Novel Cs ion selective adsorption material and preparation method thereof

Abstract

The invention belongs to the field of adsorption materials, and relates to a preparation method of a radionuclide ion absorption material, in particular to a preparation method of a novel Cs ion selective adsorption material. The method is characterized in that the hexacyanoferrate fine particles with high selective adsorption capacity on the Cs ions are encapsulated in the spherical carbon material, so that the uniform dispersity and the hydraulic property of the hexacyanoferrate particles are greatly improved, and the Cs ions are efficiently and selectively adsorbed; according to the present invention, with the spherical carbon material, the huge water resistance caused by the accumulation of the hexacyanoferrate particles is avoided, and the problems of material pulverization and chipping loss are completely avoided due to the hard and compact spherical shell of the spherical carbon material so as to provide the excellent adsorption performance on the Cs-containing radioactive wastewater treatment.

Description

Technical Field

[0001] This application belongs to the field of adsorption materials, and relates to a preparation method of a radioactive nuclide ion absorption material, and particularly relates to a novel Cs ion selective adsorption material and a preparation method thereof. Background Art

[0002] Whether the radioactive wastewater generated by the nuclear industry can be properly disposed of is one of the key links related to nuclear safety. Research and development of efficient and highly selective radioactive wastewater treatment technologies to minimize waste generation to the greatest extent is a very meaningful task in the nuclear industry. The common methods for treating radioactive wastewater are as follows: 1) Evaporation and concentration method: After the radioactive wastewater is treated by evaporation and concentration, the evaporation residue is solidified and disposed of, and the distillate is discharged after being treated by ion exchange resin. This method has high energy consumption, and due to the high salt content of the radioactive wastewater, the corrosion of the evaporation device is very serious.

[0003] 2) Natural silicoaluminate treatment method: This method uses natural silicoaluminates such as kaolin, rectorite, vermiculite, etc. with certain ion exchange capabilities to treat radioactive wastewater, in order to fix the radioactive nuclide ions inside these materials to complete the treatment of the wastewater. However, the ion exchange capabilities of these materials are limited, and the selectivity for nuclide ions is poor, generating a large amount of radioactive waste that needs to be further treated and disposed of.

[0004] 3) Zeolite treatment method: Natural zeolites or synthetic zeolites have a suitable regular spatial structure and can adsorb and treat radioactive nuclides. In theory, the exchange capacity of zeolite for Cs ions can reach 2 meq / g, but in practice, other ions such as potassium ions will strongly interfere with the removal of Cs ions, resulting in a very low adsorption capacity of zeolite. Only 10 kg of wastewater can be treated per kilogram of zeolite. Since the adsorbent cannot be regenerated in the treatment of radioactive wastewater, a large amount of radioactive waste is generated and needs to be further treated and disposed of.

[0005] 4) Ion exchange resin treatment method: Currently, most of the ion exchange resins used in nuclear facilities in China for treating medium and low-level radioactive waste liquid are strong acid and strong base types based on styrene divinylbenzene. Usually, the utilization rate of the adsorption capacity of the resin is less than 30%. The resin lacks sufficient selectivity for radioactive nuclides in medium and low-level radioactive waste liquid, and the resin is used once and not regenerated. Therefore, a large amount of radioactive waste resin is generated, and the subsequent disposal cost is quite astonishing. In addition, the resin is an organic material with poor radiation resistance, and radiation decomposition may produce methane and hydrogen, which becomes a major hidden danger for the long-term storage of radioactive waste resin.

[0006] 5) Ammonium phosphomolybdate treatment method: Ammonium phosphomolybdate for Cs +It has high selectivity. However, ammonium phosphomolybdate is composed of fine microcrystals and cannot be used in packed-bed operations, which severely limits its industrial applications. Sun Zhaoxiang et al. prepared hybrid materials of ammonium phosphomolybdate and tetravalent metal phosphates (such as Ti, Zr, Sb, etc.), achieving the granulation of ammonium phosphomolybdate (Ion Exchange and Adsorption, 12, 44 - 49, 1996; Journal of Nuclear Chemistry and Radiochemistry, 21, 76 - 82, 1999; Journal of Beijing Normal University: Natural Science Edition, 27, 339 - 343, 1991). However, the introduction of relatively expensive tetravalent metals increased the cost. According to the technical report on radioactive waste treatment released by the International Atomic Energy Agency in 2002, ammonium phosphomolybdate series materials have not been widely applied in the treatment of radioactive wastewater.

[0007] 6) Ferrocyanide treatment method: Ferrocyanide immobilized by transition metals has good selective absorption capacity for radioactive Cs + , and... With a concentration of 5 mol / L of Na + , this type of material has a selectivity coefficient for Cs + (targeting Na +)Reached 1500000 (Nuclear Science and Engineering, 137, 206 - 214, 2001). However, the mass transfer conditions inside the ferrocyanide particles are poor, and the adsorption capacity often cannot be fully utilized (Journal of Nuclear Chemistry and Radiochemistry, 23, 108 - 113, 2001). Loading ferrocyanide on a porous material support can improve the mass transfer kinetics conditions. Mardan studied the use of the solvent evaporation method, using pre - formed porous silica as the support to immobilize K2[CoFe(CN)6] (Separation and Purification Technology 16, 147 - 158, 1999). Its highest loading amount is 1.36 g - K2[CoFe(CN)6] / g - SiO2, and the solvent evaporation step needs to be repeated many times. The steps are cumbersome, consuming a large amount of organic solvents, and the possibility of practical application is small (Talanta, 17 - 23, 955, 1970). Wang Qiuping et al. prepared various materials such as calcium potassium ferrocyanide, zinc potassium ferrocyanide, and manganese potassium ferrocyanide by coprecipitation under acidic conditions, all of which have good Cs ion adsorption capacity. However, due to the poor stability of the particles, they are easily broken and pulverized during actual operation and cannot be used for the treatment of radioactive wastewater (Ion Exchange and Adsorption, 16(3), 225 - 233, 2000). Terada (Talanta 1970, 17, 955 - 963), Konecny (Radioanal. Chem., 1973, 14, 255 - 266), and Mandan (Sep. Purif. Technol., 1999, 16, 147 - 158) all reported a method of first immobilizing potassium ferrocyanide in silica gel and then using transition metal ions to convert it into a ferrocyanide absorbent. However, since the conversion reaction occurs inside the pores of silica, its rate is extremely slow, a greatly excessive amount of metal ions needs to be used, and the composition of the product of the conversion reaction is difficult to control. In addition, because the conversion reaction is difficult to proceed completely, it cannot prevent part of the potassium ferrocyanide in the silica gel from being leached and lost during the ion absorption process.

[0008] Jiang Changyin, Song Chongli (Journal of Nuclear Chemistry and Radiochemistry 1995, 17(2), 99 - 104) et al. creatively used the method of urea - formaldehyde condensation to make TiO2 spheres from TiCl4, and then immersed the TiO2 spheres in a mixture of potassium ferrocyanide (0.7 M) and hydrochloric acid (1 M) to obtain a spherical potassium titanium ferrocyanide absorbent material. As mentioned above: The specific surface area of this material is not high (14 m 2 / g), there are few internal pores, so the absorption of cesium is concentrated only in a thin layer on the surface of the particles; in addition, the particle size of the material is not uniform, and some of it will break during use. Furthermore, due to the presence of urea-formaldehyde condensate inside the material, it cannot be solidified by the commonly used heating and sintering method after cesium ion adsorption is saturated, because NO3 - When heated, the ions will oxidize the urea-formaldehyde organic matter and cause an explosion.

[0009] In order to solve these technical problems, the research team of Professor Zhao Xuan of Tsinghua University evenly dispersed the synthesized hexacyanoferrate potassium cobalt nanoparticles in alkaline silica sol, added acid to make it lose fluidity under vigorous stirring, and obtained a block material hybridized by amorphous silica and nano hexacyanoferrate potassium cobalt after drying. The particle diameter of the final product can be freely selected according to the crushing strength. Nano hexacyanoferrate potassium cobalt can be regarded as nano bricks, while amorphous silica is nano cement. The material is + 、Na + and K + Cs + A good selective adsorption effect was achieved (Nuclear Technology, 2009, 165(2), 200-208). However, the problem with this material is that as the water flows, some hexacyanoferric cobalt potassium particles will inevitably fall off, causing the effluent to turn red. When treating real radioactive Cs-containing wastewater, the shed highly active hexacyanoferric cobalt potassium particles will also adsorb Cs ions, which makes it impossible to reduce the radioactivity of the effluent to an extremely low level.

[0010] In order to improve the problems of irregular particle morphology and poor hydraulic properties of the above materials, the team used porous spherical silica or alumina to load Ti(OH)x, and then reacted it with potassium hexacyanoferrate (II) to generate spherical porous silica or alumina as carrier potassium hexacyanoferrate (acyl) adsorption material. The material has excellent spherical morphology and high particle strength, high specific surface area and minimal intragranular diffusion. In the cold test, it achieved excellent selective adsorption of Cs ions (Journal of Inorganic Chemistry, 2008, 24 (10), 1657-1663). However, the potassium hexacyanoferrate (acyl) titanate particles on the inner wall of the pores of the material have insufficient binding force with the avoidance, and the water out of the material is blue-green. In order to reduce the problem of water color, the team tried a variety of technical solutions such as silica coating, which increased the diffusion resistance of Cs ions in the particles, and also failed to stably reduce the radioactivity of the water out to a very low level in the material hot test.

[0011] It can be seen that there are two difficulties in using hexacyanoferrate materials as Cs ion adsorbents: First, the particle size of the hexacyanoferrate particles themselves is too small, and their hydraulic performance is poor, making them unable to be used directly; Second, supported hexacyanoferrate materials often fail in hot tests due to debris shedding and decolorization.

[0012] In summary, how to exert the excellent selective adsorption ability of hexacyanoferrate materials for Cs ions while avoiding the hydraulic problems caused by their fine particles, and at the same time overcome the debris shedding caused by conventional granulation processes is an industry problem for which there is no mature technical solution. To break through this technical dilemma, this technical solution creatively uses a high-surface carbon sphere material obtained by carbonizing spherical ion exchange resins as a carrier, enabling transition metal ions and soluble hexacyanoferrates to undergo a coprecipitation reaction inside the carbon spheres, and in-situ encapsulating the precipitation products inside the carbon spheres, solving the problem of granulating nano-hexacyanoferrates. Moreover, since the spherical carbon material inherits the complete and dense spherical shell formed by the suspension polymerization of ion exchange resins, water and Cs ions can pass through this spherical shell, but nano-particles cannot, which completely eliminates the phenomenon of debris shedding in the material and makes this material an excellent technical solution for highly selective adsorption of Cs. + ions. Summary of the Invention

[0013] The purpose of this application is to provide a novel Cs ion selective adsorption material and its preparation method.

[0014] In the first aspect, this application provides a preparation method for a novel Cs ion selective adsorption material, adopting the following technical solution: A preparation method for a novel Cs ion selective adsorption material, whose material carrier is a spherical carbon material obtained by carbonizing a spherical ion exchanger, and whose active component is hexacyanoferrate particles loaded inside the spherical carbon material. First, non-Group IA metal ions are loaded onto the adsorption sites inside the spherical carbon material, and then a soluble hexacyanoferrate solution is immersed inside the spherical carbon material. The non-Group IA metal ions and the soluble hexacyanoferrate undergo a coprecipitation reaction to form hexacyanoferrate particles containing non-Group IA metal ions, which are in-situ fixed inside the spherical carbon material to obtain this novel Cs ion selective adsorption material.

[0015] In a specific feasible embodiment, the spherical carbon material is obtained by carbonizing acidic or basic styrene-based ion exchange resins, preferably strongly acidic macroporous resins.

[0016] In a specific feasible embodiment, the spherical carbon material is obtained by carbonizing acidic or basic phenolic resin-based ion exchange resins, preferably strongly acidic macroporous resins.

[0017] In a specific feasible embodiment, the spherical carbon material is pre-oxidized, and the carboxyl group content on its surface is 0.1 mmol / g to 5 mmol / g.

[0018] In a specific feasible embodiment, the pre-oxidizing agent of the spherical carbon material is one or any arbitrary proportion mixture of several of HNO3, H2O2, acidic potassium permanganate, and acidic potassium dichromate.

[0019] In a specific feasible embodiment, the non-group IA metal ion is Ca 2+ , Mg 2+ , Sr 2+ , Ba 2+ , Cu 2+ , Zn 2+ , Co 2+ , Ni 2+ , Pb 2+ , Fe 3+ , Cr 3+ , La 3+ , Ag + , Mn 2+ , Al 3+ or any arbitrary proportion mixture of several of them, and its dosage is 0.1 to 3 times the amount of carboxyl substance in the spherical carbon material, preferably Ba 2+ , Cu 2+ , Zn 2+ , Co 2+ , Ni 2+ , Pb 2+ , Fe 3+ , Mn 2+ , and its dosage is preferably 0.3 to 1 times the amount of carboxyl substance in the spherical carbon material.

[0020] In a specific feasible embodiment, the soluble hexacyanoferrate is any one or any arbitrary proportion mixture of potassium hexacyanoferrate, sodium hexacyanoferrate, and ammonium hexacyanoferrate, and its dosage is 0.3 to 5 times the amount of carboxyl substance in the spherical carbon material.

[0021] In a specific feasible embodiment, the soluble hexacyanoferrate solution reacting with the non-group IA metal ions already existing inside the carbon spheres is acidic, and its [H + = 0.01 to 2 mol / L, preferably 1 mol / L.

[0022] In a specific feasible embodiment, the reaction temperature of the non-group IA metal ions inside the carbon spheres and the soluble hexacyanoferrate is 20 to 100 o °C, and the reaction time is 0.5 to 48 hr.

[0023] In a second aspect, the present application provides a novel Cs ion selective adsorption material, which is prepared by the above method.

[0024] The present application has the following beneficial effects: The hexaferrocyanide fine particles with high selective adsorption ability for Cs ions are encapsulated inside the above spherical carbon material, greatly improving the uniform dispersion and hydrodynamic performance of the hexaferrocyanide particles. While efficiently selectively adsorbing Cs ions, it avoids the huge water resistance caused by the accumulation of hexaferrocyanide particles. At the same time, due to the hard and dense spherical shell of the above spherical carbon material, the problems of material pulverization and debris loss are completely avoided, and excellent adsorption performance is shown in the treatment of Cs-containing radioactive wastewater. Description of the Drawings

[0025] Figure 1 is a process flow chart of the preparation of a novel Cs ion selective adsorption material provided by the present application; Figure 2 is a mechanism diagram of the preparation process of a novel Cs ion selective adsorption material provided by the present application; Figure 3 is a surface morphology diagram of the spherical carbon material; Figure 4 is an internal cross-sectional morphology diagram (magnified 400 times) shown after the spherical carbon material is broken; Figure 5 is an internal cross-sectional morphology diagram (magnified 40000 times) shown after the spherical carbon material is broken; Figure 6 is the pore distribution curve of the spherical carbon material used in Example 1; Figure 7 is a low-magnification scanning electron microscope photograph (magnified 120 times) of the surface of the spherical shell observed after the sample particles prepared in Example 1 are broken; Figure 8 is a high-magnification scanning electron microscope photograph (magnified 20000 times) of the surface of the spherical shell observed after the sample particles prepared in Example 1 are broken; Figure 9 is a low-magnification scanning electron microscope photograph (magnified 120 times) of the internal cross-section after the sample prepared in Example 1 is broken; Figure 10 is a high-magnification scanning electron microscope photograph (magnified 20000 times) of the internal cross-section after the sample prepared in Example 1 is broken; Description of the Reference Numerals: 1. Spherical carbon material; 2. Smooth and complete spherical shell on the surface of the spherical carbon material; 3. Porous spherical carbon particles closely packed inside the spherical carbon material; 4. Porous spherical carbon particles loaded with non-group IA metal ions inside the spherical carbon material; 5. Porous spherical carbon particles loaded with insoluble hexacyanoferrate inside the spherical carbon material. Detailed implementation manners

[0026] The technical solution of the present application will be further described below through specific implementation manners. Those skilled in the art should understand that the embodiments are only for helping to understand the present application and should not be regarded as specific limitations to the present application.

[0027] In the drawings of the present application, Figure 2 1 is the spherical carbon material, 2 is the smooth and complete spherical shell on the surface of the spherical carbon material (see Figure 3 scanning electron microscope photograph), 3 is the porous spherical carbon particles closely packed inside the spherical carbon material (see Figure 5 scanning electron microscope photograph), the mesopores of the spherical carbon material are the inter-particle pores of these porous spherical carbon particles (see Figure 5 scanning electron microscope photograph), and the micropores of the spherical carbon material are the intra-particle pores of these spherical carbon particles. 4 is the porous spherical carbon particles loaded with non-group IA metal ions inside the spherical carbon material, and 5 is the porous spherical carbon particles loaded with insoluble hexacyanoferrate inside the spherical carbon material.

[0028] Figure 3 is the surface morphology diagram of the spherical carbon material used in the technical solution, and it can be seen that its surface is complete and smooth. The broken particles in the figure are fragments obtained by deliberately breaking the carbon spheres for observing the internal structure of the spherical carbon material; Figure 4 is the internal cross-sectional morphology diagram of the spherical carbon material used in the technical solution after being broken, with a magnification of 400 times; Figure 5 is the internal cross-sectional morphology diagram of the spherical carbon material used in the technical solution after being broken, with a magnification of 40,000 times. The closely packed spherical carbon particles can be identified, with a particle size of about 100 nm, and the inter-particle pores between the particles are clearly visible, and the size of the inter-particle pores is about 10 - 40 nm; Figure 6 is the pore size distribution curve of the spherical carbon material used in Example 1 (adsorption pore volume / pore size distribution diagram characterized by the BJH method), and an obvious double pore size distribution can be seen; Figure 7 is the low-magnification scanning electron microscope photograph (magnification 120 times) of the spherical shell surface observed after the sample particles prepared in Example 1 are broken; Figure 8is a high-magnification scanning electron microscope photograph (magnification 20,000 times) of the spherical shell surface observed after the sample particles prepared in Example 1 were crushed; Figure 9 is a low-magnification scanning electron microscope photograph (magnification 120 times) of the internal cross-section after the sample prepared in Example 1 was crushed; Figure 10 is a high-magnification scanning electron microscope photograph (magnification 20,000 times) of the internal cross-section after the sample prepared in Example 1 was crushed.

[0029] In this application, the spherical carbon material obtained by carbonizing spherical ion exchange resin is first oxidized, and the oxidizing agent is selected from HNO3, H2O2, acidic potassium permanganate or acidic potassium dichromate to increase the carboxyl content of the spherical carbon material to 0.1 - 4 mmol / g. Then, an excessive amount of soluble Ca 2+ , Mg 2+ , Sr 2+ , Ba 2+ , Cu 2+ , Zn 2+ , Co 2+ , Ni 2+ , Pb 2+ , Fe 3+ , Cr 3+ , La 3+ , Ag + , Mn 2 + , Al 3+ ions or an arbitrary proportion mixture of any several of them are fully adsorbed and fixed on the carboxyl group of the spherical carbon material. The spherical carbon material loaded with metal ions is dried, and the spherical carbon material is made to absorb an acidic soluble hexacyanoferrate (sodium hexacyanoferrate, potassium hexacyanoferrate, ammonium hexacyanoferrate or an arbitrary proportion mixture of any several of them) solution by the equal-volume impregnation method. The acidity is [H + = 0.01 mol / L - 2 mol / L, and the amount of substance of the soluble hexacyanoferrate is 0.3 - 5 times the amount of substance of the metal ions adsorbed in the spherical carbon material. After the impregnation is completed, the reaction is carried out for 0.5 - 48 hr, and the reaction temperature is 20 - 100 o °C. The obtained product is fully washed until the effluent is colorless and then dried to obtain the novel Cs ion selective adsorption material.

[0030] It should be noted that the resin carbonization process is a well-established existing technology and has already been disclosed in patents or literature, such as the Chinese patent application with the patent number CN114620723A, "The Influence of Support Activation on the Etherification Activity of PW12 / Carbonized Resin Catalysts" recorded in the Journal of Liaoning Petrochemical University, etc. Those skilled in the art can clearly know this process based on the existing technology, which is not the main inventive point of this article and will not be elaborated further.

[0031] Example 1

[0032] This example requests to disclose a preparation method of a novel Cs ion selective adsorption material, which adopts the following steps: The carbon material obtained by carbonization activation of spherical ion exchange resin used in this example, its surface morphology is as Figure 3 shown, and its internal particle packing situation is as Figure 5 shown, and its pore distribution situation is as Figure 6 shown, its specific surface area is 875 m 2 / g. Weigh 1000 g of this carbon sphere material, and oxidize it with three times the volume of concentrated nitric acid HNO3 at 50 o °C for 24 hours. After the obtained carbon spheres are washed and dried, the surface carboxyl group content is measured to be 3.5 mmol / g. Prepare 2.5 L of copper nitrate solution (molar concentration 1.4 mol / L, the ratio of the molar amount of copper ions to the molar amount of carboxyl groups is 1:1) according to the molar amount equal to the carboxyl group content, and impregnate the carbon spheres after HNO3 oxidation for 10 hours. Filter out the carbon spheres, wash them with a small amount of water and then dry them. Then prepare a potassium ferricyanide solution with 0.5 times the molar amount of carboxyl groups in the carbon spheres, with the acidity [H + +]=1 mol / L, and use the equal-volume impregnation method to load it into the pores of the above carbon spheres adsorbed with copper ions. React at 80 o °C for 24 hours. Wash the carbon spheres with water until the effluent is completely colorless, and then dry them to obtain a carbon sphere material with potassium copper hexacyanoferrate loaded inside. The loading amount of the active adsorption component potassium copper hexacyanoferrate is 17%. The low-magnification scanning electron microscope photo of the surface of the broken spherical shell of this small ball material is as Figure 7 shown (magnification 120 times), and the high-magnification scanning electron microscope photo of the surface of the spherical shell is as Figure 8 shown (magnification 20000 times). The low-magnification scanning electron microscope photo of the internal cross-section after the small ball material is broken is as Figure 9 shown (magnification 120 times), and the high-magnification scanning electron microscope photo of the internal cross-section after the small ball material is broken is as Figure 10 shown (magnification 20000 times). Compare Figure 8 and Figure 10It can be seen that the surface of the small ball material is a relatively dense and flat spherical shell, while the interior is a porous structure; through EDX analysis, it is known that on the surface of the small ball material, the atomic percentage of potassium element is 1.78%, the atomic percentage of iron element is 0.71%, and the atomic percentage of copper element is 0.66% ( Figure 8 ), while on the internal cross-section of the small ball material, the atomic percentage of potassium element is 3.3%, the atomic percentage of iron element is 1.54%, and the atomic percentage of copper element is 1.02% ( Figure 10 ), which is significantly higher than the percentage of each element in the outer shell of the small ball. It can be seen that most of the potassium copper hexacyanoferrate is encapsulated inside the carbon ball, while the content of potassium copper hexacyanoferrate on the surface is small. Moreover, because it is fixed inside the relatively dense spherical carbon layer, it is not easy to powder and generate debris. The selective absorption ability of this material for Cs ions is characterized by absorbing 1 mg / L of Cs ions in H ions, Na ions, and K ions with concentrations of 1 mol / L, 0.5 mol / L, and 0.1 mol / L respectively, and the adsorption time is 12 h. The distribution coefficient of the adsorbent is calculated according to the formula (0.2 g of adsorbent, 50 mL of absorbent solution): Kd = ( C 0 - C 1 ) F / C 1 In the formula C 0 : The concentration of Cs ions in the solution before adsorption (=1000 μg / L); C 1 : The concentration of ions in the solution after adsorption (mg / L); F : The mass ratio of the absorbent solution volume to the adsorbent mass (50 / 0.2 = 250 mL / g).

[0033] The concentration of Cs ions in the liquid after absorption is shown in Table 1: Table 1 Concentration of Cs ions in the liquid in Example 1 Interfering ions and concentrations Final concentration of Cs ions (μg / L) <![CDATA[H + 1mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[H + 0.5 mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[H + 0.1mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[Sodium + 0.1 mol / L (sodium chloride)]]> 1.85 134740 <![CDATA[Sodium + 0.5 mol / L (sodium chloride)]]> 3.33 74694 <![CDATA[Sodium + 1 mol / L (sodium chloride)]]> 4.43 56108 <![CDATA[K + 0.1mol / L (KCl)]]> 8.61 28776 <![CDATA[K + 0.5mol / L (KCl)]]> 42.2 5679 <![CDATA[K + 1mol / L (KCl)]]> 103 2175 From the adsorption test results, it can be seen that the presence of H + has no effect on the material's adsorption of Cs ions at all, which is completely incomparable to ion exchange resin materials. The material still shows a strong capturing ability for Cs ions under the interference of Na + and K + . Its adsorption effect under the same conditions significantly exceeds the potassium hexacyanoferrate titanium material reported by Tsinghua University, and it is an excellent choice for treating radioactive Cs ion-containing wastewater.

[0034] Example 2 This embodiment requests to disclose a preparation method of a novel Cs ion selective adsorption material, which adopts the following steps: The carbon material obtained by carbonizing spherical ion exchange resin and the like used in this embodiment has a carbonization preparation process of simple inert gas carbonization. Its specific surface area is 518 m 2 / g, pore volume 0.69 mL / g, and average pore diameter 5.29 nm. Weigh 1000 g of this carbon sphere material, and oxidize it with twice the volume of H2O2 at 40 o °C for 8 hours. After the obtained carbon spheres are washed and dried, the surface carboxyl content is measured to be 0.1 mmol / g. Prepare 2.5 L of barium nitrate solution according to 3 times the molar ratio of the carboxyl content (the molar ratio of barium ions to carboxyl groups is 3:1), and impregnate the carbon spheres after H2O2 oxidation for 10 hours. Filter out the carbon spheres, wash them with a small amount of water, and then dry them. Then prepare a sodium ferrocyanide solution 5 times the molar amount of carboxyl groups in the carbon spheres, with the acidity [H + =0.01 mol / L, and load it into the pores of the above-mentioned carbon spheres adsorbed with barium ions by the method of equal volume impregnation. React at 100 o °C for 24 hours. Wash the carbon spheres with water until the effluent is completely colorless, and then dry them to obtain a carbon sphere material with sodium barium hexacyanoferrate loaded inside. The loading amount of the active adsorption component sodium barium hexacyanoferrate is 4.5%. The selective absorption ability of this material for Cs ions is characterized by absorbing 1 mg / L of Cs ions in H ions, Na ions, and K ions with concentrations of 1 mol / L, 0.5 mol / L, and 0.1 mol / L respectively. The adsorption time is 12 h, and the distribution coefficient of the adsorbent is calculated according to the formula (the absorbent is 0.2 g, and the absorption solution is 50 mL): Kd Kd = ( C 0 C0 - C 1 Ce) F / C 1 where C 0 C0: Cs ion concentration in the solution before adsorption (=1000 μg / L); C 1 Ce: ion concentration in the solution after adsorption (mg / L); F V / m: mass ratio of the absorption solution volume to the adsorbent mass (50 / 0.2 = 250 mL / g).

[0035] The Cs ion concentration in the liquid after absorption is shown in Table 2: Table 2 Cs ion concentration in the liquid in Example 2 Interfering ions and concentrations Final concentration of Cs ions (μg / L) <![CDATA[H + 1mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[H + 0.5 mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[H + 0.1mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[Sodium + 0.1 mol / L (sodium chloride)]]> 7.43 33397 <![CDATA[Sodium + 0.5 mol / L (sodium chloride)]]> 10.2 24260 <![CDATA[Sodium + 1 mol / L (sodium chloride)]]> 14.8 16641 <![CDATA[K + 0.1mol / L (KCl)]]> 13.5 18268 <![CDATA[K + 0.5mol / L (KCl)]]> 91.7 2476 <![CDATA[K + 1mol / L (KCl)]]> 192 1052 From the adsorption test results, it can be seen that H+ The presence has no impact on the material's adsorption of Cs ions at all, which is incomparable to ion exchange resin materials. The material still exhibits strong capturing ability for Cs ions under the interference of Na + and K + . However, compared with Example 1, since the loading amount of the active component is slightly less and the specific surface area of the raw material carbon spheres is slightly lower, the adsorption effect is slightly worse. However, because Ba 2+ ions are loaded in it, it has good shielding ability for the γ-rays released by radioactive Cs ions and is an excellent choice for treating wastewater containing radioactive Cs ions.

[0036] Example 3 This example requests to disclose a preparation method of a novel Cs ion selective adsorption material, which adopts the following steps: The carbon material obtained by carbonization and activation of spherical ion exchange resin used in this example has a specific surface area of 1025 m 2 / g, a pore volume of 0.95 mL / g, and an average pore diameter of 3.71 nm. Weigh 1000 g of this carbon sphere material and use four times the volume of 0.25 mol / L acidic K2Cr2O7 ([H + =0.5 mol / L) to oxidize it at 90 o °C for 24 hours. After the obtained carbon spheres are washed and dried, the surface carboxyl content is measured to be 5 mmol / g. Prepare 2.5 L of zinc chloride solution according to 0.1 times the molar ratio of the carboxyl content (the molar ratio of zinc ions to carboxyl ions is 3:1), and impregnate the carbon spheres oxidized by K2Cr2O7 for 20 hr. Filter out the carbon spheres, wash them with a small amount of water, and then dry them. Then prepare ammonium hexacyanoferrate solution with 0.3 times the molar amount of carboxyl groups in the carbon spheres, with the acidity [H + =2 mol / L, and use the equal-volume impregnation method to load it into the pores of the above carbon spheres adsorbed with zinc ions. React at 20 o °C for 0.5 hr. Wash the carbon spheres with water until the effluent is completely colorless, and then dry them to obtain carbon sphere materials with ammonium hexacyanoferrozinc loaded inside. The loading amount of the active adsorption component ammonium hexacyanoferrozinc is 1.31%. The selective absorption ability of this material for Cs ions is characterized by absorbing 1 mg / L of Cs ions in H ions, Na ions, and K ions with concentrations of 1 mol / L, 0.5 mol / L, and 0.1 mol / L respectively, with an adsorption time of 12 h. Calculate the distribution coefficient of the adsorbent according to the formula (the adsorbent is 0.2 g and the absorption liquid is 50 mL): Kd = ( C 0 - C 1 ) F / C1 In the formula C 0 : The concentration of Cs ions in the solution before adsorption (= 1000 μg / L); C 1 : The concentration of ions in the solution after adsorption (mg / L); F : The mass ratio of the volume of the absorbent solution to the mass of the adsorbent (50 / 0.2 = 250 mL / g).

[0037] The concentration of Cs ions in the liquid after absorption is shown in Table 3: Table 3 Concentration of Cs ions in the liquid in Example 3 Interfering ions and concentrations Final concentration of Cs ions (μg / L) <![CDATA[H + 1mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[H + 0.5mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[H + 0.1mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[Sodium + 0.1 mol / L (sodium chloride)]]> 15.1 16306 <![CDATA[Sodium + 0.5 mol / L (sodium chloride)]]> 23.3 10480 <![CDATA[Sodium + 1 mol / L (sodium chloride)]]> 40.1 5984 <![CDATA[K + 0.1mol / L (KCl)]]> 30.2 8028 <![CDATA[K + 0.5mol / L (KCl)]]> 146 1462 <![CDATA[K + 1mol / L (KCl)]]> 233 823 From the adsorption test results, it can be seen that the presence of H + has no effect on the adsorption of Cs ions by the material at all, which is completely incomparable to the ion exchange resin material. The material still shows a certain ability to capture Cs ions under the interference of Na + and K + . However, compared with Example 1, because the loading amount of the active component is too small, the adsorption effect is slightly worse. The reason for the low loading amount may also be that the ammonium ions provided by ammonium hexacyanoferrate have a certain complexation shielding effect on zinc, resulting in insufficient reaction between ammonium hexacyanoferrate and zinc ions. Moreover, the low reaction temperature and short reaction time may also be the reasons for the low loading amount.

[0038] Example 4 This example requests to disclose a preparation method of a novel Cs ion selective adsorption material, which adopts the following steps: The carbon material obtained by carbonizing and activating spherical ion exchange resin used in this example has a specific surface area of 831 m 2 / g, a pore volume of 0.69 mL / g, and an average pore diameter of 3.80 nm. Weigh 1000 g of this carbon sphere material and use five times the volume of 0.03 mol / L acidic KMnO4 ([H + =0.5 mol / L) to oxidize it at 70 o °C for 4 hours. After the obtained carbon spheres are washed and dried, the surface carboxyl group content is measured to be 2 mmol / g. Prepare 2.5 L of cobalt chloride solution according to 0.7 times the molar ratio of the carboxyl group content (the molar ratio of barium ions to carboxyl groups is 0.7:1), and impregnate the carbon spheres after KMnO4 oxidation for 10 hours. Filter out the carbon spheres, wash them with a small amount of water, and then dry them. Then prepare a potassium hexacyanoferrate solution twice the molar amount of the carboxyl groups in the carbon spheres, with an acidity of [H + =1 mol / L, and load it into the pores of the above carbon spheres adsorbed with cobalt ions by the method of equal volume impregnation at 100 oReact at 48 h under C. After the carbon spheres are fully washed with water until the effluent water is completely colorless, dry them to obtain a carbon sphere material with potassium hexacyanoferrate cobalt loaded inside. The loading amount of the active adsorption component potassium hexacyanoferrate cobalt is 10.2%. The selective absorption ability of this material for Cs ions is characterized by absorbing 1 mg / L of Cs ions in H ions, Na ions, and K ions with concentrations of 1 mol / L, 0.5 mol / L, and 0.1 mol / L respectively. The adsorption time is 12 h. Calculate the distribution coefficient of the adsorbent according to the formula (the adsorbent is 0.2 g and the absorption liquid is 50 mL): Kd = ( C 0 - C 1 ) F / C 1 In the formula C 0 : The concentration of Cs ions in the solution before adsorption (= 1000 μg / L); C 1 : The concentration of ions in the solution after adsorption (mg / L); F : The mass ratio of the absorption liquid volume to the adsorbent mass (50 / 0.2 = 250 mL / g).

[0039] The concentration of Cs ions in the liquid after absorption is shown in Table 4: Table 4 Concentration of Cs ions in the liquid in Example 4 Interfering ions and concentrations Final concentration of Cs ions (μg / L) <![CDATA[H + 1mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[H + 0.5 mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[H + 0.1mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[Sodium + 0.1 mol / L (sodium chloride)]]> 1.02 244848 <![CDATA[Sodium + 0.5 mol / L (sodium chloride)]]> 2.87 86858 <![CDATA[Sodium + 1 mol / L (Sodium Chloride)]]> 3.71 67135 <![CDATA[K + 0.1mol / L (KCl)]]> 7.42 33442 <![CDATA[K + 0.5mol / L (KCl)]]> 29.6 8196 <![CDATA[K + 1mol / L (KCl)]]> 98.3 2293 From the adsorption test results, it can be seen that the presence of H + has no effect on the material's adsorption of Cs ions at all, which is completely incomparable to ion exchange resin materials. The material still shows a strong capturing ability for Cs ions under the interference of Na + and K + . However, compared with Example 1, since Co 2+ ions are used as the precipitating agent for potassium hexacyanoferrate, the obtained potassium hexacyanoferrate cobalt shows good selective absorption ability for Cs ions and is an excellent choice for treating radioactive Cs ion-containing wastewater.

[0040] Example 5 This example requests to disclose a preparation method of a novel Cs ion selective adsorption material, which adopts the following steps: The carbon material obtained by carbonizing and activating spherical ion exchange resin used in this example has a specific surface area of 875 m 2 / g, a pore volume of 0.787 mL / g, and an average pore diameter of 3.6 nm. Weigh 1000 g of this carbon sphere material and use three times the volume of concentrated nitric acid HNO3 at 40o Oxidize at 120 °C for 12 hours. After washing and drying the obtained carbon spheres, the carboxyl content on their surface is measured to be 2.5 mmol / g. Prepare 2.5 L of magnesium sulfate solution according to the molar amount twice that of the carboxyl content (the molar ratio of magnesium ions to carboxyl groups is 2:1), and immerse the carbon spheres oxidized by HNO₃ for 10 hours. Filter out the carbon spheres, wash them with a small amount of water, and then dry them. Then prepare potassium ferricyanide solution with a molar amount twice that of the carboxyl groups in the carbon spheres, with the acidity [H + ⁺] = 1 mol / L, and load it into the pores of the above carbon spheres adsorbed with magnesium ions by the method of equal-volume immersion. React at 60 o °C for 10 hours. Wash the carbon spheres thoroughly with water until the effluent is completely colorless, and then dry them to obtain a carbon sphere material with potassium ferricyanide-magnesium loaded inside. The loading amount of the active adsorption component potassium ferricyanide-magnesium is 7.31%. The selective absorption ability of this material for Cs ions is characterized by absorbing 1 mg / L of Cs ions in H⁺, Na⁺, and K⁺ solutions with concentrations of 1 mol / L, 0.5 mol / L, and 0.1 mol / L respectively, with an adsorption time of 12 hours. Calculate the distribution coefficient of the adsorbent according to the formula (the adsorbent is 0.2 g and the absorption solution is 50 mL): Kd Kd = ( C 0 C₀ C 1 - C F ) / C 1 where C 0 C₀: the concentration of Cs ions in the solution before adsorption (= 1000 μg / L); C 1 C: the concentration of ions in the solution after adsorption (mg / L); F V / m: the mass ratio of the absorption solution volume to the adsorbent mass (50 / 0.2 = 250 mL / g).

[0041] The concentration of Cs ions in the liquid after absorption is shown in Table 5: Table 5 Concentration of Cs ions in the liquid in Example 5 Interfering ions and concentrations Final concentration of Cs ions (μg / L) <![CDATA[H + 1mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[H + 0.5 mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[H + 0.1 mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[Sodium + 0.1 mol / L (sodium chloride)]]> 6.48 38330 <![CDATA[Sodium + 0.5 mol / L (sodium chloride)]]> 9.21 26894 <![CDATA[Sodium + 1 mol / L (sodium chloride)]]> 17.3 14201 <![CDATA[K + 0.1mol / L (KCl)]]> 15.4 15983 <![CDATA[K + 0.5mol / L (KCl)]]> 76.8 3005 <![CDATA[K + 1mol / L (KCl)]]> 185.5 1098 From the adsorption test results, it can be seen that the presence of H + ⁺ has no effect on the material's adsorption of Cs ions at all, which is completely incomparable to ion exchange resin materials. The material still shows a strong capturing ability for Cs ions under the interference of Na + ⁺ and K + ⁺. Since the raw material magnesium sulfate is inexpensive and the adsorption performance of the material is medium, this material also has certain application value.

[0042] Example 6 This embodiment requests to disclose a preparation method of a novel Cs ion selective adsorption material, which adopts the following steps: The carbon material obtained by carbonization and activation of spherical ion exchange resin used in this embodiment has a specific surface area of 831 m 2 / g, a pore volume of 0.69 mL / g, and an average pore diameter of 3.80 nm. Weigh 1000 g of this carbon sphere material, and use three times the volume of 5 mol / L HNO3 to oxidize it at 50 o °C for 7 hours. After the obtained carbon spheres are washed and dried, the surface carboxyl group content is measured to be 2.6 mmol / g. Prepare 2.5 L of nickel chloride solution according to the molar ratio equal to the carboxyl group content (the molar ratio of nickel ions to carboxyl groups is 1:1), and impregnate the carbon spheres after HNO3 oxidation for 10 hours. Filter out the carbon spheres, wash them with a small amount of water, and then dry them. Then prepare a potassium ferricyanide solution with a molar amount one time that of the carboxyl groups in the carbon spheres, with an acidity of [H + =1 mol / L, and load it into the pores of the above-mentioned carbon spheres adsorbed with nickel ions by the method of equal volume impregnation. React at 80 o °C for 24 hours. Wash the carbon spheres with water until the effluent is completely colorless, and then dry them to obtain a carbon sphere material with potassium nickel ferrocyanide loaded inside. The loading amount of the active adsorption component potassium nickel ferrocyanide is 8.1%. The selective absorption ability of this material for Cs ions is characterized by absorbing 1 mg / L of Cs ions in H ions, Na ions, and K ions with concentrations of 1 mol / L, 0.5 mol / L, and 0.1 mol / L respectively, with an adsorption time of 12 hours. Calculate the distribution coefficient of the adsorbent according to the formula (0.2 g of adsorbent, 50 mL of absorption solution): Kd = ( C 0 - C 1 ) F / C 1 In the formula C 0 : Cs ion concentration in the solution before adsorption (=1000 μg / L); C 1 : Ion concentration in the solution after adsorption (mg / L); F : Mass ratio of the absorption solution volume to the adsorbent mass (50 / 0.2 = 250 mL / g).

[0043] The Cs ion concentration in the liquid after absorption is shown in Table 6: Table 6 Cs ion concentration in the liquid in Example 6 Interfering ions and concentrations Final concentration of Cs ions (μg / L) <![CDATA[H + 1mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[H + 0.5 mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[H + 0.1 mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[Sodium + 0.1 mol / L (sodium chloride)]]> 5.98 41556 <![CDATA[Sodium + 0.5 mol / L (sodium chloride)]]> 10.2 24260 <![CDATA[Sodium + 1 mol / L (sodium chloride)]]> 19.3 12703 <![CDATA[K + 0.1mol / L (KCl)]]> 17.5 14036 <![CDATA[K + 0.5 mol / L (KCl)]]> 88.6 2572 <![CDATA[K + 1mol / L (KCl)]]> 173.1 1194 From the adsorption test results, it can be seen that H+ The presence has no impact on the material's adsorption of Cs ions at all, which is incomparable to ion exchange resin materials. The material still exhibits strong capturing ability for Cs ions under the interference of Na + and K + and is an excellent choice for treating radioactive Cs ion-containing wastewater.

[0044] Example 7 This example requests to disclose a preparation method of a novel Cs ion-selective adsorption material, which adopts the following steps: The carbon material obtained by carbonizing and activating spherical ion exchange resin used in this example has a specific surface area of 831 m 2 / g, a pore volume of 0.69 mL / g, and an average pore diameter of 3.80 nm. Weigh 1000 g of this carbon sphere material, and use three times the volume of 5 mol / L HNO3 to oxidize it at 50 o °C for 7 hours. After the obtained carbon spheres are washed and dried, the surface carboxyl content is measured to be 2.6 mmol / g. Prepare 2.5 L of manganese nitrate solution according to the molar ratio equal to the carboxyl content (the molar ratio of manganese ions to carboxyl groups is 1:1), and impregnate the carbon spheres after HNO3 oxidation for 10 hours. Filter out the carbon spheres, wash them with a small amount of water, and then dry them. Then prepare a potassium ferricyanide solution with a molar amount one time that of the carboxyl groups in the carbon spheres, with the acidity [H + =1 mol / L, and use the equal-volume impregnation method to load it into the pores of the above carbon spheres adsorbed with manganese ions. React at 80 o °C for 24 hours. Wash the carbon spheres with water until the effluent is completely colorless, and then dry them to obtain a carbon sphere material with potassium ferricyanomanganate loaded inside. The loading amount of the active adsorption component potassium ferricyanomanganate is 7.33%. The selective absorption ability of this material for Cs ions is characterized by absorbing 1 mg / L of Cs ions in H ions, Na ions, and K ions with concentrations of 1 mol / L, 0.5 mol / L, and 0.1 mol / L respectively, with an adsorption time of 12 hours. Calculate the distribution coefficient of the adsorbent according to the formula (the absorbent is 0.2 g, and the absorption solution is 50 mL): Kd = ( C 0 - C 1 ) F / C 1 In the formula C 0 : The concentration of Cs ions in the solution before adsorption (=1000 μg / L); C 1 : The concentration of ions in the solution after adsorption (mg / L); F: Mass ratio of the volume of the absorbent liquid to the mass of the adsorbent (50 / 0.2 = 250 mL / g).

[0045] The Cs ion concentration in the liquid after absorption is shown in Table 7: Table 7 Cs ion concentration in the liquid in Example 7 Interfering ions and concentrations Final concentration of Cs ions (μg / L) <![CDATA[H + 1mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[H + 0.5mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[H + 0.1mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[Sodium + 0.1 mol / L (sodium chloride)]]> 3.46 72004 <![CDATA[Sodium + 0.5 mol / L (sodium chloride)]]> 4.71 52829 <![CDATA[Na + 1mol / L (NaCl)]]> 6.55 37918 <![CDATA[K + 0.1mol / L (KCl)]]> 9.47 26149 <![CDATA[K + 0.5mol / L (KCl)]]> 58.1 4052 <![CDATA[K + 1mol / L (KCl)]]> 119.8 1837 From the adsorption test results, it can be seen that the presence of H + has no effect on the material's adsorption of Cs ions at all, which is completely incomparable to ion exchange resin materials. The material still shows a strong ability to capture Cs ions under the interference of Na + and K + , making it an excellent choice for treating radioactive Cs ion-containing wastewater.

[0046] Example 8 This example requests to disclose a preparation method of a novel Cs ion selective adsorption material, which adopts the following steps: The carbon material obtained by carbonization and activation of spherical ion exchange resin used in this example has a specific surface area of 831 m 2 / g, a pore volume of 0.69 mL / g, and an average pore diameter of 3.80 nm. Weigh 1000 g of this carbon sphere material and oxidize it with three times the volume of 5 mol / L HNO3 at 50 o °C for 7 hours. After the obtained carbon spheres are washed and dried, the surface carboxyl group content is measured to be 2.6 mmol / g. Prepare 2.5 L of ferric nitrate solution according to the molar ratio equal to the carboxyl group content (the molar ratio of ferric ions to carboxyl groups is 0.5:1), and impregnate the carbon spheres oxidized by HNO3 for 10 hours. Filter out the carbon spheres, wash them with a small amount of water, and then dry them. Then prepare a potassium ferrocyanide solution with a molar amount 1 time that of the carboxyl groups in the carbon spheres, with the acidity [H + = 1 mol / L, and load it into the pores of the above carbon spheres adsorbed with ferric ions by the method of equal volume impregnation. React at 80 o °C for 24 hours. Wash the carbon spheres with water until the effluent is completely colorless, and then dry them to obtain a carbon sphere material with potassium ferrocyanoferrate loaded inside. The loading amount of the active adsorption component potassium ferrocyanoferrate is 6.81%. The selective absorption ability of this material for Cs ions is characterized by absorbing 1 mg / L of Cs ions in H ions, Na ions, and K ions with concentrations of 1 mol / L, 0.5 mol / L, and 0.1 mol / L respectively, with an adsorption time of 12 hours. Calculate the distribution coefficient of the adsorbent according to the formula (the adsorbent is 0.2 g, and the absorbent liquid is 50 mL): Kd = ( C 0 - C 1 ) F / C 1 wherein C 0 : the concentration of Cs ions in the solution before adsorption (= 1000 μg / L); C 1 : the ion concentration in the solution after adsorption (mg / L); F : the mass ratio of the volume of the absorbent solution to the mass of the adsorbent (50 / 0.2 = 250 mL / g).

[0047] The concentration of Cs ions in the liquid after absorption is shown in Table 8: Table 8 Concentration of Cs ions in the liquid in Example 8 Interfering ions and concentrations Final concentration of Cs ions (μg / L) <![CDATA[H + 1mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[H + 0.5 mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[H + 0.1mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[Sodium + 0.1 mol / L (sodium chloride)]]> 2.98 83642 <![CDATA[Sodium + 0.5 mol / L (sodium chloride)]]> 5.12 48578 <![CDATA[Sodium + 1 mol / L (Sodium Chloride)]]> 6.46 38450 <![CDATA[K + 0.1mol / L (KCl)]]> 10.5 23559 <![CDATA[K + 0.5mol / L (KCl)]]> 55.7 4238 <![CDATA[K + 1mol / L (KCl)]]> 108.9 2046 From the results of the adsorption test, it can be seen that the presence of H + has no effect on the adsorption of Cs ions by the material at all, which is incomparable to the ion exchange resin material. The material still shows a strong ability to capture Cs ions under the interference of Na + and K + , and it is an excellent choice for treating radioactive Cs ion-containing wastewater.

[0048] Example 9 This example requests to disclose a preparation method of a novel Cs ion selective adsorption material, which adopts the following steps: The carbon material obtained by carbonization and activation of spherical ion exchange resin used in this example has a specific surface area of 831 m 2 / g, a pore volume of 0.69 mL / g, and an average pore diameter of 3.80 nm. Weigh 1000 g of this carbon sphere material and oxidize it with three times the volume of 5 mol / L HNO3 at 50 o °C for 7 hours. After the obtained carbon spheres are washed and dried, the surface carboxyl content is measured to be 2.6 mmol / g. Prepare 2.5 L of lanthanum nitrate solution according to the molar ratio equal to the carboxyl content (the molar ratio of lanthanum ions to carboxyl groups is 0.5:1), impregnate the carbon spheres oxidized by HNO3 for 10 hours, filter out the carbon spheres, wash them with a small amount of water and then dry them. Then prepare a potassium ferrocyanide solution with a molar amount one time that of the carboxyl groups in the carbon spheres, with the acidity [H + =1 mol / L, and load it into the pores of the above carbon spheres adsorbed with lanthanum ions by the method of equal volume impregnation. 80 oReact at 24 °C for 24 hours. After washing the carbon spheres thoroughly with water until the effluent is completely colorless, dry them to obtain a carbon sphere material with potassium hexacyanoferrate(III) lanthanum loaded inside. The loading amount of the active adsorption component potassium hexacyanoferrate(III) lanthanum is 9.12% (due to the relatively large atomic weight of lanthanum). The selective absorption ability of this material for Cs ions is characterized by absorbing 1 mg / L of Cs ions in H⁺, Na⁺, and K⁺ solutions with concentrations of 1 mol / L, 0.5 mol / L, and 0.1 mol / L respectively, and the adsorption time is 12 hours. Calculate the distribution coefficient of the adsorbent according to the formula (0.2 g of adsorbent, 50 mL of absorption solution): Kd = ( C 0 - C 1 ) F / C 1 Where C 0 : The concentration of Cs ions in the solution before adsorption (= 1000 μg / L); C 1 : The concentration of ions in the solution after adsorption (mg / L); F : The mass ratio of the volume of the absorption solution to the mass of the adsorbent (50 / 0.2 = 250 mL / g).

[0049] The concentration of Cs ions in the liquid after absorption is shown in Table 9: Table 9 Concentration of Cs ions in the liquid in Example 9 Interfering ions and concentrations Final concentration of Cs ions (μg / L) <![CDATA[H + 1mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[H + 0.5 mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[H + 0.1mol / L (HCl)]]> <1 μg / L (not detectable) >249750 <![CDATA[Sodium + 0.1 mol / L (sodium chloride)]]> 4.26 58435 <![CDATA[Sodium + 0.5 mol / L (sodium chloride)]]> 6.88 36087 <![CDATA[Sodium + 1 mol / L (sodium chloride)]]> 7.96 31157 <![CDATA[K + 0.1mol / L (KCl)]]> 13.1 18834 <![CDATA[K + 0.5mol / L (KCl)]]> 58.4 4031 <![CDATA[K + 1mol / L (KCl)]]> 120.9 1818 From the adsorption test results, it can be seen that the presence of H + has no effect on the material's adsorption of Cs ions at all, which is completely incomparable to ion exchange resin materials. The material still shows a strong capture ability for Cs ions under the interference of Na + and K + , and it is an excellent choice for treating radioactive Cs ion-containing wastewater.

[0050] Comparative Example 1 The carbon material obtained by carbonization and activation of spherical ion exchange resin used in this example has a specific surface area of 831 m 2 / g, a pore volume of 0.69 mL / g, and an average pore diameter of 3.80 nm. Weigh 1000 g of this carbon sphere material, and measure that the surface carboxyl content is 0.05 mmol / g. Immerse the carbon spheres in 2.5 L of a 0.2 mol / L copper nitrate solution for 10 hours. Filter out the carbon spheres, wash them with a small amount of water, and then dry them. Then take 1 mol of potassium hexacyanoferrate, and the acidity [H += 1 mol / L, and was loaded into the pores of the carbon spheres adsorbed with copper nitrate by the equal - volume impregnation method. React at 80 o °C for 24 h. After washing the carbon spheres with water until the effluent was completely colorless, they were dried to obtain a carbon sphere material with potassium copper hexacyanoferrate loaded inside. The loading amount of the active adsorption component potassium copper hexacyanoferrate was only 0.08%. The reason is that the carbon spheres have too weak a fixing ability for copper ions, and the copper ions escape after washing, leaving too little residual copper ions. Therefore, the content of potassium copper hexacyanoferrate produced after reacting with potassium hexacyanoferrate is too low. The selective absorption ability of this material for Cs ions was characterized by absorbing 1 mg / L of Cs ions in H⁺, Na⁺, and K⁺ solutions with concentrations of 1 mol / L, 0.5 mol / L, and 0.1 mol / L respectively. The adsorption time was 12 h. The distribution coefficient of the adsorbent was calculated according to the formula (the absorbent was 0.2 g and the absorbent solution was 50 mL): Kd = ( C 0 - C 1 ) F / C 1 In the formula C 0 : The concentration of Cs ions in the solution before adsorption (= 1000 μg / L); C 1 : The concentration of ions in the solution after adsorption (mg / L); F : The mass ratio of the absorbent solution volume to the mass of the adsorbent (50 / 0.2 = 250 mL / g).

[0051] The concentration of Cs ions in the liquid after absorption is shown in Table 10: Table 10 Concentration of Cs ions in the liquid in Comparative Example 1 Interfering ions and concentrations Final concentration of Cs ions (μg / L) <![CDATA[H + 1mol / L (HCl)]]> 59.7 3938 <![CDATA[H + 0.5mol / L (HCl)]]> 67.3 3465 <![CDATA[H + 0.1mol / L (HCl)]]> 79.9 2879 <![CDATA[Sodium + 0.1 mol / L (sodium chloride)]]> 87.1 2620 <![CDATA[Sodium + 0.5 mol / L (sodium chloride)]]> 96.5 2340 <![CDATA[Sodium + 1 mol / L (sodium chloride)]]> 188.7 1075 <![CDATA[K + 0.1mol / L (KCl)]]> 232.9 823 <![CDATA[K + 0.5mol / L (KCl)]]> 317.6 537 <![CDATA[K + 1mol / L (KCl)]]> 517.8 233 From the adsorption test results, due to the too low content of the active component, the adsorption activity of the material for Cs ions is not good.

[0052] Comparative Example 2 The carbon material obtained by carbonization and activation of spherical ion - exchange resin used in this example has a specific surface area of 831 m 2 ² / g, a pore volume of 0.69 mL / g, and an average pore diameter of 3.80 nm. Weigh 1000 g of this carbon sphere material, and measure that the surface carboxyl content is 0.05 mmol / g. Load 2.5 L of 0.2 mol / L cobalt nitrate solution into it, impregnate the carbon spheres for 10 h, filter out the carbon spheres without washing and directly dry them. Then take 1 mol of potassium hexacyanoferrate and load it into the pores of the above - mentioned carbon spheres adsorbed with cobalt nitrate by the equal - volume impregnation method. 80o React at C for 24 hours. After thoroughly washing the carbon spheres with water until the effluent water is completely colorless, dry them to obtain a carbon sphere material with potassium hexacyanoferrate cobalt loaded inside. The loading amount of the active adsorption component potassium hexacyanoferrate cobalt is only 0.03%. The reason is that the cobalt ions in the carbon spheres are not fixed and are soluble cobalt nitrate. When encountering the hexacyanoferrate solution, they dissolve quickly, react with potassium hexacyanoferrate on the surface of the carbon spheres, blocking the potassium hexacyanoferrate solution from entering the interior of the carbon spheres. Potassium hexacyanoferrate cobalt is only generated in a very small area on the outer shell of the carbon spheres, and a large amount of this potassium hexacyanoferrate cobalt is lost during subsequent washing. This is also the reason why it is difficult for the washing water to become colorless during the subsequent washing process of this material. Due to the too low content of potassium hexacyanoferrate cobalt in the material, its adsorption performance for Cs ions is not good. The selective absorption ability of this material for Cs ions is characterized by absorbing 1 mg / L of Cs ions in H ions, Na ions, and K ions with concentrations of 1 mol / L, 0.5 mol / L, and 0.1 mol / L respectively. The adsorption time is 12 hours. Calculate the distribution coefficient of the adsorbent according to the formula (the absorbent is 0.2 g, and the absorbent solution is 50 mL): Kd = ( C 0 - C 1 ) F / C 1 In the formula C 0 : The concentration of Cs ions in the solution before adsorption (=1000 μg / L); C 1 : The concentration of ions in the solution after adsorption (mg / L); F : The mass ratio of the absorbent solution volume to the mass of the adsorbent (50 / 0.2 = 250 mL / g).

[0053] The concentration of Cs ions in the liquid after absorption is shown in Table 11: Table 11 Concentration of Cs ions in the liquid in Comparative Example 2 Interfering ions and concentrations Final concentration of Cs ions (μg / L) <![CDATA[H + 1mol / L (HCl)]]> 202.8 983 <![CDATA[H + 0.5 mol / L (HCl)]]> 315.7 542 <![CDATA[H + 0.1mol / L (HCl)]]> 376.2 414 <![CDATA[Sodium + 0.1 mol / L (sodium chloride)]]> 396.5 380 <![CDATA[Sodium + 0.5 mol / L (sodium chloride)]]> 454.3 300 <![CDATA[Sodium + 1 mol / L (Sodium Chloride)]]> 496.8 253 <![CDATA[K + 0.1mol / L (KCl)]]> 512.7 238 <![CDATA[K + 0.5mol / L (KCl)]]> 812.1 57.8 <![CDATA[K + 1mol / L (KCl)]]> 886.4 32 From the adsorption test results, it can be seen that due to the too low content of the active component, the adsorption activity of the material for Cs ions is not good.

Claims

1. A preparation method of a novel Cs ion selective adsorption material, characterized in that Its material carrier is a spherical carbon material obtained by carbonizing a spherical ion exchanger, and its active component is hexacyanoferrate particles loaded inside the spherical carbon material. First, non-group IA metal ions are loaded onto the adsorption sites inside the spherical carbon material, and then a soluble hexacyanoferrate solution is immersed inside the spherical carbon material. The non-group IA metal ions and the soluble hexacyanoferrate undergo a coprecipitation reaction to form hexacyanoferrate particles containing non-group IA metal ions, which are in-situ fixed inside the spherical carbon material to obtain this novel Cs ion-selective adsorption material.

2. The preparation method of a novel Cs ion selective adsorption material according to claim 1, characterized in that, The spherical carbon material is obtained by carbonizing an acidic or basic styrene-based ion exchange resin.

3. The preparation method of a novel Cs ion selective adsorption material according to claim 1, characterized in that, The spherical carbon material is obtained by carbonizing an acidic or basic phenolic resin-based ion exchange resin.

4. The preparation method of a novel Cs ion selective adsorption material according to claim 1, characterized in that, The spherical carbon material is pre-oxidized, and its surface carboxyl content is 0.1 mmol / g to 5 mmol / g.

5. The preparation method of a novel Cs ion selective adsorption material according to claim 4, wherein, The pre-oxidant of the spherical carbon material is one or any arbitrary proportion mixture of HNO3, H2O2, acidic potassium permanganate, and acidic potassium dichromate.

6. The preparation method of a novel Cs ion selective adsorption material according to claim 1, characterized in that, The non-group IA metal ion described above is Ca 2+ , Mg 2+ , Sr 2+ , Ba 2+ , Cu 2+ , Zn 2+ , Co 2+ , Ni 2+ , Pb 2+ , Fe 3+ , Cr 3+ , La 3+ , Ag + , Mn 2 + , Al 3+ Any one or any mixture of several of them in any proportion, and the dosage is 0.1 to 3 times the amount of carboxyl groups in the spherical carbon material.

7. The preparation method of a novel Cs ion selective adsorption material according to claim 1, characterized in that, The soluble hexacyanoferrate is any one or any arbitrary proportion mixture of potassium hexacyanoferrate, sodium hexacyanoferrate, and ammonium hexacyanoferrate, and its dosage is 0.3 to 5 times the amount of carboxyl substance in the spherical carbon material.

8. The preparation method of a novel Cs ion selective adsorption material according to claim 1, characterized in that, The soluble hexacyanoferrate solution that reacts with non-group IA metal ions already present inside the carbon spheres is acidic, with its [H + = 0.01 to 2 mol / L.

9. The preparation method of a novel Cs ion selective adsorption material according to claim 1, characterized in that, The reaction temperature of non-group IA metal ions inside the carbon spheres and soluble hexacyanoferrates is 20~100 o °C, and the reaction time is 0.5~48 hr.

10. A novel Cs ion selective adsorption material, characterized in that, Prepared by the preparation method according to any one of claims 1 to 9.

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