less than 5 nm and not more than 50 nm from the viewpoint of enlarging the adsorption surface area.
However, the MFe 2 O 4 superparamagnetic nanoparticles included in the magnetic adsorbent of the present invention can form clusters from the viewpoint of enhancing integration and magnetic separation efficiency by magnetic force, It is easy to increase the integration and magnetic separation efficiency by increasing the adsorption force and the adsorption rate by the adsorbent. The size of such clusters may be in the range of 10 to 1000 nm, preferably in the range of 50 to 500 nm, more preferably in the range of 50 to 300 nm, in view of the balance of dispersibility, specific surface area and self- Lt; / RTI >
As described above, the saturation magnetization of the magnetic adsorbent provided in the present invention based on the superparamagnetic nano-particles or clusters thereof may be 5 emu / g or more, preferably 10 emu / g or more from the viewpoint of enhancing the efficiency of integration by magnetic force emu / g or more, more preferably 20 emu / g or more. The larger the saturation magnetization is, the higher the coupling efficiency with respect to the magnet is, but from the viewpoint of availability, it is usually 220 emu / g or less.
Another aspect of the present invention provides a magnetic adsorbent produced by the method of the present invention described above.
Therefore, the magnetic adsorbent of the present invention may be a magnetic adsorbent having a transition metal-ferrocyanide complex (adsorbing effective substance on the surface layer) formed on the surface of the super magnetic nanoparticles (core part), and the super- The description of the ferrocyanide complex is as described above, so it is omitted.
The magnetic adsorbent may be for adsorbing radioactive cesium.
The magnetic adsorbent of the present invention may be specifically for removing radioactive materials contained in liquids, particularly radiation cesium. The present invention aims to provide a method for producing a magnetic adsorbent for removing radioactive materials from a contaminated radioactive material by injecting the radioactive material into a liquid containing the radioactive material, and a magnetic adsorbent therefor. The liquid to be subjected to decontamination, that is, the liquid containing the radioactive material is not particularly limited as long as it does not deviate from the spirit of the present invention. A suitable example is an aqueous solvent such as a radioactive contaminated liquid or an aqueous solvent containing a part of an organic solvent, but it may also be applied to an organic solvent system. The liquid to be subjected to the recovery of the present invention is, for example, water such as rainwater, ground water, snow melted water, sea water, river water, lake water, pond water tank, etc., soil water including contaminated soil, , Washing water such as contaminated dust dispersed water, contaminated wastes, cleaning water such as apparatus and machine, transportation equipment for people, animals, cargo such as three-wheeled vehicle, bicycle, motorcycle, automobile, train, train, ship, , Water supplied to the water in the water supplied to the water supply, water collected from the sewage, sludge, purified water, water dispersed in the ashes including the radioactive material, beverages including foods such as milk, juice and tea, and harvested tea leaves Water, contaminated liquid and cleansing water derived from other animals, plants and microorganisms. The water supplied to the water supply and the tap water is the water supplied to each household, the industrial water, the agricultural water Water, Forestry and Livestock Industry Division It may include water used in industry.
The above liquid may be a waste liquid containing radioactive cesium, which is particularly a problem due to an accident at a nuclear power plant. Radioactive cesium is one of the substances that occurs during uranium nuclear disintegration, which is used as fuel for nuclear power plants.
As described above, since the magnetic adsorbent provided in the present invention is based on the superparamagnetic nanoparticles or clusters thereof, it is possible to form a magnetic adsorbent which is easily magnetically separated by having a high magnetic property. In the case of a conventional adsorbent which is not a magnetic adsorbent, a means such as centrifugal separation is used as a method for recovering particles adsorbing a radioactive substance. Therefore, it takes a long time to centrifuge with the centrifugal separator and it has hindered the efficient recovery of radioactive materials from a large amount of radioactive contaminated liquid. Alternatively, as a method for recovering particles adsorbing a radioactive substance, there has been a method of adding a precipitate or a flocculant to precipitate it. However, this requires a facility and time for sedimentation, so that a large amount of radioactive contaminated liquid can be efficiently recovered . Since the magnetic adsorbent of the present invention has no cross-linking intermediate between the core and the adsorbent, the amount of adsorbed (adsorbing ability) per g of the magnetic adsorbent is increased, but the size of the magnetic material is also increased. It is advantageous in that a high efficiency and a large number of recovery are possible.
The recovery may be achieved by depositing the magnetic adsorbent by immersing it in a radioactive contaminant by using any magnetic force accumulating means. After integration, recovery can be completed by stopping the self-generation of the magnetic force accumulating means. That is, by collecting and collecting the magnetic adsorbent by the magnetic force of the magnetic force accumulating means, it is possible to easily and efficiently recycle the magnetic core. The magnetic adsorbent may be collected and separated by depositing or bringing the magnetic force accumulating means to the outer wall of the vessel without being immersed in the radioactive contamination liquid.
After the TMI nuclear accident or Fukushima nuclear accident, the major nuclear species, cesium, was adsorbed by using zeolite to decontaminate pools, rivers and streams polluted with radioactive materials. However, in an environment with high salt concentration, the efficiency of removing radioactive cesium was low, There was a problem that was not easy.
The method of producing a magnetic adsorbent of the present invention is a method of producing a magnetic adsorbent, which comprises a superporous magnetic nanoparticle (core) on which a magnetic adsorbent is based and a transition metal-ferrocyanide which is an adsorbing effective substance synthesized adhering to the surface of the core, As a method for synthesizing and attaching the transition metal-ferrocyanide directly on the nanoparticles, since there is no intermediate substance, the adsorption amount and the magnitude of the magnetization per g of the finally obtained magnetic adsorbent are increased. Therefore, the adsorption efficiency of the magnetic adsorbent, The recovery efficiency can be maximized. Accordingly, the magnetic adsorbent provided in the present invention can function as a highly efficient adsorbent for removing radioactive nuclides rarely present in rivers, rivers, pools, etc. after an accident. In addition, the recovery efficiency depends on the magnetization value of the magnetic adsorbent. The magnetic adsorbent of the present invention, as described above, is not only increased in magnetization per g of the magnetic adsorbent, but also formed by forming super-magnetic nanoparticles (clusters) And is an excellent magnetic adsorbent having a high magnetization value capable of recovering the adsorbent even under a low magnetic field.
In addition, the method of producing a magnetic adsorbent of the present invention can adhere while directly synthesizing a transition metal-ferrocyanide in situ on the surface of a superpowder nanoparticle, It is possible to easily control the amount of the introduced magnetic nanoparticles and to control the components thereof so as to contain various transition metals as superparamagnetic nanoparticles, it is possible to produce a magnetic adsorbent for cesium removal, in which various transition metal- have.
That is, the present invention provides a magnetic adsorbent which is excellent in removal efficiency of radioactive cesium and can recover the adsorbent with high efficiency by an external magnetic field in various environments, and a method for producing the same.
By using the magnetic adsorbent production method of the present invention and the magnetic adsorbent obtained therefrom, it is possible to efficiently cope with the restoration of a widely contaminated environment with radioactive cesium in the event of a serious accident such as an accident in future Fukushima nuclear power plant, It is expected that environmental pollution can be reduced significantly. It is also expected to be useful for removing radionuclides in liquid wastes at nuclear power plants.
FIG. 1 shows X-ray diffraction (XRD) analysis results of the magnetic nanoclusters (MNC) prepared in Example 1. FIG.
FIG. 2 is a transmission electron microscope (TEM) photograph of the magnetic nanoparticle cluster (MNC) prepared in Example 1. FIG.
FIG. 3 shows X-ray diffraction (XRD) analysis results of the magnetic nanoparticle clusters and the magnetic adsorbent prepared in Example 1. FIG.
FIG. 4 is a transmission electron microscope (TEM) photograph showing the magnetic adsorbent prepared in Example 1. FIG. From the left are MNC @ PB-1, MNC @ PB-2, and MNC @ PB-3.
FIG. 5 is a Fourier transform infrared spectroscopy (FT-IR) analysis result of the magnetic nanoparticle cluster and the magnetic adsorbent prepared in Example 1. FIG.
6 is a digital image showing the results of magnetic recovery using the external magnet of the magnetic adsorbent prepared in Example 1. Fig.
7 is an X-ray diffraction (XRD) analysis result of the magnetic cluster (Zn-MNC) prepared in Example 2. Fig.
8 is a transmission electron microscope (TEM) photograph of the magnetic cluster (Zn-MNC) prepared in Example 2. Fig.
9 is a transmission electron microscope (TEM) photograph showing the magnetic adsorbent prepared in Example 2. Fig. Zn-MNC @ ZnFC-1 and Zn-MNC @ ZnFC-2 from the left.
10 is a Fourier transform infrared spectroscopy (FT-IR) analysis result of the magnetic nanoparticle cluster and the magnetic adsorbent prepared in Example 2. FIG.
11 is a digital image showing the result of magnetic recovery using the external magnet of the magnetic adsorbent prepared in Example 2. Fig.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Example One: Fe - Ferrocyanide Synthesized Magnetic Adsorbent Production
2.7 g of FeCl 3 .6H 2 O (Sigma Aldrich) and 7.2 g of sodium acetate (Sigma Aldrich) were added to 100 mL of ethylene glycol (Sigma Aldrich) and stirred for 30 minutes or more to prepare a homogeneous solution. The above mixture was transferred into a Teflon-lined stainless steel autoclave (Hanul Engineering Co., Ltd.), the autoclave was locked, and the reaction was carried out at 200 ° C for 8 hours in an electric oven. After the completion of the reaction, the temperature of the reactor was lowered to room temperature, water and ethanol were alternately added to the resultant product, and the unreacted material and excess water and ethanol were removed using a magnet to obtain a precipitate. The obtained precipitate was dried under reduced pressure at 60 DEG C to obtain magnetic nanoparticle clusters. Then, 1 mmol / L, 2 mmol / L, a concentration of 5 mmol / L K 4 Fe ( CN) after creating the 6 aqueous solution, respectively, 0.1 mol / L by using a HCL K of 4 Fe (CN) 6 aqueous solution Lt; / RTI > was adjusted to 2. After the magnetic nanoparticle clusters prepared above were dispersed in water, the pH of the aqueous solution was adjusted to 2 using 0.1 mol / L of HCl. At this time, after adjusting the concentration of the final magnetic nanoparticles clustered to 0.5g / L, prepared previously into the moisture K 4 Fe (CN) to the first magnetic nanoparticle clusters aqueous solution of a 6: K was added to a final 1 4 Fe (CN ) 6 was added to 0.5 mmol / L. 1 mmol / L and 2.5 mmol / L, respectively. (CN) 6 or FeFe (CN) 6 at the surface of the superparamagnetic nanoparticle cluster reacts with Fe (CN) 6 present in the aqueous solution by dissolving iron ions on the surface of the superpowder nanoparticles by HCl Ananide complexes were confirmed by X-ray diffraction (XRD) analysis (FIG. 3), transmission electron microscope (TEM) photograph (FIG. 4) and FT-IR analysis (FIG. MNC @ PB-1, MNC @ PB-2, MNC @ PB-3) were added to the magnetic adsorbent samples with the final concentration of added K 4 Fe (CN) 6 of 0.5 mmol / L, 1 mmol / Respectively. 4, the XRD peak of the hexagonal Fe-ferrocyanide (Prussian blue (PB)) synthesized on the surface of the nanoparticles increases as the amount of K 4 Fe (CN) 6 added increases , And K 4 Fe (CN) 6, the particle size of Fe-ferrocyanide synthesized on the surface of the nanoparticles increases. In the FT-IR analysis result of FIG. 5, a peak indicating CN can be seen.
The data in Table 1 are the result of measuring the average particle size and the surface charge value of the magnetic adsorbent synthesized in Example 1 above. As the amount of K 4 Fe (CN) 6 added increases, the particles of Fe-ferrocyanide synthesized on the clusters become larger and the average size of all the adsorbents increases. For the same reason, Fe-ferrocyanide (-) value of the magnetic adsorbent synthesized due to the increase of the surface charge value of the magnetic adsorbent.
Example 2: Preparation of magnetic adsorbent having Zn - ferrocyanide synthesized
0.42 g of ZnCl 2 (Sigma Aldrich), 1.52 g of FeCl 3 .6H 2 O (Sigma Aldrich) and 2.4 g of sodium acetate (Sigma Aldrich) were added to 90 mL of ethylene glycol (Sigma Aldrich) made. The mixture was transferred into a Teflon-lined stainless steel autoclave (Hanul Engineering Co., Ltd.), and the autoclave was closed. The autoclave was placed in an electric oven and reacted at 200 ° C for 8 hours. After the completion of the reaction, the temperature of the reactor was lowered to room temperature, water and ethanol were alternately added to the resultant product, and the unreacted material and excess water and ethanol were removed using a magnet to obtain a precipitate. The obtained precipitate was dried under reduced pressure at 60 DEG C to obtain magnetic nanoparticle clusters. Thereafter, a K 4 Fe (CN) 6 aqueous solution having a concentration of 1 mmol / L and 2 mmol / L was prepared, and the pH of the K 4 Fe (CN) 6 aqueous solution was adjusted to 2 Respectively. After the magnetic nanoparticle clusters prepared above are dispersed in water, the pH of the aqueous solution is adjusted to 2 by using 0.1 mol / L of HCl. At this time, after the semi-fit, the concentration of the final magnetic nanoparticles clustered to 0.5 g / L, prepared previously into the moisture K 4 Fe (CN) 6
Test Example :
The radioactive cesium contained in the water was evaluated by using the magnetic adsorbent prepared in Examples 1 and 2 by the following method.
The adsorbent prepared in Examples 1 and 2 was added to an aqueous solution containing radioactive cesium to a concentration of 0.05 to 0.2 mg / mL and shaken for 2 hours to adsorb the radioactive cesium in the aqueous solution to the adsorbent. The magnetic adsorbent was then recovered using a magnetic field to remove radioactive cesium in the aqueous solution. The radioactivity (activity, Bq / g) of the radioactive cesium solution before and after removing the radioactive cesium as the adsorbent was measured using a radioactive cesium atom analyzer (high purity germanium detector). The results of radioactive cesium removal are shown in Tables 2 and 3 below.
The magnetic adsorbents prepared in Examples 1 and 2 exhibited a very high efficiency of removing radioactive cesium of 99% or more even at a small amount of 0.05 mg / mL, and the adsorption removal efficiency of 99 %, Which is similar to the removal efficiency of 99%. That is, considering that the salt concentration of seawater is 3000 ppm, the magnetic adsorbents prepared in Examples 1 and 2 can also be used for purification of seawater contaminated with radioactive cesium.
Compared to the adsorbent performance of the following patent (No. 10-1429560), the results in Tables 2 and 3 show that the radioactive cesium removal performance is greatly improved (improved radioactive cesium removal rates at the same concentration and similar initial radioactive cesium concentration, Even at a lower concentration of 0.05 mg / mL, the initial radioactive cesium amount was more than four times higher, but still showing a higher removal efficiency).
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, Of the right.
Claims (12)
(ii) preparing an aqueous solution of an alkali metal salt of hexacyanoferrate (III) or an alkali metal salt of hexacyanoferrate (II);
(iii) preparing a reaction solution by mixing the precursor solution, the aqueous hexacyanoferrate (III) alkali metal salt solution or the aqueous hexacyanoferrate (II) alkali metal salt solution; And
(iv) adjusting the pH of the reaction solution to 0.5 to 3 to form AMFe (CN) 6 or MFe (CN) 6 complex on the surface of the superpowder magnetic nanoparticles,
Further comprising adjusting the pH of both the precursor solution of step (i) and the aqueous solution of step (ii) to 0.5 to 3,
Wherein A is an alkali metal,
M is Fe, Co, Ni, Cu or Zn,
Wherein the MFe 2 O 4 superparamagnetic nanoparticles form a cluster having a size of 50 to 300 nm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190051748A (en) | 2017-11-06 | 2019-05-15 | 한국원자력연구원 | Composition of removing radionuclide and method for removing radionuclide using the same |
| KR102211750B1 (en) | 2020-01-20 | 2021-02-03 | 엔스펙트라 주식회사 | Magnetic adsorbent and method for radioactive cesium treatment using same |
| KR20210029666A (en) * | 2019-09-06 | 2021-03-16 | 한국원자력연구원 | Adsorbent of radionuclide and preparing method of the same and removal method of radionuclide using the same |
| US10971276B2 (en) | 2017-11-06 | 2021-04-06 | Korea Atomic Energy Research Institute | Composition for removing radionuclide and method for removing radionuclide using the same |
| CN115282969A (en) * | 2022-01-04 | 2022-11-04 | 榆林学院 | Magnetic NiFe 2 O 4 Preparation method and application of nanosphere |
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| KR20140091264A (en) * | 2013-01-11 | 2014-07-21 | 한국원자력연구원 | Manufacturing method of adsorbent based on magnetic nanoparticles for radioactive cesium |
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| KR20140091264A (en) * | 2013-01-11 | 2014-07-21 | 한국원자력연구원 | Manufacturing method of adsorbent based on magnetic nanoparticles for radioactive cesium |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190051748A (en) | 2017-11-06 | 2019-05-15 | 한국원자력연구원 | Composition of removing radionuclide and method for removing radionuclide using the same |
| US10971276B2 (en) | 2017-11-06 | 2021-04-06 | Korea Atomic Energy Research Institute | Composition for removing radionuclide and method for removing radionuclide using the same |
| KR20210029666A (en) * | 2019-09-06 | 2021-03-16 | 한국원자력연구원 | Adsorbent of radionuclide and preparing method of the same and removal method of radionuclide using the same |
| KR102337203B1 (en) | 2019-09-06 | 2021-12-09 | 한국원자력연구원 | Adsorbent of radionuclide and preparing method of the same and removal method of radionuclide using the same |
| KR102211750B1 (en) | 2020-01-20 | 2021-02-03 | 엔스펙트라 주식회사 | Magnetic adsorbent and method for radioactive cesium treatment using same |
| CN115282969A (en) * | 2022-01-04 | 2022-11-04 | 榆林学院 | Magnetic NiFe 2 O 4 Preparation method and application of nanosphere |
| CN115282969B (en) * | 2022-01-04 | 2024-03-08 | 榆林学院 | Magnetic NiFe 2 O 4 Preparation method and application of nanospheres |
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