Ion exchange material for efficient nuclide separation and preparation method and application method thereof

Abstract

The invention relates to the technical field of ion exchange separation of nuclides, and particularly discloses an ion exchange material for efficient nuclide separation as well as a preparation method and an application method of the ion exchange material aiming at the problems that an existing metal ion doped zirconium phosphate composite material is unstable in material form, insufficient in acid and alkali resistance and poor in adsorption effect. Comprising the following steps: taking sodium phosphate powder and zirconium oxychloride octahydrate powder, and performing solid-phase grinding and uniform mixing to obtain a primary mixture; placing the primary mixture in a closed environment, performing hydrothermal treatment, cooling, taking out, washing and drying to obtain zirconium phosphate; adding zirconium phosphate into the sodium alginate solution, heating and stirring to obtain a mixed dispersion liquid; dropwise adding the mixed dispersion liquid into a zirconium nitrate cross-linking agent, standing for reaction, filtering, washing and drying in the shade to obtain the ion exchange material. The zirconium nitrate crosslinking technology is adopted, the preparation process is simple, the cost is low, the material stability is high, the nuclide ion adsorption effect is better, and the wide pH value adaptability is achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ion exchange separation of nuclides, in particular to an ion exchange material for efficient nuclide separation and a preparation method and application method thereof. BACKGROUND

[0002] The effective use of nuclear energy has shown great advantages in alleviating energy crisis and environmental problems, but in the process of development, radioactive nuclides are inevitably produced and released into the environment, causing serious threats to ecological environment safety. Among them, the most common high-heat-emitting nuclide 90 Sr has the characteristics of high heat emission, long half-life and strong biological toxicity, which will cause serious pollution to humans and the natural environment. Strontium, which is similar in nature to calcium, is an important component of human bones and teeth, and is mainly absorbed by the human body through water and food. If 90 Sr enters the human body and accumulates in the bones, it will cause damage to bone marrow and bone tissue, and significantly increase the incidence of leukemia and bone tumors. Therefore, how to remove radioactive nuclides 90 Sr has attracted widespread attention from more and more scientists, and if it can be separated and recovered, and effectively utilized (as a radioactive source or a heat source), not only can it effectively reduce the volume of glass solidification body in the spent fuel reprocessing process, greatly reducing the disposal cost, but also can be used as a radioactive source in medical and industrial fields.

[0003] How to efficiently separate and remove 90 Sr and other radioactive nuclides from nuclear waste liquid has become a problem that needs to be solved. At present, there are many methods for removing strontium elements in aqueous solution, such as extraction separation, chemical precipitation method, adsorption separation, ion exchange and membrane separation method. Among them, the ion exchange method mainly exchanges the ions in the ion exchanger with the radioactive ions in the high-level waste liquid, selectively removes the radioactive nuclides, and then removes the radioactive nuclides.

[0004] And the ion exchanger can be divided into inorganic ion exchanger and organic ion exchanger, among which the inorganic ion exchanger has good stability and radiation resistance, and plays an important role in the treatment of radioactive nuclides. Zirconium phosphate, as a kind of layered solid acid, has large specific surface area, surface charge and ion exchange performance, and also has the advantages of high chemical stability and high thermal stability, and is widely used in the separation and treatment of radioactive nuclides. For example, the patent with publication number CN119114034A provides a modified zirconium phosphate / resin composite material and a preparation method thereof, and a method for recovering nuclides in nuclear waste liquid. The modified zirconium phosphate and resin material are used as adsorbents to adsorb and separate the nuclides in the nuclear waste liquid.

[0005] However, existing nuclide ion exchange materials doped with metal ions, as mentioned above, can selectively adsorb nuclides, but they cannot be directly used as adsorption column packing materials. Moreover, the materials have poor morphological stability, resulting in low adsorption capacity and narrow pH adaptability in terms of adsorption effect. Consequently, they exhibit low removal rates for strontium ions and the like in practical industrial applications. Summary of the Invention

[0006] The purpose of this invention is to solve the problems of unstable material morphology, insufficient acid and alkali resistance, and poor adsorption effect of existing metal ion-doped zirconium phosphate composite materials.

[0007] This invention is achieved through the following technical solution: This invention provides a method for preparing ion exchange materials for efficient nuclide separation, comprising the following steps: S1 Take sodium phosphate powder and zirconium oxychloride octahydrate powder, grind them in the solid phase, mix them evenly, and obtain the initial mixture; S2 The initial mixture is placed in a closed environment for hydrothermal treatment, cooled and removed, washed and dried to obtain zirconium phosphate powder; S3 Zirconium phosphate powder was added to sodium alginate solution, heated and stirred to obtain a mixed dispersion of zirconium phosphate and sodium alginate; S4. A zirconium phosphate-sodium alginate mixed dispersion is added dropwise to zirconium nitrate crosslinking agent, allowed to stand for reaction, and then filtered, washed and air-dried in sequence to obtain the ion exchange material.

[0008] Preferably, in step S1, the mass ratio of sodium phosphate powder to zirconium oxychloride octahydrate powder is 1:1~5.

[0009] Preferably, in steps S2 and S3, the mass concentration of sodium alginate solution is 0.5~2.0wt%, and the mass ratio of zirconium phosphate powder to sodium alginate solution is 5~30:1.

[0010] Preferably, the hydrothermal reaction temperature is 80~160℃ and the reaction time is 8~24h.

[0011] Preferably, in step S4, the static reaction time is 5~20h.

[0012] Preferably, the zirconium nitrate crosslinking agent comprises zirconium nitrate with a mass concentration of 1.5 to 2.5 wt%.

[0013] Preferably, the zirconium nitrate crosslinking agent further includes cerium nitrate and glutaraldehyde, and the mass ratio of zirconium nitrate to cerium nitrate and glutaraldehyde is 60~80:10~20:5~15.

[0014] Preferably, the preparation method of the zirconium nitrate crosslinking agent includes the following steps: Take zirconium nitrate and cerium nitrate according to the specified amounts, add them to deionized water, heat to 60-80℃, stir at 200-400 r / min for 40-100 min until completely dissolved; then add glutaraldehyde aqueous solution dropwise, continue stirring for 20-30 min to obtain crosslinked zirconium nitrate crosslinking agent with a mass concentration of 1.5-3.0 wt%, and keep it at 50-70℃ for later use.

[0015] This invention provides a method for applying the above-mentioned ion exchange material for efficient nuclide separation, comprising the following steps: Add the ion exchange material to simulated nuclear waste liquid with a nuclide ion concentration of 50-200 mg / L at a dosage ratio of 1 mg: 0.5-2 mL, mix well, and stir and shake at 150-200 r / min for 10-360 min at 40-60℃. Filter to complete the nuclide separation. The filtered ion exchange material is then acid-washed and used for regeneration and recycling.

[0016] The technical solution of the present invention has the following beneficial effects: The ion exchange material proposed in this invention uses zirconium phosphate as the matrix and sodium alginate as the carrier. This spherical ion exchange material is prepared through zirconium nitrate crosslinking technology. The preparation process is simple and low-cost, and the material exhibits strong stability, wide pH adaptability, and significant adsorption capacity for strontium in solution, showing broad application prospects in the field of radioactive waste treatment. Details are as follows: (1) This invention uses zirconium nitrate as a crosslinking agent. This is to address the problems of poor material stability and weak acid and alkali resistance of existing radionuclide ion exchange separators. Zirconium ions with stronger specific coordination ability are used, which can simultaneously form multiple coordination bonds with the carboxyl group of sodium alginate and the hydroxyl group of zirconium phosphate, thereby significantly improving the structural stability of the beads and enabling them to maintain morphological stability and radionuclide ion removal rate in a wider pH range.

[0017] Furthermore, this invention constructs a more optimized composite zirconium nitrate crosslinking agent. Based on zirconium nitrate, cerium nitrate and glutaraldehyde are introduced as auxiliary crosslinking components. Through multiple synergistic interactions of ion coordination, covalent bonding, and hydrogen bonding, the interfacial interactions with the carboxyl and hydroxyl groups of sodium alginate and the hydroxyl groups of zirconium phosphate are strengthened, avoiding problems such as uneven crosslinking density and insufficient long-term stability that may exist with single zirconium nitrate crosslinking. In detail, zirconium nitrate, as the main crosslinking agent, Zr... 4+ It forms stable ionic coordination bonds with the carboxyl groups of sodium alginate and bridges the coordination with the hydroxyl groups of zirconium phosphate, forming the core framework of the cross-linked network; cerium nitrate, as a rare earth auxiliary cross-linking agent, has the characteristics of small radius and high charge density, and can form multinuclear coordination complexes with multiple carboxyl or hydroxyl groups, filling the gap in single Zr. 4+The cross-linking gaps increase the cross-linking density; glutaraldehyde, as an organic cross-linking aid, forms covalent cross-links by condensing the aldehyde group with the hydroxyl groups on the surface of sodium alginate and zirconium phosphate, thus constructing a dual network with ionic and covalent bonds, which enhances the material's resistance to swelling and mechanical stability.

[0018] (2) The present invention uses a mixture of sodium phosphate and zirconium oxychloride octahydrate for solid-phase grinding and hydrothermal reaction in an in-situ synthesis process. This process can produce highly crystalline zirconium phosphate powder with more uniform particle size and more abundant surface hydroxyl groups in one step, which significantly improves its compatibility with sodium alginate carrier. This solves the problems of poor dispersibility and unstable structure of existing radionuclide ion exchange separators from the source. Moreover, the process used in the preparation is simpler and can also improve the performance of material morphology stability, high adsorption capacity and strong acid and alkali resistance. In other words, it can achieve the effect of cost reduction and efficiency improvement as a whole. Attached Figure Description

[0019] Figure 1 This is a morphology diagram of the ion exchange material in Example 1; Figure 2 The infrared spectrum of the ion exchange material in Example 1; Figure 3 These are morphological images of the ion exchange material in Example 1 after immersion in different pH environments; Figure 4 Sr, the ion exchange material pair in Example 1 2+ Removal rate change curve. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, they are performed according to conventional conditions or conditions recommended by the manufacturer; where the manufacturers of the instruments, equipment, reagents, or raw materials used are not specified, they are all conventional products that can be purchased commercially.

[0021] This invention provides an ion exchange material for efficient nuclide separation, the preparation method of which includes the following steps: (1) Take sodium phosphate powder and zirconium oxychloride octahydrate powder in a mass ratio of 1:1~5, place them in an agate mortar, grind for 10~90 minutes until they are mixed evenly to obtain the initial mixture.

[0022] (2) Place the initial mixture in a polytetrafluoroethylene reactor, seal it, and then place it in an oven at a certain temperature. Heat it to 80~160℃ for hydrothermal treatment. The hydrothermal reaction lasts for 8~24 hours. After the treatment is completed and cooled to room temperature, take it out, wash it with anhydrous ethanol and deionized water until neutral, and dry it to obtain highly crystalline zirconium phosphate powder.

[0023] (3) Take an appropriate amount of sodium alginate powder, place it in a beaker, add deionized water, and sonicate it at 45~65kHz for 20-50 minutes, stopping for 1-3 minutes after every 3-8 minutes of sonication; heat it to 60-80℃ and stir it at 200~400r / min for 40-100 minutes to prepare a sodium alginate solution with a mass concentration of 0.5~2.0wt%.

[0024] (4) Take the zirconium phosphate powder prepared above at a mass ratio of 5~30:1, add it to the prepared sodium alginate solution, heat it to 60-80℃, stir it at 200~400r / min for 40~100min, so that the zirconium phosphate powder is evenly dispersed in the sodium alginate solution, and obtain zirconium phosphate-sodium alginate mixed dispersion.

[0025] (5) Take an appropriate amount of zirconium nitrate, dissolve it in deionized water, heat it to 60-80℃, stir it at 200-400r / min for 40-100min, and prepare a zirconium nitrate aqueous solution with a mass concentration of 1.5-2.5wt%, which is the zirconium nitrate crosslinking agent.

[0026] Furthermore, this invention suggests that those skilled in the art can further add cerium nitrate and glutaraldehyde as auxiliary crosslinking components to the zirconium nitrate crosslinking agent based on actual application effects, forming a multi-component composite crosslinking system, and controlling the mass ratio of zirconium nitrate to cerium nitrate and glutaraldehyde to be 60~80:10~20:5~15. The specific preparation process is as follows: zirconium nitrate and cerium nitrate are measured and added to deionized water, heated to 60-80℃, and stirred at 200-400 r / min for 40-100 min until completely dissolved; then, glutaraldehyde aqueous solution is added dropwise, and stirring continues for 20-30 min to obtain a crosslinked zirconium nitrate crosslinking agent with a mass concentration of 1.5-3.0 wt%, which is then kept at 50-70℃ for later use.

[0027] (6) The zirconium phosphate-sodium alginate mixed dispersion is added dropwise to the zirconium nitrate crosslinking agent and left to stand at 30~70℃ for 5~20h to form spherical zirconium phosphate-sodium alginate composite ion exchange microbeads. After filtration, washing and air drying, white zirconium phosphate-sodium alginate composite powder is obtained, which is the ion exchange material, wherein the mass fraction of zirconium phosphate is 50~95%.

[0028] This invention synthesizes a zirconium phosphate matrix by solid-phase grinding of sodium phosphate and zirconium oxychloride octahydrate followed by high-temperature hydrothermal treatment, which improves the stability of the crystal structure. The zirconium phosphate matrix is ​​then further treated with a sodium alginate carrier and zirconium nitrate crosslinking technology to form a spherical ion exchange material with high adsorption capacity, facilitating adsorption column packing. This ion exchange material exhibits wider pH adaptability and stronger acid and alkali resistance, achieves high radionuclide separation and removal rates in simulated nuclear wastewater containing strontium ions, and boasts a simple and lower-cost preparation process, demonstrating strong applicability and feasibility in industrial radioactive wastewater treatment.

[0029] When using the ion exchange material proposed in this invention to treat simulated nuclear waste containing strontium ions, the specific steps include: Ion exchange material is added to simulated nuclear waste liquid, mixed evenly, and stirred and shaken at 150-200 r / min for 10-360 min at 40-60℃. After filtration, the ion exchange material can be used to adsorb strontium ions to achieve the effect of nuclide separation. The filtered ion exchange material can be regenerated and recycled after acid washing.

[0030] Among them, Sr in simulated nuclear waste liquid 2+ The concentration is 50~200mg / L, and the ratio of ion exchange material to simulated nuclear waste liquid is 1mg:0.5-2mL.

[0031] Example 1 Step 1: Take 3g of sodium phosphate powder and 4g of zirconium oxychloride octahydrate powder, place them in an agate mortar, grind for 30 minutes until they are mixed evenly, then transfer the mixed material into a polytetrafluoroethylene reactor, seal it, and place it in an 80℃ oven for hydrothermal treatment for 8 hours. After cooling to room temperature, take it out of the polytetrafluoroethylene reactor, wash the reaction product with anhydrous ethanol and deionized water until neutral, and dry it to obtain zirconium phosphate powder material.

[0032] Step 2: Take 1g of sodium alginate powder, place it in a beaker, add 200mL of deionized water, sonicate at 45kHz for 30min, with a 2min pause every 5min of sonication, heat to 70℃, and stir at 200r / min for 60min to obtain sodium alginate solution; take 5g of zirconium phosphate powder, add it to the sodium alginate solution, heat at 70℃, and stir at 200r / min for 60min to disperse the zirconium phosphate powder evenly in the sodium alginate solution to obtain a mixed dispersion.

[0033] Step 3: Take another 4g of zirconium nitrate, dissolve it in 200mL of deionized water, heat it at 70℃, and stir it at 200r / min for 60min to obtain zirconium nitrate crosslinking agent; add the mixed dispersion obtained in step 2 dropwise into zirconium nitrate crosslinking agent, let it stand at about 50℃ for 5h, and then filter, wash and air dry in sequence to obtain white ion exchange material.

[0034] Example 2 Step 1: Take 6g of sodium phosphate powder and 8g of zirconium oxychloride octahydrate powder, place them in an agate mortar, grind for 40 minutes until they are mixed evenly, then transfer the mixed material into a polytetrafluoroethylene reactor, seal it, and place it in an 80℃ oven for hydrothermal treatment for 8 hours. After cooling to room temperature, take it out of the polytetrafluoroethylene reactor, wash the reaction product with anhydrous ethanol and deionized water until neutral, and dry it to obtain zirconium phosphate powder material.

[0035] Step 2: Take 1g of sodium alginate powder, place it in a beaker, add 200mL of deionized water, sonicate at 45kHz for 30min, with a 2min pause every 5min of sonication, heat to 70℃, and stir at 200r / min for 60min to obtain sodium alginate solution; take 5g of zirconium phosphate powder, add it to the sodium alginate solution, heat at 70℃, and stir at 200r / min for 60min to disperse the zirconium phosphate powder evenly in the sodium alginate solution to obtain a mixed dispersion.

[0036] Step 3: Take another 4g of zirconium nitrate, dissolve it in 200mL of deionized water, heat it at 70℃, and stir it at 200r / min for 60min to obtain zirconium nitrate crosslinking agent; add the mixed dispersion obtained in step 2 dropwise into zirconium nitrate crosslinking agent, let it stand at about 50℃ for 5h, and then filter, wash and air dry in sequence to obtain ion exchange material.

[0037] Example 3 Step 1: Take 6g of sodium phosphate powder and 8g of zirconium oxychloride octahydrate powder, place them in an agate mortar, grind for 60 minutes until they are evenly mixed, then transfer the mixed material into a polytetrafluoroethylene reactor, seal it, and place it in a 100℃ oven for hydrothermal treatment for 12 hours. After cooling to room temperature, take it out of the polytetrafluoroethylene reactor, wash the reaction product with anhydrous ethanol and deionized water until neutral, and dry it to obtain zirconium phosphate powder material.

[0038] Step 2: Take 1g of sodium alginate powder, place it in a beaker, add 200mL of deionized water, sonicate at 45kHz for 30min, with a 2min pause every 5min of sonication, heat to 70℃, and stir at 200r / min for 60min to obtain sodium alginate solution; take 5g of zirconium phosphate powder, add it to the sodium alginate solution, heat at 70℃, and stir at 200r / min for 60min to disperse the zirconium phosphate powder evenly in the sodium alginate solution to obtain a mixed dispersion.

[0039] Step 3: Take another 4g of zirconium nitrate, dissolve it in 200mL of deionized water, heat it at 70℃, and stir it at 200r / min for 60min to obtain zirconium nitrate crosslinking agent; add the mixed dispersion obtained in step 2 dropwise into zirconium nitrate crosslinking agent, let it stand at about 50℃ for 5h, and then filter, wash and air dry in sequence to obtain ion exchange material.

[0040] Example 4 Step 1: Take 6g of sodium phosphate powder and 8g of zirconium oxychloride octahydrate powder, place them in an agate mortar, grind for 60 minutes until they are mixed evenly, then transfer the mixed material into a polytetrafluoroethylene reactor, seal it, and place it in a 160℃ oven for hydrothermal treatment for 12 hours. After cooling to room temperature, take it out of the polytetrafluoroethylene reactor, wash the reaction product with anhydrous ethanol and deionized water until neutral, and dry it to obtain zirconium phosphate powder material.

[0041] Step 2: Take 2g of sodium alginate powder, place it in a beaker, add 400mL of deionized water, sonicate at 45kHz for 30min, with a 2min pause every 5min of sonication, heat to 70℃, and stir at 200r / min for 60min to obtain sodium alginate solution; take 15g of zirconium phosphate powder, add it to the sodium alginate solution, heat at 70℃, and stir at 200r / min for 60min to disperse the zirconium phosphate powder evenly in the sodium alginate solution to obtain a mixed dispersion.

[0042] Step 3: Take another 4g of zirconium nitrate, dissolve it in 200mL of deionized water, heat it at 70℃, and stir it at 200r / min for 60min to obtain zirconium nitrate crosslinking agent; add the mixed dispersion obtained in step 2 dropwise into zirconium nitrate crosslinking agent, let it stand at about 50℃ for 5h, and then filter, wash and air dry in sequence to obtain ion exchange material.

[0043] Example 5 Step 1: Take 6g of sodium phosphate powder and 8g of zirconium oxychloride octahydrate powder, place them in an agate mortar, grind for 90 minutes until they are evenly mixed, then transfer the mixed material into a polytetrafluoroethylene reactor, seal it, and place it in a 120℃ oven for hydrothermal treatment for 24 hours. After cooling to room temperature, take it out of the polytetrafluoroethylene reactor, wash the reaction product with anhydrous ethanol and deionized water until neutral, and dry it to obtain zirconium phosphate powder material.

[0044] Step 2: Take 2g of sodium alginate powder, place it in a beaker, add 200mL of deionized water, sonicate at 45kHz for 30min, with a 2min pause every 5min of sonication, heat to 70℃, and stir at 300r / min for 60min to obtain sodium alginate solution; take 10g of zirconium phosphate powder, add it to the sodium alginate solution, heat at 70℃, and stir at 200r / min for 60min to disperse the zirconium phosphate powder evenly in the sodium alginate solution to obtain a mixed dispersion.

[0045] Step 3: Take another 3g of zirconium nitrate, dissolve it in 200mL of deionized water, heat it at 70℃, and stir it at 200r / min for 60min to obtain zirconium nitrate crosslinking agent; add the mixed dispersion obtained in step 2 dropwise into zirconium nitrate crosslinking agent, let it stand at about 50℃ for 5h, and then filter, wash and air dry in sequence to obtain ion exchange material.

[0046] Example 6 Step 1: Take 6g of sodium phosphate powder and 8g of zirconium oxychloride octahydrate powder, place them in an agate mortar, grind for 90 minutes until they are mixed evenly, then transfer the mixed material into a polytetrafluoroethylene reactor, seal it, and place it in a 100℃ oven for hydrothermal treatment for 16 hours. After cooling to room temperature, take it out of the polytetrafluoroethylene reactor, wash the reaction product with anhydrous ethanol and deionized water until neutral, and dry it to obtain zirconium phosphate powder material.

[0047] Step 2: Take 1.5g of sodium alginate powder, place it in a beaker, add 200mL of deionized water, sonicate at 65kHz for 30min, with a 2min pause every 5min of sonication, heat to 70℃, and stir at 300r / min for 60min to obtain sodium alginate solution; take 20g of zirconium phosphate powder, add it to the sodium alginate solution, heat at 70℃, and stir at 400r / min for 60min to disperse the zirconium phosphate powder evenly in the sodium alginate solution to obtain a mixed dispersion.

[0048] Step 3: Take another 3g of zirconium nitrate, dissolve it in 200mL of deionized water, heat it at 70℃, and stir it at 200r / min for 60min to obtain zirconium nitrate crosslinking agent; add the mixed dispersion obtained in step 2 dropwise into zirconium nitrate crosslinking agent, let it stand at about 50℃ for 5h, and then filter, wash and air dry in sequence to obtain ion exchange material.

[0049] Example 7 Step 1: Take 5g of sodium phosphate powder and 10g of zirconium oxychloride octahydrate powder, place them in an agate mortar, grind for 90 minutes until they are evenly mixed, then transfer the mixed material into a polytetrafluoroethylene reactor, seal it, and place it in a 100℃ oven for hydrothermal treatment for 16 hours. After cooling to room temperature, take it out of the polytetrafluoroethylene reactor, wash the reaction product with anhydrous ethanol and deionized water until neutral, and dry it to obtain zirconium phosphate powder material.

[0050] Step 2: Take 1.5g of sodium alginate powder, place it in a beaker, add 200mL of deionized water, sonicate at 65kHz for 30min, with a 2min pause every 5min of sonication, heat to 70℃, and stir at 300r / min for 60min to obtain sodium alginate solution; take 20g of zirconium phosphate powder, add it to the sodium alginate solution, heat at 70℃, and stir at 400r / min for 60min to disperse the zirconium phosphate powder evenly in the sodium alginate solution to obtain a mixed dispersion.

[0051] Step 3: Take another 3g of zirconium nitrate, dissolve it in 200mL of deionized water, heat it at 70℃, and stir it at 200r / min for 60min to obtain zirconium nitrate crosslinking agent; add the mixed dispersion obtained in step 2 dropwise into zirconium nitrate crosslinking agent, let it stand at about 50℃ for 10h, and then filter, wash and air dry in sequence to obtain ion exchange material.

[0052] Example 8 Step 1: Take 5g of sodium phosphate powder and 15g of zirconium oxychloride octahydrate powder, place them in an agate mortar, grind for 90 minutes until they are evenly mixed, then transfer the mixed material into a polytetrafluoroethylene reactor, seal it, and place it in a 150℃ oven for hydrothermal treatment for 24 hours. After cooling to room temperature, take it out of the polytetrafluoroethylene reactor, wash the reaction product with anhydrous ethanol and deionized water until neutral, and dry it to obtain zirconium phosphate powder material.

[0053] Step 2: Take 1.5g of sodium alginate powder, place it in a beaker, add 200mL of deionized water, sonicate at 45kHz for 30min, with a 2min pause every 5min of sonication, heat to 70℃, and stir at 300r / min for 60min to obtain sodium alginate solution; take 20g of zirconium phosphate powder, add it to the sodium alginate solution, heat at 70℃, and stir at 400r / min for 60min to disperse the zirconium phosphate powder evenly in the sodium alginate solution to obtain a mixed dispersion.

[0054] Step 3: Take another 4g of zirconium nitrate, dissolve it in 200mL of deionized water, heat it at 70℃, and stir it at 200r / min for 60min to obtain zirconium nitrate crosslinking agent; add the mixed dispersion obtained in step 2 dropwise into zirconium nitrate crosslinking agent, let it stand at about 50℃ for 8h, and then filter, wash and air dry in sequence to obtain ion exchange material.

[0055] Example 9 Step 1: Take 5g of sodium phosphate powder and 20g of zirconium oxychloride octahydrate powder, place them in an agate mortar, grind for 90 minutes until they are evenly mixed, then transfer the mixed material into a polytetrafluoroethylene reactor, seal it, and place it in a 150℃ oven for hydrothermal treatment for 24 hours. After cooling to room temperature, take it out of the polytetrafluoroethylene reactor, wash the reaction product with anhydrous ethanol and deionized water until neutral, and dry it to obtain zirconium phosphate powder material.

[0056] Step 2: Take 1.5g of sodium alginate powder, place it in a beaker, add 200mL of deionized water, sonicate at 45kHz for 30min, with a 2min pause every 5min of sonication, heat to 70℃, and stir at 300r / min for 60min to obtain sodium alginate solution; take 20g of zirconium phosphate powder, add it to the sodium alginate solution, heat at 70℃, and stir at 400r / min for 60min to disperse the zirconium phosphate powder evenly in the sodium alginate solution to obtain a mixed dispersion.

[0057] Step 3: Take another 4g of zirconium nitrate, dissolve it in 200mL of deionized water, heat it at 70℃, and stir it at 200r / min for 60min to obtain zirconium nitrate crosslinking agent; add the mixed dispersion obtained in step 2 dropwise into zirconium nitrate crosslinking agent, let it stand at about 50℃ for 8h, and then filter, wash and air dry in sequence to obtain ion exchange material.

[0058] Example 10 Step 1: Take 3g of sodium phosphate powder and 4g of zirconium oxychloride octahydrate powder, place them in an agate mortar, grind for 30 minutes until they are mixed evenly, then transfer the mixed material into a polytetrafluoroethylene reactor, seal it, and place it in an 80℃ oven for hydrothermal treatment for 8 hours. After cooling to room temperature, take it out of the polytetrafluoroethylene reactor, wash the reaction product with anhydrous ethanol and deionized water until neutral, and dry it to obtain zirconium phosphate powder material.

[0059] Step 2: Take 1g of sodium alginate powder, place it in a beaker, add 200mL of deionized water, sonicate at 45kHz for 30min, with a 2min pause every 5min of sonication, heat to 70℃, and stir at 200r / min for 60min to obtain sodium alginate solution; take 5g of zirconium phosphate powder, add it to the sodium alginate solution, heat at 70℃, and stir at 200r / min for 60min to disperse the zirconium phosphate powder evenly in the sodium alginate solution to obtain a mixed dispersion.

[0060] Step 3: Take another 3.2g of zirconium nitrate and 0.6g of cerium nitrate, dissolve them in 200mL of deionized water, heat at 70℃, stir at 200r / min for 60min, then slowly add a 25% pentanediol aqueous solution containing 0.2g of pentanediol, and continue stirring for 25min to obtain zirconium nitrate crosslinking agent; add the mixed dispersion obtained in step 2 dropwise into zirconium nitrate crosslinking agent, let stand at about 50℃ for 5h, and then filter, wash and air dry in sequence to obtain ion exchange material.

[0061] Example 11 Step 1: Take 6g of sodium phosphate powder and 8g of zirconium oxychloride octahydrate powder, place them in an agate mortar, grind for 60 minutes until they are evenly mixed, then transfer the mixed material into a polytetrafluoroethylene reactor, seal it, and place it in a 100℃ oven for hydrothermal treatment for 12 hours. After cooling to room temperature, take it out of the polytetrafluoroethylene reactor, wash the reaction product with anhydrous ethanol and deionized water until neutral, and dry it to obtain zirconium phosphate powder material.

[0062] Step 2: Take 1g of sodium alginate powder, place it in a beaker, add 200mL of deionized water, sonicate at 45kHz for 30min, with a 2min pause every 5min of sonication, heat to 70℃, and stir at 200r / min for 60min to obtain sodium alginate solution; take 5g of zirconium phosphate powder, add it to the sodium alginate solution, heat at 70℃, and stir at 200r / min for 60min to disperse the zirconium phosphate powder evenly in the sodium alginate solution to obtain a mixed dispersion.

[0063] Step 3: Take another 2.8g of zirconium nitrate and 0.8g of cerium nitrate, dissolve them in 200mL of deionized water, heat at 70℃, stir at 200r / min for 60min, then slowly add a 25% pentanediol aqueous solution containing 0.4g of pentanediol, and continue stirring for 30min to obtain zirconium nitrate crosslinking agent; add the mixed dispersion obtained in step 2 dropwise into zirconium nitrate crosslinking agent, let stand at about 50℃ for 12h, and then filter, wash and air dry in sequence to obtain ion exchange material.

[0064] Example 12 Step 1: Take 6g of sodium phosphate powder and 8g of zirconium oxychloride octahydrate powder, place them in an agate mortar, grind for 90 minutes until they are evenly mixed, then transfer the mixed material into a polytetrafluoroethylene reactor, seal it, and place it in a 120℃ oven for hydrothermal treatment for 24 hours. After cooling to room temperature, take it out of the polytetrafluoroethylene reactor, wash the reaction product with anhydrous ethanol and deionized water until neutral, and dry it to obtain zirconium phosphate powder material.

[0065] Step 2: Take 2g of sodium alginate powder, place it in a beaker, add 200mL of deionized water, sonicate at 45kHz for 30min, with a 2min pause every 5min of sonication, heat to 70℃, and stir at 300r / min for 60min to obtain sodium alginate solution; take 10g of zirconium phosphate powder, add it to the sodium alginate solution, heat at 70℃, and stir at 200r / min for 60min to disperse the zirconium phosphate powder evenly in the sodium alginate solution to obtain a mixed dispersion.

[0066] Step 3: Take another 2.4g of zirconium nitrate and 0.8g of cerium nitrate, dissolve them in 200mL of deionized water, heat at 70℃, stir at 300r / min for 60min, then slowly add a 25% pentanediol aqueous solution containing 0.8g of pentanediol, and continue stirring for 25min to obtain zirconium nitrate crosslinking agent; add the mixed dispersion obtained in step 2 dropwise into zirconium nitrate crosslinking agent, let stand at about 50℃ for 10h, and then filter, wash and air dry in sequence to obtain ion exchange material.

[0067] Example 13 Step 1: Take 6g of sodium phosphate powder and 8g of zirconium oxychloride octahydrate powder, place them in an agate mortar, grind for 90 minutes until they are mixed evenly, then transfer the mixed material into a polytetrafluoroethylene reactor, seal it, and place it in a 100℃ oven for hydrothermal treatment for 16 hours. After cooling to room temperature, take it out of the polytetrafluoroethylene reactor, wash the reaction product with anhydrous ethanol and deionized water until neutral, and dry it to obtain zirconium phosphate powder material.

[0068] Step 2: Take 1.5g of sodium alginate powder, place it in a beaker, add 200mL of deionized water, sonicate at 65kHz for 30min, with a 2min pause every 5min of sonication, heat to 70℃, and stir at 300r / min for 60min to obtain sodium alginate solution; take 20g of zirconium phosphate powder, add it to the sodium alginate solution, heat at 70℃, and stir at 400r / min for 60min to disperse the zirconium phosphate powder evenly in the sodium alginate solution to obtain a mixed dispersion.

[0069] Step 3: Take another 3.0g of zirconium nitrate and 0.4g of cerium nitrate, dissolve them in 200mL of deionized water, heat at 70℃, stir at 300r / min for 60min, then slowly add a 25% pentanediol aqueous solution containing 0.6g of pentanediol, and continue stirring for 30min to obtain zirconium nitrate crosslinking agent; add the mixed dispersion obtained in step 2 dropwise into zirconium nitrate crosslinking agent, let stand at about 50℃ for 12h, and then filter, wash and air dry in sequence to obtain ion exchange material.

[0070] Example 14 Step 1: Take 5g of sodium phosphate powder and 15g of zirconium oxychloride octahydrate powder, place them in an agate mortar, grind for 90 minutes until they are evenly mixed, then transfer the mixed material into a polytetrafluoroethylene reactor, seal it, and place it in a 150℃ oven for hydrothermal treatment for 24 hours. After cooling to room temperature, take it out of the polytetrafluoroethylene reactor, wash the reaction product with anhydrous ethanol and deionized water until neutral, and dry it to obtain zirconium phosphate powder material.

[0071] Step 2: Take 1.5g of sodium alginate powder, place it in a beaker, add 200mL of deionized water, sonicate at 45kHz for 30min, with a 2min pause every 5min of sonication, heat to 70℃, and stir at 300r / min for 60min to obtain sodium alginate solution; take 20g of zirconium phosphate powder, add it to the sodium alginate solution, heat at 70℃, and stir at 400r / min for 60min to disperse the zirconium phosphate powder evenly in the sodium alginate solution to obtain a mixed dispersion.

[0072] Step 3: Take another 2.6g of zirconium nitrate and 0.6g of cerium nitrate, dissolve them in 200mL of deionized water, heat at 70℃, stir at 300r / min for 60min, then slowly add a 25% pentanediol aqueous solution containing 0.8g of pentanediol, and continue stirring for 25min to obtain zirconium nitrate crosslinking agent; add the mixed dispersion obtained in step 2 dropwise into zirconium nitrate crosslinking agent, let stand at about 50℃ for 8h, and then filter, wash and air dry in sequence to obtain ion exchange material.

[0073] Example 15 Step 1: Take 5g of sodium phosphate powder and 20g of zirconium oxychloride octahydrate powder, place them in an agate mortar, grind for 90 minutes until they are evenly mixed, then transfer the mixed material into a polytetrafluoroethylene reactor, seal it, and place it in a 150℃ oven for hydrothermal treatment for 24 hours. After cooling to room temperature, take it out of the polytetrafluoroethylene reactor, wash the reaction product with anhydrous ethanol and deionized water until neutral, and dry it to obtain zirconium phosphate powder material.

[0074] Step 2: Take 1.5g of sodium alginate powder, place it in a beaker, add 200mL of deionized water, sonicate at 45kHz for 30min, with a 2min pause every 5min of sonication, heat to 70℃, and stir at 300r / min for 60min to obtain sodium alginate solution; take 20g of zirconium phosphate powder, add it to the sodium alginate solution, heat at 70℃, and stir at 400r / min for 60min to disperse the zirconium phosphate powder evenly in the sodium alginate solution to obtain a mixed dispersion.

[0075] Step 3: Take another 2.8g of zirconium nitrate and 0.6g of cerium nitrate, dissolve them in 200mL of deionized water, heat at 70℃, stir at 300r / min for 60min, then slowly add a 25% pentanediol aqueous solution containing 0.6g of pentanediol, and continue stirring for 30min to obtain zirconium nitrate crosslinking agent; add the mixed dispersion obtained in step 2 dropwise into zirconium nitrate crosslinking agent, let stand at about 50℃ for 12h, and then filter, wash and air dry in sequence to obtain ion exchange material.

[0076] Comparative Example 1 Step 1: Take 3g of sodium phosphate powder and 4g of zirconium oxychloride octahydrate powder, place them in an agate mortar, grind for 30 minutes until they are mixed evenly, then transfer the mixed material into a polytetrafluoroethylene reactor, seal it, and place it in an 80℃ oven for hydrothermal treatment for 8 hours. After cooling to room temperature, take it out of the polytetrafluoroethylene reactor, wash the reaction product with anhydrous ethanol and deionized water until neutral, and dry it to obtain zirconium phosphate powder material.

[0077] Step 2: Take 1g of sodium alginate powder, place it in a beaker, add 200mL of deionized water, sonicate at 45kHz for 30min, with a 2min pause every 5min of sonication, heat to 70℃, and stir at 200r / min for 60min to obtain sodium alginate solution; take 5g of zirconium phosphate powder, add it to the sodium alginate solution, heat at 70℃, and stir at 200r / min for 60min to disperse the zirconium phosphate powder evenly in the sodium alginate solution to obtain a mixed dispersion.

[0078] Step 3: Take another 4g of calcium chloride, dissolve it in 200mL of deionized water, heat it at 70℃, stir at 200r / min for 60min to obtain a calcium chloride aqueous solution; add the mixed dispersion obtained in step 2 dropwise into the calcium chloride aqueous solution, let it stand for 12h, and then filter, wash and air dry in sequence to obtain the ion exchange material.

[0079] Comparative Example 2 Step 1: Take 3g of sodium phosphate powder and 4g of zirconium oxychloride octahydrate powder, place them in an agate mortar, grind for 30 minutes until they are mixed evenly, then transfer the mixed material into a polytetrafluoroethylene reactor, seal it, and place it in an 80℃ oven for hydrothermal treatment for 8 hours. After cooling to room temperature, take it out of the polytetrafluoroethylene reactor, wash the reaction product with anhydrous ethanol and deionized water until neutral, and dry it to obtain zirconium phosphate powder material.

[0080] Step 2: Take 1g of sodium alginate powder, place it in a beaker, add 200mL of deionized water, sonicate at 45kHz for 30min, with a 2min pause every 5min of sonication, heat to 70℃, and stir at 200r / min for 60min to obtain sodium alginate solution; take 5g of zirconium phosphate powder, add it to the sodium alginate solution, heat at 70℃, and stir at 200r / min for 60min to disperse the zirconium phosphate powder evenly in the sodium alginate solution to obtain a mixed dispersion.

[0081] Step 3: Take another 3.4g of zirconium nitrate, dissolve it in 200mL of deionized water, heat it at 70℃, stir at 200r / min for 60min, then slowly add a 25% pentanediol aqueous solution containing 0.6g of pentanediol, and continue stirring for 25min to obtain zirconium nitrate crosslinking agent; add the mixed dispersion obtained in step 2 dropwise into zirconium nitrate crosslinking agent, let it stand at about 50℃ for 5h, and then filter, wash and air dry in sequence to obtain ion exchange material.

[0082] Comparative Example 3 Step 1: Take 3g of sodium phosphate powder and 4g of zirconium oxychloride octahydrate powder, place them in an agate mortar, grind for 30 minutes until they are mixed evenly, then transfer the mixed material into a polytetrafluoroethylene reactor, seal it, and place it in an 80℃ oven for hydrothermal treatment for 8 hours. After cooling to room temperature, take it out of the polytetrafluoroethylene reactor, wash the reaction product with anhydrous ethanol and deionized water until neutral, and dry it to obtain zirconium phosphate powder material.

[0083] Step 2: Take 1g of sodium alginate powder, place it in a beaker, add 200mL of deionized water, sonicate at 45kHz for 30min, with a 2min pause every 5min of sonication, heat to 70℃, and stir at 200r / min for 60min to obtain sodium alginate solution; take 5g of zirconium phosphate powder, add it to the sodium alginate solution, heat at 70℃, and stir at 200r / min for 60min to disperse the zirconium phosphate powder evenly in the sodium alginate solution to obtain a mixed dispersion.

[0084] Step 3: Take another 3.4g of zirconium nitrate and 0.6g of cerium nitrate, dissolve them in 200mL of deionized water, heat at 70℃, and stir at 200r / min for 60min to obtain zirconium nitrate crosslinking agent; add the mixed dispersion obtained in step 2 dropwise into zirconium nitrate crosslinking agent, let it stand at about 50℃ for 5h, and then filter, wash and air dry in sequence to obtain ion exchange material.

[0085] Test case Samples: Ion exchange materials prepared in Examples 1-15 and Comparative Examples 1-3 (1) The ion exchange material samples prepared in Example 1 were taken, and their morphology was observed. Infrared spectroscopy was used to measure the samples, and the results are as follows: Figure 1 and Figure 2 As shown. (2) Take Sr 2+ A simulated solution containing the target ion with an initial concentration of 150 mg / L and a pH of approximately 7 was divided into several portions. Each portion of the simulated solution was treated with an ion exchange material sample corresponding to one of Examples 1-15 and Comparative Examples 1-3, respectively. Specifically, the ion exchange material sample was mixed with the simulated solution at a solid-liquid ratio of 1 mg:1 mL at 40°C, stirred at 200 r / min, and adsorbed for 360 min, followed by separation and filtration. The separated solid material was soaked in a 5% nitric acid solution for 60 min, then washed until neutral to obtain a regenerable and recyclable ion exchange material, which was then used for Sr. 2+ The adsorption separation process was repeated 5 times.

[0087] During the above processing, Sr was measured at different stages using an ICP-OES inductively coupled plasma atomic emission spectrometer. 2+ The concentrations were then summarized in Table 1 below: Table 1. Results of adsorption performance determination for different samples (3) Different ion exchange material samples were taken and immersed in solutions with different pH values. Taking the ion exchange material sample from Example 1 as an example, the morphology after immersion in different solutions was observed under an optical electron microscope, and the results are as follows. Figure 3 As shown. Taking ion exchange material samples from Examples 1, 11, and Comparative Example 1 as examples, they were immersed in solutions of different pH values ​​for 72 hours, and their acid and alkali resistance was measured. The results are summarized in Table 2 below: Table 2. Results of acid and alkali resistance tests on samples of different ion exchange materials.

[0089] Different ion exchange material samples were taken and Sr was measured at different times. 2+ Removal rate. Taking the ion exchange material sample from Example 1 as an example, the Sr removal rate was measured at different times. 2+ The removal rate was calculated and plotted as a curve, such as... Figure 4 As shown. Again, using the ion exchange material samples from Examples 1, 11, and Comparative Example 1 as examples, the Sr of different samples was measured. 2+ The removal rate varies over time, and the results are summarized in Table 3 below: Table 3 Adsorption kinetics of different ion exchange materials

[0090] The above experiments and results demonstrate that the ion exchange material prepared using zirconium nitrate as a crosslinking agent, as proposed in this invention, exhibits significant adsorption effects in terms of material stability and adsorption capacity. Furthermore, the multi-component composite zirconium nitrate crosslinking system shows even more significant improvements in material stability and adsorption capacity. Therefore, it can be concluded that the ion exchange material proposed in this invention, prepared using zirconium nitrate crosslinking technology, not only boasts a simple and low-cost preparation process but also exhibits strong material stability, wide pH adaptability, and a significant adsorption capacity for strontium in solution.

[0091] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for the preparation of ion exchange material for efficient nuclide separation, characterized in that, The preparation method comprises the following steps: S1: taking sodium phosphate powder and zirconium oxychloride octahydrate powder, grinding in solid phase, mixing uniformly to obtain a primary mixture; S2: placing the primary mixture in a closed environment, and performing hydrothermal treatment, taking out after cooling, washing and drying to obtain zirconium phosphate powder; S3: adding the zirconium phosphate powder into a sodium alginate solution, and heating and stirring to obtain a zirconium phosphate-sodium alginate mixed dispersion liquid; S4: adding the zirconium phosphate-sodium alginate mixed dispersion liquid into a zirconium nitrate crosslinking agent dropwise, and standing for reaction, and then performing filtration, washing and drying in sequence to obtain the ion exchange material.

2. The method for preparing an ion exchange material for efficient nuclide separation according to claim 1, characterized by, In step S1, the mass ratio of the sodium phosphate powder to the zirconium oxychloride octahydrate powder is 1:1-5.

3. The method for preparing an ion exchange material for efficient nuclide separation according to claim 1, characterized by, In steps S2 and S3, the mass concentration of the sodium alginate solution is 0.5-2.0 wt%, and the mass ratio of the zirconium phosphate powder to the sodium alginate solution is 5-30:

1.

4. The method for preparing an ion exchange material for efficient nuclide separation according to claim 3, characterized by, The hydrothermal reaction temperature is 80-160 ℃, and the reaction time is 8-24 h.

5. The method for preparing an ion exchange material for efficient nuclide separation according to claim 1, characterized by, In step S4, the standing reaction time is 5-20 h.

6. The method for producing an ion exchange material for high-efficiency nuclide separation according to any one of claims 1 to 5, characterized by, The zirconium nitrate crosslinking agent comprises zirconium nitrate with a mass concentration of 1.5-2.5 wt%.

7. The method for preparing an ion exchange material for efficient nuclide separation according to claim 6, characterized by, The zirconium nitrate crosslinking agent further comprises cerium nitrate and glutaraldehyde, and the mass ratio of the zirconium nitrate to the cerium nitrate and the glutaraldehyde is 60-80:10-20:5-15.

8. The method for preparing an ion exchange material for efficient nuclide separation according to claim 7, characterized by, The preparation method of the zirconium nitrate crosslinking agent comprises the following steps: The zirconium nitrate and the cerium nitrate are taken in a certain amount, added into deionized water, heated to 60-80 ℃, and stirred at a speed of 200-400 r / min for 40-100 min until completely dissolved; then the glutaraldehyde aqueous solution is added dropwise, and the stirring is continued for 20-30 min to prepare the crosslinking zirconium nitrate crosslinking agent with a mass concentration of 1.5-3.0 wt%, which is placed at 50-70 ℃ for standby.

9. An ion exchange material for efficient nuclide separation, which is prepared by the preparation method in any one of claims 1-8.

10. A method of using the ion exchange material for efficient nuclide separation according to claim 9, characterized in that, The preparation method comprises the following steps: The ion exchange material is added into a simulated nuclear waste liquid with a nuclide ion concentration of 50-200 mg / L in a use amount ratio of 1 mg:0.5-2 mL, mixed uniformly, stirred and oscillated at a speed of 150-200 r / min at 40-60 ℃ for 10-360 min, and filtered to complete the nuclide separation; the filtered ion exchange material is subjected to acid washing and then used for regeneration and recycling.

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