Preparation method of solid bubble type rubidium and cesium adsorbent

Abstract

The invention relates to a solid bubble type rubidium, cesium and thallium adsorbent as well as a preparation method and application thereof, belongs to the technical field of rubidium, cesium and thallium adsorption, and solves the problems of low adsorption efficiency, low capacity, complex process steps, environmental pollution and difficulty in recovery and regeneration when rubidium, cesium and thallium are extracted from Prussian blue (PB) and analogues (PBAs) thereof in the prior art. The method comprises the following steps: activating solid bubbles, and reacting with a silanization reagent; dipping the modified solid bubbles into a solution containing [Fe (CN) 6] < 3->, dropwise adding a transition metal salt solution, and reacting; the PB or PBAs adsorbent is grafted on the surface of the solid bubble matrix through in-situ growth, and the matrix is spherical and has a relatively high specific surface area, so that the dispersion of the adsorbent can be promoted, and the adsorption performance on rubidium, cesium and thallium is effectively improved; the recycling difficulty of the adsorbent can be reduced due to the characteristic of low density, the adsorbent is endowed with excellent cycling stability due to relatively high mechanical strength and a stable material, the adsorbent can be recycled for a long time, and the cost is reduced; the preparation method is simple and environment-friendly, and industrial application is easy to realize.

Description

Technical Field

[0001] This invention relates to the field of rubidium, cesium, and thallium adsorption technology, and particularly to a solid bubble-type rubidium, cesium, and thallium adsorbent, its preparation method, and its application. Background Technology

[0002] Alkali metals rubidium and cesium possess excellent chemical activity and photoelectric properties, finding wide applications in high-tech industries such as fiber optic telecommunications systems and aerospace. With the rapid development of industries such as information, aviation, and nuclear energy, the demand for rubidium and cesium is gradually increasing. As mineral resources dwindle, people are paying increasing attention to rubidium and cesium resources stored in salt lake brines, as their extraction has significant strategic importance. However, with the rapid development of human industrial activities, the content of heavy metals in water is gradually increasing, posing a serious threat to ecological security and human health. Among them, thallium, as a typical rare heavy metal element, mainly exists in water as a monovalent (Tl) element. + ) and a small amount of trivalent (Tl) 3+ It exists in form. Tl + Thallium has extremely high mobility and bioavailability, and can easily accumulate in the human body through drinking water and the food chain, leading to irreversible damage to nerves, kidneys and hair follicles. It is far more toxic to organisms than lead, cadmium and mercury. Therefore, the development of environmentally friendly and efficient thallium removal reagents is of great practical significance.

[0003] Various separation techniques have been explored for the efficient separation and recovery of metal ions in aqueous phases, such as precipitation, liquid-phase extraction, membrane separation, and adsorption. Precipitation is easy to operate and efficient, but its high cost makes large-scale application difficult. Liquid-phase extraction has the advantages of fast reaction rate and batch processing capability, but the use of organic extractants can easily cause environmental pollution. Membrane separation, as a low-energy purification technology, requires high energy consumption. Among these methods, adsorption is considered one of the most promising due to its simple operation, low cost, and environmental friendliness.

[0004] Prussian blue (PB) and its analogues (PBAs), as inorganic adsorbents, offer a promising material platform for the extraction and separation of alkali metals rubidium and cesium, as well as the removal of heavy metal thallium. In particular, PBAs have attracted widespread attention from researchers due to their high selectivity, high adsorption capacity, good stability, rapid adsorption kinetics, and excellent regeneration performance. PBAs are materials with unique structural properties, and their molecular formula is M[Fe(CN)6] (where M is Fe). 3+ Cu 2 + Co 2+ wait).

[0005] Currently, although nanoscale PBAs can be synthesized through a simple co-precipitation method, nanoscale PBAs adsorbents have problems such as being difficult to disperse and prone to aggregation during aqueous solution extraction. This not only hinders the adsorption process but also makes it difficult to effectively recover the adsorbent from the aqueous solution.

[0006] To overcome these problems, researchers have explored methods for immobilizing nanoscale PBA adsorbent particles onto functional materials such as polymer matrices, carbon, layered double hydroxides, clay, and magnetic materials. However, these methods often employ complex multi-step processes, increasing preparation time and economic costs. Furthermore, the use of toxic reagents during the reaction process poses a certain degree of harm to the natural environment. In addition, existing immobilized PBA adsorbents generally have high densities, exhibiting slow adsorption rates due to mass transfer limitations. Their overall adsorption performance may decrease due to recombination, and high-density particles are prone to fragmentation due to collisions, leading to uncontrollable losses during regeneration. These shortcomings further limit their large-scale industrial application. Summary of the Invention

[0007] In view of the above analysis, the present invention aims to provide a solid bubble-type rubidium, cesium, and thallium adsorbent, its preparation method, and its application, in order to solve at least one of the problems of low adsorption efficiency, low capacity, complex process steps, environmental pollution, and difficulty in recycling and regenerating when extracting rubidium, cesium, and thallium from the aqueous phase using Prussian blue (PB) and its analogues (PBAs) in the prior art.

[0008] In a first aspect, embodiments of the present invention provide a method for preparing a solid bubble-type rubidium-cesium-thallium adsorbent, the method comprising:

[0009] S1: Solid bubbles are activated using an alkaline solution;

[0010] S2: React the activated solid bubbles from step S1 with a silanizing agent to obtain modified solid bubbles;

[0011] S3: Impregnate the modified solid bubbles with a solution containing [Fe(CN)6]. 3- In a solution, a transition metal salt solution is added dropwise, and a reaction is carried out to obtain a composite rubidium-cesium-thallium adsorbent with a solid bubble surface that is Prussian blue or a Prussian blue analogue.

[0012] Furthermore, in step S1, the alkaline solution is an aqueous solution of sodium hydroxide or potassium hydroxide with a concentration of 0.5-5 mol / L.

[0013] Furthermore, the solid bubble is one or more of hollow glass microspheres, insulated glass microspheres, fly ash cenospheres, and ceramic bubbles, and the density of the solid bubble is 0.1–0.90 g / cm³. 3The particle size is 10-1000μm, and the compressive strength is 1MPa to 200MPa.

[0014] Furthermore, in step S1, the specific steps of the activation treatment are to place the solid bubbles in the strong alkaline solution at a solid-liquid ratio of 10 to 100 g / L and stir.

[0015] Furthermore, in step S2, the silanizing agent is one or more of 3-aminopropyltriethoxysilane, bis-[3-(trimethoxysilyl)propyl]ethylenediamine, and 3-mercaptopropyltrimethoxysilane;

[0016] Furthermore, the mass ratio of the solid bubble to the silanizing agent is 1:0.5 to 4.

[0017] Furthermore, in step S2, the reaction specifically involves mixing the solid bubbles with the silanizing agent in a solvent and reacting at a temperature of 40–80°C for 2–12 hours.

[0018] Furthermore, in step S3, the solid bubbles react with the [Fe(CN)6]-containing... 3- The mass ratio of the solution is 1-5:50, and the [Fe(CN)6] solution... 3- The concentration is 0.1-0.4 mol / L.

[0019] Furthermore, in step S3, the metal ion in the transition metal salt is Fe. 2+ Mn 2+ Co 2+ Ni 2+ Cu 2+ Zn 2+ At least one of the following; the concentration of the transition metal salt solution is 0.1-0.4 mol / L.

[0020] Secondly, embodiments of the present invention provide a solid bubble-type rubidium-cesium-thallium adsorbent, which is prepared by the above-described preparation method.

[0021] Thirdly, embodiments of the present invention provide an application of a solid bubble-type rubidium-cesium-thallium adsorbent in nuclear waste treatment, salt lake extraction, water heavy metal pollution, and electronic waste resource utilization.

[0022] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0023] 1. Compared with existing solidified or non-solidified nanoscale PB or PBAs particle adsorbents, this invention grafts PB or PBAs adsorbents onto the surface of a solid bubble matrix through in-situ growth. The spherical matrix with a large specific surface area promotes adsorbent dispersion, inhibits aggregation, and effectively improves the adsorption performance of rubidium, cesium, and thallium, including adsorption efficiency and adsorption capacity. The low density of the solid bubbles allows the prepared composite adsorbent to spontaneously float to the surface during aqueous phase extraction, reducing operational energy consumption and adsorbent recovery difficulty through efficient solid-liquid separation. In addition, the high mechanical strength and stable material of the solid bubbles endow the adsorbent with excellent cycle stability, which is beneficial for long-term recycling in industrial applications. Furthermore, the preparation method of the composite adsorbent of this invention is simple and environmentally friendly, with mild reaction conditions, low cost, and easy to scale up production.

[0024] 2. This invention regulates the particle size of solid bubbles, providing the largest possible specific surface area to graft more PB or PBAs, thereby enabling the low-density composite adsorbent to have good dispersibility during use and preventing aggregation.

[0025] 3. This invention regulates the concentration of the strong alkaline solution and its ratio with the solid bubbles to be etched, which not only achieves surface degreasing but also enables further surface etching, improves interface roughness, and increases the mechanical sites for the modified groups introduced by the subsequent silanization reaction to attach to the surface of the solid bubbles. By adjusting the ratio between the solid bubbles and the silanization reagent, the content of active adsorbent that can be grafted onto the surface of the solid bubbles by the rubidium, cesium, and thallium adsorbent prepared by the subsequent in-situ reaction is increased, thereby improving the ion adsorption efficiency of the solid bubble-type rubidium, cesium, and thallium adsorbent.

[0026] 4. This invention regulates the interaction between solid bubbles and [Fe(CN)6]. 3- The formulation ratio ensures that the grafting amount of PB or PBA adsorbent generated in situ is sufficient to improve adsorption efficiency, while also enabling the density of the prepared solid bubble-type rubidium-cesium-thallium adsorbent to be less than 1 g / cm³. 3 This ensures that the adsorbent can be rapidly separated and recovered through spontaneous flotation during the adsorption process, thereby reducing operational energy consumption and recovery difficulty.

[0027] 5. Compared with existing nano-sized PB or PBA particle adsorbents, the solid bubble-type rubidium-cesium-thallium adsorbent prepared by the method of this invention has higher adsorption efficiency and adsorption capacity. The initial adsorption capacity for cesium is ≥33 mg / g, and the initial adsorption capacity for rubidium is ≥30 mg / g. After 10 cycles, the adsorbent recovery rate is not less than 95%, and the adsorption capacity retention rate relative to the initial adsorption capacity is ≥95%. The removal rate of thallium can reach 98.1%. When used for water treatment, this composite adsorbent exhibits excellent adsorption performance, recyclability, and cycle stability.

[0028] In this invention, the above-described technical solutions can be combined with each other to achieve more preferred combinations. Other features and advantages of this invention will be set forth in the following description, and some advantages may become apparent from the description or be learned by practicing the invention. The objects and other advantages of this invention can be realized and obtained from what is particularly pointed out in the description and drawings. Attached Figure Description

[0029] The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. Throughout the drawings, the same reference numerals denote the same parts.

[0030] Figure 1 The graphs show the rubidium and cesium adsorption capacity of the adsorbents prepared in Example 1, Comparative Example 1, and Comparative Example 4 as a function of adsorption time.

[0031] Figure 2 The rubidium and cesium adsorption capacity retention rates of the adsorbents prepared in Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3 after 10 cycles of adsorption are shown.

[0032] Figure 3 This is a graph showing the adsorption capacity of the adsorbent prepared in Example 1 for rubidium, cesium, and other metal ions. Detailed Implementation

[0033] The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which constitute a part of the present invention and are used together with the embodiments of the present invention to illustrate the principles of the present invention, but are not intended to limit the scope of the present invention.

[0034] Prussian blue (PB) and its analogues (PBAs) are materials with unique structural properties, and their molecular formula is M[Fe(CN)6] (where M is Fe). 3+ Cu 2+ Co 2+ PBAs, in particular, have attracted widespread attention from researchers due to their high selectivity, high adsorption capacity, good stability, rapid adsorption kinetics and good regeneration performance. They have been widely used for the selective extraction of rubidium and cesium from salt lake brines and for the removal of thallium in water pollution treatment.

[0035] Although nanoscale PBAs can be synthesized using a simple co-precipitation method, their use in aqueous solution extraction presents challenges such as poor dispersion and easy aggregation, hindering the adsorption process and making effective recovery from aqueous solutions difficult. To overcome these issues, researchers have explored methods for immobilizing nanoscale PBA adsorbent particles on functional materials such as polymer matrices, carbon, layered double hydroxides, clay, and magnetic materials. However, these methods often employ complex multi-step processes, increasing preparation time and economic costs. Furthermore, the use of toxic reagents during the reaction process poses a certain degree of harm to the natural environment. Additionally, existing immobilized PBA adsorbents generally have high density, exhibiting mass transfer limitations and slow adsorption rates. Their overall adsorption performance may decrease due to recombination, and high-density particles are prone to fragmentation upon collision, leading to uncontrollable losses during regeneration. These shortcomings further limit their large-scale industrial application.

[0036] According to a specific embodiment of the present invention, the present invention provides a method for preparing a solid bubble-type rubidium-cesium-thallium adsorbent, the method comprising:

[0037] S1: Solid bubbles are activated using an alkaline solution;

[0038] S2: React the activated solid bubbles from step S1 with a silanizing agent to obtain modified solid bubbles;

[0039] S3: Impregnate the modified solid bubbles with a solution containing [Fe(CN)6]. 3- In a solution, a transition metal salt solution is added dropwise, and a reaction is carried out to obtain a rubidium-cesium-thallium adsorbent with a solid bubble surface composited with Prussian blue or a Prussian blue analogue.

[0040] Specifically, in step S1, the alkaline solution is preferably an aqueous solution of sodium hydroxide or potassium hydroxide, more preferably an aqueous solution of sodium hydroxide.

[0041] More specifically, in step S1, the concentration of the sodium hydroxide aqueous solution is 0.5-5 mol / L, which can be 0.5 mol / L, 0.7 mol / L, 1 mol / L, 1.3 mol / L, 1.5 mol / L, 1.8 mol / L, 2.0 mol / L, 2.5 mol / L, 3 mol / L, 3.5 mol / L, 4 mol / L, 4.5 mol / L, or 5 mol / L. If the concentration of the strong alkali solution is too high, it will lead to excessive surface etching, which will not only damage the surface morphology and structural integrity of the solid bubbles, but may also reduce mechanical strength and even cause particle breakage. If the concentration of the strong alkali solution is too low, the surface of the solid bubbles will not be thoroughly cleaned, resulting in poor etching effect, excessive etching time, or failure to etch the solid bubbles.

[0042] Specifically, in step S1, the solid bubble is a type of material consisting of a solid shell surrounding a large number of closed gas cavities inside, preferably one or more of hollow glass microspheres, insulated glass microspheres, fly ash cenospheres, and ceramic bubbles.

[0043] More specifically, in step S1, the particle size of the solid bubbles is 10-1000 μm, and can be exemplary sizes such as 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 850 μm, 900 μm, and 1000 μm. Preferably, using solid bubble materials with uniform particle size distribution is beneficial for uniformly grafting rubidium, cesium, and thallium adsorbents onto their surfaces, thereby enabling the prepared solid bubble-type rubidium, cesium, and thallium adsorbent to have better dispersibility during use, avoiding aggregation, and thus improving its rubidium, cesium, and thallium adsorption performance and recycling and regeneration performance.

[0044] Specifically, the compressive strength of the solid bubbles is between 1 MPa and 200 MPa, and can be 1 MPa, 10 MPa, 20 MPa, 30 MPa, 50 MPa, 80 MPa, 100 MPa, 150 MPa, 200 MPa, etc., as exemplary parameters. Higher compressive strength can give the composite material high stability, which is beneficial to improving its service life. The compressive strength of the solid bubbles after loading active substances remains unchanged.

[0045] Specifically, in step S1, the activation treatment involves placing the solid bubbles in the strong alkaline solution at a solid-liquid ratio of 10-100 g / L and stirring. The solid-liquid ratio can be 10 g / L, 20 g / L, 30 g / L, 40 g / L, 50 g / L, 60 g / L, 70 g / L, 80 g / L, 90 g / L, or 100 g / L. This invention, by controlling the solid-liquid ratio during the activation process, ensures the effective etching and activation of the solid bubbles by the strong alkaline solution while improving production costs and efficiency.

[0046] To promote the etching of solid bubbles by the strong alkaline solution, the etching temperature needs to be controlled between 40-80℃. Specific temperatures include 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, and 80℃. If the temperature is too low, the etching rate will be too slow, but if it is too high, it may cause splashing of the strong alkaline solution.

[0047] To ensure the etching effect, this invention requires stirring the solution during the etching process and controlling the etching time to be 2-12 hours, specifically 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours, and 12 hours. If the time is too short, the etching effect will be poor and the roughening treatment of the solid bubble surface will be insufficient. If the time is too long, the solution will damage the surface structure of the solid bubble and will also affect the subsequent loading of rubidium, cesium, and thallium adsorbents.

[0048] It should be noted that in order to remove the residual alkali and moisture on the surface of the material after etching and obtain solid bubbles that are easy to perform subsequent functionalization, the present invention requires processing of the solid bubbles after etching.

[0049] Specifically, in step (1), the etched solution is subjected to solid-liquid separation. The floating solid product is rinsed with deionized water until neutral and then dried at a drying temperature of 40–100°C for 4–12 hours. A higher drying temperature is beneficial for removing residual moisture, but it should not be too high, otherwise it may damage the microporous structure of the surface. It should also not be too low, otherwise the moisture evaporation rate will be too slow and the drying will not be thorough. Sufficient time is beneficial for moisture evaporation, but it should not be too long, otherwise it will lead to low energy efficiency.

[0050] This invention regulates the concentration of the strong alkaline solution and its ratio with the solid bubbles to be etched, enabling not only surface degreasing but also further surface etching to improve interface roughness. Furthermore, by introducing hydroxyl groups onto the surface of the solid bubbles, it enhances surface reactivity, thereby significantly improving the effective and uniform grafting of the introduced groups onto the interface in the subsequent silanization reaction.

[0051] It should be noted that, in order to achieve a strong chemical bond between the Prussian blue (PB) or its analogues (PBAs) active layer and the solid bubble surface, the present invention requires the introduction of specific modifying functional groups on the solid bubble surface to construct a functionalized interface that is conducive to the in-situ growth of Prussian blue, preferably by introducing amino or thiol functional groups.

[0052] Specifically, in step S2, the solid bubbles activated in step S1 are reacted with a silanizing agent to obtain amino or thiol-modified solid bubbles.

[0053] More specifically, in step S2, the silanizing agent is selected from at least one of 3-aminopropyltriethoxysilane (APTES), bis-[3-(trimethoxysilyl)propyl]ethylenediamine (DAMO), or 3-mercaptopropyltrimethoxysilane (MPTMS).

[0054] More specifically, in step S2, the mass ratio of the solid bubble to the silanizing agent is 1:0.5 to 4, and can be 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, or 1:4. If the amount of silane coupling agent is too low, the surface modification will be incomplete and unable to provide sufficient nucleation sites for the subsequent growth of the active component; if the amount is too high, a self-condensation reaction may occur, forming an unstable and uneven graft layer, which will reduce coupling efficiency and increase economic costs.

[0055] Specifically, in step S2, the step of preparing amino or thiol-modified solid bubbles is as follows: the solid bubbles hydroxylated on the surface in step S1 are added to the mixed solution composed of the silanizing reagent and the solvent, reacted, and after solid-liquid separation, the floating solid product is washed three times with deionized water and ethanol and then dried to obtain amino or thiol-modified solid bubbles.

[0056] More specifically, in step S2, the reaction temperature is 40–80°C and the time is 2–12 hours. At lower temperatures or times, it is difficult to provide continuous reaction motive force, which is insufficient to support the formation of a complete and dense monolayer of the silane coupling agent on the surface of the solid bubble. Conversely, when the temperature exceeds 80°C or the time is too long, the self-condensation side reaction of the silane coupling agent on the surface of the solid bubble will be aggravated, posing a risk of damaging the carrier structure.

[0057] More specifically, in step S2, the solvent used is one or more of deionized water, ethanol, and toluene.

[0058] This invention adjusts the ratio between solid bubbles and silanizing reagents, as well as the reaction conditions between them, to increase the content of active adsorbent grafted onto the surface of solid bubbles in subsequent in-situ reactions, thereby improving the adsorption efficiency of solid bubble-type rubidium-cesium-thallium adsorbents.

[0059] It should be noted that the modified solid bubbles obtained through the above process steps have functionalized surfaces. The amino or thiol groups contained on the surface of the solid bubbles can specifically anchor precursor ions, assisting in the construction of functionalized interfaces on the carrier surface, transforming the homogeneous precipitation reaction into an interface-guided heterogeneous nucleation reaction, thereby realizing the in-situ generation and stable grafting of Prussian blue (PB) or its analogues (PBAs) with active adsorption function on the surface of the solid bubbles.

[0060] Specifically, in step (3), the modified solid bubbles are impregnated with a solution containing [Fe(CN)6]. 3- In a solution, a transition metal salt solution is added dropwise, and a reaction is carried out to obtain a rubidium-cesium-thallium adsorbent composed of solid bubbles and Prussian blue or a Prussian blue analogue.

[0061] More specifically, in step S3, the solution contains [Fe(CN)6].3 The concentration of [Fe(CN)6] is 0.1-0.4 mol / L, which can be 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, or 0.4 mol / L. 3 If the concentration of [Fe(CN)6] is too high, the reaction driving force will be too strong, the nucleation rate will be too fast, and a uniform and effective adsorption layer cannot be formed. 3- Too low a concentration will result in a weak reaction driving force, slow interface growth and low loading, leading to low production efficiency.

[0062] More specifically, in step S3, the solid bubbles react with the [Fe(CN)6]-containing... 3- The mass ratio of the solution is 1-5:50, specifically 1:50, 2:50, 3:50, 4:50, or 5:50. If the mass ratio is too high, the denser solid bubbles will hinder the contact between reactants, leading to reduced productivity. If the mass ratio is too low, there will be a relative excess of [Fe(CN)6] in the solution. 3- Nucleation continues on the surface of the active layer, which is very easy to fall off during subsequent use, affecting cycle stability.

[0063] Specifically, in step S3, after adding the modified solid bubbles to [Fe(CN)6] using a coordination modifier... 3- The pH of the solution is adjusted to 2-3 to control the hydrolysis rate of transition metal salt ions in the later stages, thus enabling controllable heterogeneous nucleation reactions. Citric acid or hydrochloric acid is preferably used as a coordination regulator.

[0064] More specifically, in step S3, [Fe(CN)6] with modified solid bubbles will be added. 3- The solution is subjected to isothermal oscillation at a temperature of 40-80℃ and the transition metal salt solution is added, which is beneficial to promote the directional growth of crystals on the surface of solid bubbles and promote the stable formation of the active layer. The isothermal temperature can be 40℃, 50℃, 60℃, 70℃, or 80℃. The temperature should not be too high to avoid violent solvent evaporation and excessive crystal growth that could cause structural collapse.

[0065] More specifically, in step S3, the metal ion in the transition metal salt is Fe. 2+ Mn 2+ Co 2+ Ni 2+ Cu 2+ Zn 2+ At least one of the following; preferably Fe 2+ Mn 2+ Co 2+ Cu 2+ Zn 2+ .

[0066] More specifically, in step S3, the concentration of the transition metal salt solution is 0.1-0.4 mol / L, which can be 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, or 0.4 mol / L. If the concentration of the transition metal salt solution is too high, the reaction rate will be too fast, the nucleation reaction will be uneven, and an unstable active layer will be formed, affecting stability and cycle life. If the concentration is too low, the active layer loading will be low, resulting in low production efficiency.

[0067] It should be noted that, in order to control the nucleation reaction rate and form a uniform and stable active layer, the present invention limits the method of adding the transition metal salt solution.

[0068] Specifically, in step S3, the transition metal salt solution is added to [Fe(CN)6] by dropwise addition. 3- In the solution, the dropping rate should be controlled within the range of 1-5 mL / min, which can be 1 mL / min, 2 mL / min, 3 mL / min, 4 mL / min, or 5 mL / min. If the dropping rate is too high, the nucleation reaction will be violent, resulting in the formation of an uneven active layer. If the dropping rate is too low, the reaction driving force will be insufficient, the crystal growth rate will be too slow, and the dropping time will be too long, resulting in low production efficiency and lack of economic viability.

[0069] Specifically, in step S3, the reaction time is 4-24 hours, which can be 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, or 24h. If the time is too short, the reaction will be incomplete; if the time is too long, the crystals will coarsen further, reducing the structural advantages, and it will not be in line with the principle of economy.

[0070] Specifically, in step S3, after the reaction is completed, the reaction product is separated into solid and liquid components. The floating solid product is washed three times with deionized water and ethanol and then dried.

[0071] This invention regulates the interaction between solid bubbles and [Fe(CN)6]. 3- The proportions of the raw materials, as well as the method of adding transition metal salts and the reaction time, are carefully controlled to ensure that the raw materials react fully. This ensures the in-situ generation of PB or PBA adsorbent grafts to improve adsorption efficiency, while also achieving a density of less than 1 g / cm³ for the resulting solid bubble-type rubidium-cesium-thallium adsorbent. 3 This ensures that the adsorbent can be rapidly separated and recovered through spontaneous flotation during the adsorption process, thereby reducing operational energy consumption and recovery difficulty.

[0072] Compared with existing nanoscale PB or PBA particle adsorbents, the solid bubble-type rubidium-cesium-thallium adsorbent prepared by the method of this invention has higher adsorption efficiency and adsorption capacity. The initial adsorption capacity for cesium is ≥33 mg / g, and the initial adsorption capacity for rubidium is ≥30 mg / g. After 10 cycles, the adsorbent recovery rate is not less than 95%, and the adsorption capacity retention rate relative to the initial adsorption capacity is ≥95%. The removal rate of thallium can reach 98.1%, demonstrating excellent adsorption performance, recyclability, and cycle stability.

[0073] According to another specific embodiment of the present invention, the present invention provides a solid bubble-type rubidium-cesium-thallium adsorbent, which is prepared by the above-described preparation method.

[0074] Specifically, the density of the solid bubble-type rubidium-cesium-thallium adsorbent is less than 1 g / cm³. 3 This ensures that the adsorbent can be rapidly separated and recovered through spontaneous flotation during the adsorption process, thereby reducing operational energy consumption and recovery difficulty.

[0075] Specifically, the solid bubble type rubidium-cesium-thallium adsorbent comprises a modified solid bubble matrix and nano-sized PB or PBA particle adsorbent grafted onto the surface of the matrix. The surface of the solid bubble matrix is ​​activated by etching with an alkaline solution and modified with amino or thiol groups using a silanizing agent. This promotes the grafting of the in-situ generated nano-sized PB or PBA particle adsorbent onto the solid bubble surface, increasing the strength of the bond between the two.

[0076] Compared with existing nanoscale PB or PBA particle adsorbents, the solid bubble-type rubidium-cesium-thallium adsorbent of this invention has higher adsorption efficiency and adsorption capacity. The initial adsorption capacity for cesium is ≥33 mg / g, and the initial adsorption capacity for rubidium is ≥30 mg / g. After 10 cycles, the adsorbent recovery rate is not less than 95%, and the adsorption capacity retention rate relative to the initial adsorption capacity is ≥95%. The removal rate of thallium can reach 98.1%, demonstrating excellent adsorption performance, recyclability, and cycle stability.

[0077] According to another specific embodiment of the present invention, the present invention provides an application of a solid bubble-type rubidium-cesium-thallium adsorbent in nuclear waste treatment, salt lake extraction, and electronic waste resource utilization.

[0078] According to some preferred embodiments of the present invention, a solid bubble-type adsorbent is used to adsorb and extract rubidium and cesium from salt lake brine, wherein the rubidium in the salt lake brine is Cs 2+ 、Rb 2+The concentration range is 0.1-100 mg / L and 1-200 mg / L, the pH is 5-10, the adsorption temperature is 20-60℃, the time is 1-24h, and the amount of solid bubble adsorbent used is 0.1-10 mg / mL.

[0079] The solid bubble-type rubidium, cesium, and thallium adsorbent of this invention has excellent adsorption performance, recyclability, and cycle stability. Moreover, the preparation method is simple and environmentally friendly, the reaction conditions are mild, environmentally friendly, low-cost, and easy to scale up. It combines technological innovation and practicality, significantly reduces the cost of rubidium, cesium, and thallium metal recycling, and promotes the efficient and environmentally friendly development and utilization of metal resources.

[0080] The present invention will be further explained and illustrated below through examples and comparative examples.

[0081] Example 1

[0082] This embodiment provides a method for preparing a solid bubble-type rubidium, cesium, and thallium adsorbent, specifically including the following steps:

[0083] S1: Weigh 15g of hollow glass microspheres (density 0.18g / cm³). 3 Hollow glass microspheres (with a median particle size of 85 μm and a compressive strength of 108 MPa) were placed in 300 mL of 0.5 mol / L sodium hydroxide solution and stirred at 200 rpm for 2 h in an 80 °C water bath. After the reaction was completed, the microspheres were centrifuged and washed three times with ethanol and deionized water, respectively. They were then dried in an oven to obtain activated hollow glass microspheres.

[0084] S2: Weigh 10g of the activated hollow glass microspheres obtained in step S1, place them in a 500mL beaker, add 150mL of anhydrous ethanol, 150mL of pure water and 10mL of APTES, stir in an 80℃ water bath for 2h, after solid-liquid separation, wash the floating solid product three times with deionized water and anhydrous ethanol, and then dry it in an oven to obtain the modified hollow glass microspheres.

[0085] S3: Weigh 2g of the modified hollow glass microspheres obtained in step (2) and add them to 50mL of a 0.15mol / L K3[Fe(CN)6] solution. Shake for 10min until well mixed, then adjust the pH of the solution to 2.5 using citric acid as a coordination regulator. Add 50mL of a 0.1mol / L FeCl2 solution dropwise to the system at a rate of 2mL / min while continuously shaking. The mixture is then kept at 80℃ and shaken for 12h. After solid-liquid separation, wash the floating solid product three times with deionized water and anhydrous ethanol, and then dry it in an oven.

[0086] Two 0.025g portions of the prepared adsorbent were added to 100mL solutions containing 10mg / L rubidium ions and 10mg / L cesium ions, respectively. The solutions were placed in a constant-temperature shaker for adsorption. Samples were taken at regular intervals (e.g., 5min, 10min, 15min, 30min) to determine the ion concentration. The adsorption capacity of the material for rubidium and cesium was calculated using ICP-OES. The experimental results are shown below. Figure 1 As shown, from Figure 1 It was found that adsorption equilibrium was reached after 2 hours. Based on the effective active material, the adsorption capacity for rubidium reached 36.74 mg / g, and the adsorption capacity for cesium ions reached 38.91 mg / g. After 10 cycles, the adsorption capacity retention rates for rubidium and cesium were 96.67% and 95.63%, respectively. This demonstrates that the composite adsorbent has a high adsorption capacity for both rubidium and cesium. 0.025 g of powder was added to 100 mL of solution containing Na... + K + Ca 2+ Mg 2+ 、Rb 2+ Cs 2+ Cyclic selectivity was determined in simulated seawater solutions with a concentration of 10 mg / L. Figure 3 The novel adsorbent exhibits significant adsorption selectivity for rubidium and cesium ions.

[0087] Example 2

[0088] This embodiment provides a method for preparing a solid bubble-type rubidium, cesium, and thallium adsorbent, specifically including the following steps:

[0089] S1: Weigh 20g of hollow glass microspheres (density 0.38g / cm³). 3 The median particle size was 10 μm and the compressive strength was 200 MPa. The particles were placed in 250 mL of 0.1 mol / L sodium hydroxide solution and stirred at 200 rpm for 4 h in an 80 °C water bath. After the reaction was completed, the particles were centrifuged and washed three times with ethanol and deionized water, respectively. The particles were then dried in an oven to obtain activated hollow glass microspheres.

[0090] S2: Weigh 10g of activated hollow glass microspheres and place them in a 500mL beaker. Add 250mL of anhydrous ethanol, 50mL of pure water and 5mL of DAMO. Stir in a 60℃ water bath for 4h. After solid-liquid separation, wash the floating solid product three times with deionized water and anhydrous ethanol and then dry it in an oven to obtain modified hollow glass microspheres.

[0091] S3: Weigh 4g of modified hollow glass microspheres and add them to 60mL of 0.3mol / L K3[Fe(CN)6] solution. Shake for 10min until well mixed. Adjust the pH of the solution to 2.5 using hydrochloric acid as a complexing agent. Add 40mL of 0.3mol / L Co(NO3)2 solution dropwise to the system at a rate of 1mL / min while continuously shaking. Incubate the mixture at 40℃ with constant temperature shaking for 24h. After solid-liquid separation, wash the floating solid product three times with deionized water and anhydrous ethanol, and then dry it in an oven.

[0092] Two 0.025g portions of the prepared adsorbent were added to 100mL solutions containing 10mg / L rubidium ions and 10mg / L cesium ions, respectively. The solutions were placed in a constant-temperature shaker for adsorption. Samples were taken at regular intervals to measure the ion concentrations in the solutions. The adsorption capacity of the material for rubidium and cesium was calculated using ICP-OES. Experimental results showed that adsorption equilibrium was reached after 2 hours. Based on the effective active material, the adsorption equilibrium capacity for rubidium reached 34.58mg / g, and the adsorption capacity for cesium ions reached 36.49mg / g.

[0093] Example 3

[0094] This embodiment provides a method for preparing a solid bubble-type rubidium, cesium, and thallium adsorbent, specifically including the following steps:

[0095] S1: Weigh 20g of hollow glass microspheres (density 0.61g / cm³). 3 The microspheres (with a median particle size of 394 μm and a compressive strength of 22 MPa) were placed in 500 mL of 1 mol / L sodium hydroxide solution and stirred at 200 rpm for 2 h in a 50 °C water bath. After the reaction was completed, the microspheres were centrifuged and washed three times with ethanol and deionized water, respectively. They were then dried in an oven to obtain activated aluminum hollow glass microspheres.

[0096] S2: Weigh 10g of activated hollow glass microspheres and place them in a container. Add 250mL of anhydrous ethanol, 50mL of pure water and 20mL of MPTMS. Stir in a 50℃ water bath for 2 hours. After solid-liquid separation, wash the floating solid product three times with deionized water and anhydrous ethanol and then dry it in an oven to obtain modified aluminum hollow glass microspheres.

[0097] S3: Weigh 3g of modified hollow glass microspheres and add them to 70mL of 0.25mol / L K3[Fe(CN)6] solution. Shake for 10min until well mixed. Adjust the pH of the solution to 3 using citric acid as a complexing agent. Add 30mL of 0.35mol / L CuCl2 solution dropwise to the system at a rate of 1mL / min while continuously shaking. Incubate the mixture at 100℃ for 6h under constant temperature shaking. After solid-liquid separation, wash the floating solid product three times with deionized water and anhydrous ethanol, and then dry it in an oven.

[0098] Two 0.025g portions of the prepared adsorbent were added to 100mL solutions containing 10mg / L rubidium ions and 10mg / L cesium ions, respectively. The solutions were placed in a constant-temperature shaker for adsorption. Samples were taken at regular intervals to measure the ion concentration. The adsorption capacity of the material for rubidium and cesium was calculated using ICP-OES. Experimental results showed that adsorption equilibrium was reached after 2 hours. Based on the effective active material, the adsorption equilibrium capacity for rubidium reached 33.08mg / g, and the adsorption capacity for cesium ions reached 34.56mg / g.

[0099] Example 4

[0100] This embodiment provides a method for preparing a solid bubble-type rubidium, cesium, and thallium adsorbent, specifically including the following steps:

[0101] S1: Weigh 20g of fly ash cenospheres (density 0.58g / cm³). 3 The fly ash celery pellets (with a median particle size of 1000 μm and a compressive strength of 1 MPa) were placed in 500 mL of 1 mol / L sodium hydroxide solution and stirred in a 50 °C water bath for 2 h. After the reaction was completed, the pellets were centrifuged and washed three times with ethanol and deionized water, respectively. They were then dried in an oven to obtain activated fly ash celery pellets.

[0102] S2: Weigh 10g of the activated fly ash cenospheres from step S2 and place them in a 500mL beaker. Add 250mL of anhydrous ethanol, 50mL of pure water and 20mL of MPTMS. Stir in a 50℃ water bath for 2 hours. After solid-liquid separation, wash the floating solid product three times with deionized water and anhydrous ethanol and then dry it in an oven to obtain modified fly ash cenospheres.

[0103] S3: Weigh 1g of modified fly ash cenospheres and add them to 50mL of 0.15mol / L K3[Fe(CN)6] solution. Shake for 10min until well mixed. Then, use hydrochloric acid as a coordination regulator to adjust the pH of the solution to 2. Add 50mL of 0.1mol / L ZnCl2 solution dropwise to the system at a rate of 1mL / min while continuously shaking. The mixture is kept at 60℃ and shaken for 12h. After solid-liquid separation, wash the floating solid product three times with deionized water and anhydrous ethanol and then dry it in an oven.

[0104] Two 0.025g portions of the prepared adsorbent were added to 100mL solutions containing 10mg / L rubidium ions and 10mg / L cesium ions, respectively. The solutions were placed in a constant-temperature shaker for adsorption. Samples were taken at regular intervals to measure the ion concentration. The adsorption capacity of the material for rubidium and cesium was calculated using ICP-OES. Experimental results showed that adsorption equilibrium was reached after 2 hours. Based on the effective active material, the adsorption equilibrium capacity for rubidium reached 30.64mg / g, and the adsorption capacity for cesium ions reached 33.90mg / g.

[0105] Example 5

[0106] This embodiment provides a method for preparing a solid bubble-type rubidium, cesium, and thallium adsorbent, specifically including the following steps:

[0107] S1: Weigh 20g of ceramic bubbles (density 0.90g / cm³). 3 The median particle size was 477 μm and the compressive strength was 18 MPa. The particles were placed in 500 mL of 1 mol / L sodium hydroxide solution and stirred at 200 rpm for 2 h in a 50 °C water bath. After the reaction was completed, the particles were centrifuged and washed three times with ethanol and deionized water, respectively. The particles were then dried in an oven to obtain activated ceramic bubbles.

[0108] S2: Weigh 10g of the activated ceramic bubbles from step S2 and place them in a 500mL beaker. Add 250mL of anhydrous ethanol, 50mL of pure water and 20mL of MPTMS. Stir in a 50℃ water bath for 2 hours. After solid-liquid separation, wash the floating solid product three times with deionized water and anhydrous ethanol and then dry it in an oven to obtain modified ceramic bubbles.

[0109] S3: Weigh 1g of the modified ceramic bubbles and add them to 50mL of a 0.2mol / L K3[Fe(CN)6] solution. Shake for 10min until well mixed. Adjust the pH of the solution to 2.5 using citric acid as a coordination regulator. Add 50mL of a 0.1mol / L MnCl2 solution dropwise to the system at a rate of 4mL / min while continuously shaking. The mixture is then kept at 100℃ and shaken for 4h. After solid-liquid separation, wash the floating solid product three times with ethanol and deionized water, respectively, and dry it in a 60℃ oven for 8h to obtain the rubidium adsorbent.

[0110] Two 0.025g portions of the prepared adsorbent were added to 100mL solutions containing 10mg / L rubidium ions and 10mg / L cesium ions, respectively. The solutions were placed in a constant-temperature shaker for adsorption. Samples were taken at regular intervals to measure the ion concentration. The adsorption capacity of the material for rubidium and cesium was calculated using ICP-OES. Experimental results showed that adsorption equilibrium was reached after 2 hours. Based on the effective active material, the adsorption equilibrium capacity for rubidium reached 36.74mg / g, and the adsorption capacity for cesium ions reached 37.86mg / g.

[0111] Example 6

[0112] This embodiment provides a method for preparing a solid bubble-type rubidium, cesium, and thallium adsorbent, specifically including the following steps:

[0113] S1: Weigh 15g of hollow glass microspheres (density 0.18g / cm³). 3 Hollow glass microspheres (with a median particle size of 85 μm and a compressive strength of 108 MPa) were placed in 300 mL of 0.5 mol / L sodium hydroxide solution and stirred at 200 rpm for 2 h in an 80 °C water bath. After the reaction was completed, the microspheres were centrifuged and washed three times with ethanol and deionized water, respectively. They were then dried in an oven to obtain activated hollow glass microspheres.

[0114] S2: Weigh 10g of the activated hollow glass microspheres obtained in step S1, place them in a 500mL beaker, add 150mL of anhydrous ethanol, 150mL of pure water and 10mL of APTES, stir in an 80℃ water bath for 2h, after solid-liquid separation, wash the floating solid product three times with deionized water and anhydrous ethanol, and then dry it in an oven to obtain the modified hollow glass microspheres.

[0115] S3: Weigh 2g of the modified hollow glass microspheres obtained in step (2) and add them to 50mL of a 0.15mol / L K3[Fe(CN)6] solution. Shake for 10min until well mixed, then adjust the pH of the solution to 2.5 using citric acid as a coordination regulator. Add 50mL of a 0.1mol / L FeCl2 solution dropwise to the system at a rate of 2mL / min while continuously shaking. The mixture is then kept at 80℃ and shaken for 12h. After solid-liquid separation, wash the floating solid product three times with deionized water and anhydrous ethanol, and then dry it in an oven.

[0116] Two 0.5g portions of the prepared adsorbent were added to 100mL of a solution containing 500μg / L thallium ions, respectively, and placed in a constant-temperature shaker for adsorption. Samples were taken at regular intervals to measure the ion concentration in the solution. The adsorption capacity of the material for thallium was calculated using ICP-OES. Experimental results showed that adsorption equilibrium was reached after 1 hour. Based on the effective active material, the thallium removal rate reached 98.1%, and the adsorption equilibrium capacity reached 98.1μg / g.

[0117] Comparative Example 1

[0118] This comparative example uses a precipitation method to prepare Prussian blue powder adsorbent, specifically including the following steps:

[0119] Prepare 50 mL of a 0.1 mol / L K3[Fe(CN)6] solution, shake for 10 min until well mixed, then adjust the pH of the solution to 2.5 using citric acid as a coordination regulator. Add 50 mL of a 0.1 mol / L FeCl3 solution dropwise to the system at a rate of 2 mL / min while continuously shaking. Incubate the mixture at 80 °C with shaking for 12 h. After the reaction is complete, centrifuge and wash three times with ethanol and deionized water respectively, then dry in a 60 °C oven for 8 h to obtain Prussian blue.

[0120] 0.025 g of the prepared adsorbent was added to 100 mL of a 10 mg / L rubidium-cesium ion solution and placed on a shaker until adsorption equilibrium was reached. Samples were taken at regular intervals to measure the ion concentration in the solution. The adsorption capacity of the material for rubidium and cesium was calculated using ICP-OES based on the effective active material. Experimental results showed that adsorption equilibrium was reached after 6 hours of adsorption, with an equilibrium adsorption capacity of 33.82 mg / g for rubidium and 35.11 mg / g for cesium ions. After 10 cycles, the adsorption capacity retention rates for rubidium and cesium were 84.37% and 83.77%, respectively.

[0121] Comparative Example 2

[0122] This comparative example uses solid bubbles without activation pretreatment to prepare a composite rubidium-cesium adsorbent, specifically including the following steps:

[0123] (1) Weigh 10g of hollow glass microspheres (density 0.18g / cm³). 3 The median particle size was 85 μm and the compressive strength was 108 MPa. The particles were placed in a 500 mL beaker, and 150 mL of anhydrous ethanol, 150 mL of pure water and 10 mL of APTES were added. The mixture was stirred in an 80 °C water bath for 2 h. After solid-liquid separation, the floating solid product was washed three times with deionized water and anhydrous ethanol and then dried in an oven. The modified hollow glass microspheres were obtained.

[0124] (2) Weigh 1g of modified hollow glass microspheres and add them to 50mL of 0.1mol / L K3[Fe(CN)6] solution. Shake for 10min until well mixed. Then, adjust the pH of the solution to 2.5 using citric acid as a coordination regulator. Add 50mL of 0.1mol / L FeCl2 solution dropwise to the system at a rate of 2mL / min while continuously shaking. The mixture is kept at 80℃ and shaken for 12h. After the reaction, the solid and liquid are separated. The floating solid product is washed three times with ethanol and deionized water respectively, and dried in an oven at 60℃ for 8h to obtain the composite adsorbent.

[0125] 0.025 g of the prepared composite adsorbent was added to 100 mL of a 10 mg / L rubidium-cesium ion solution and placed on a shaker until adsorption equilibrium was reached. Samples were taken at regular intervals to measure the ion concentration in the solution. The adsorption capacity of the material for rubidium and cesium was calculated using ICP-OES. Experimental results showed that adsorption equilibrium was reached after 2 hours. Based on the effective active material, the adsorption equilibrium capacity for rubidium reached 35.66 mg / g, and the adsorption capacity for cesium ions reached 36.03 mg / g. After 10 cycles, the adsorption capacity retention rates for rubidium and cesium were 68.61% and 66.57%, respectively.

[0126] Comparative Example 3

[0127] This comparative example uses solid bubbles without silanizing reagent modification to prepare a composite rubidium-cesium adsorbent, specifically including the following steps:

[0128] (1) Weigh 15g of hollow glass microspheres (density 0.18g / cm³). 3 The particles (with a median particle size of 85 μm and a compressive strength of 108 MPa) were placed in 300 mL of 0.5 mol / L sodium hydroxide solution and stirred in an 80 °C water bath for 2 h. After solid-liquid separation, the floating solid product was washed three times with deionized water and anhydrous ethanol and then dried in an oven to obtain activated surface-hydroxylated hollow glass microspheres.

[0129] (2) Weigh 1g of surface-hydroxylated hollow glass microspheres and add them to 50mL of 0.1mol / L K3[Fe(CN)6] solution. Shake for 10min until well mixed. Then, use citric acid as a coordination regulator to adjust the pH of the solution to 2.5. Under continuous shaking, add 50mL of 0.1mol / L FeCl2 solution dropwise to the system at a rate of 2mL / min. The mixture is kept at 80℃ and shaken for 12h. After the reaction, the solid and liquid are separated, washed three times with ethanol and deionized water respectively, and dried in an oven at 60℃ for 8h to obtain the composite adsorbent.

[0130] 0.025 g of the prepared adsorbent was added to 100 mL of a 10 mg / L rubidium-cesium ion solution and placed on a shaker until adsorption equilibrium was reached. Samples were taken at regular intervals to measure the ion concentration in the solution. The adsorption capacity of the material for rubidium and cesium was calculated using ICP-OES. Experimental results showed that adsorption was achieved after 2 hours. Based on the effective active material, the adsorption equilibrium capacity for rubidium reached 36.05 mg / g, and the adsorption capacity for cesium ions reached 37.28 mg / g. After 10 cycles, the adsorption capacity retention rates for rubidium and cesium were 75.78% and 74.31%, respectively.

[0131] Comparative Example 4

[0132] The comparative preparation of Prussian blue polymer microspheres rubidium-cesium adsorbent specifically includes the following steps:

[0133] (1) Prepare 50 mL of 0.1 mol / L K3[Fe(CN)6] solution, shake for 10 min until well mixed, then adjust the pH of the solution to 2.5 using citric acid as a coordination regulator. Add 50 mL of 0.1 mol / L FeCl3 solution dropwise to the system at a rate of 2 mL / min while continuously shaking. The mixture is then kept at 80 °C and shaken for 12 h. After the reaction is complete, centrifuge and wash three times with ethanol and deionized water respectively, and dry in an oven at 60 °C for 8 h to obtain Prussian blue.

[0134] (2) Weigh 0.1 g of cyclodextrin and add it to 10 mL of N,N-dimethylpyrrolidone. After it is completely dissolved, add 0.5 g of Prussian blue powder and disperse it evenly. Finally, add 1 g of amine-oxime-modified polypropylene (AOPAN) and stir for 6 h to obtain a polymer solution with suitable viscosity. Add the solution dropwise to deionized water using a disposable dropper. After aging for 5 h, collect the microsphere product by hand and wash it three times with deionized water. After drying, Prussian blue microspheres can be obtained.

[0135] (3) 0.025 g of the prepared adsorbent was added to 100 mL of a rubidium-cesium ion solution with a concentration of 10 mg / L. The solution was shaken on a shaker until adsorption equilibrium was reached. Samples were taken at regular intervals to measure the ion concentration in the solution. The adsorption capacity of the material for rubidium and cesium was calculated using ICP-OES based on the effective active material. The experimental results showed that adsorption equilibrium was reached after 12 h of adsorption. The adsorption equilibrium capacity for rubidium reached 24.07 mg / g, and the adsorption capacity for cesium ions reached 25.18 mg / g. After 10 cycles, the adsorption capacity retention rates of rubidium and cesium were 88.45% and 83.71%, respectively.

[0136] Figure 1 This diagram shows the adsorption capacity of the adsorbent samples prepared in Example 1, Comparative Examples 1 and 4 of this invention for rubidium and cesium at different times. Figure 1 It can be seen that the adsorption capacity of all samples gradually increases with time; however, in the initial adsorption stage, the sample of Example 1 showed a significantly higher adsorption rate than that of Comparative Example 1 and Comparative Example 4, and the sample of Example 1 reached equilibrium at 120 min, while Comparative Example 1 and Comparative Example 4 had not yet reached equilibrium. This is due to its high dispersion characteristics, which allow metal ions in the solution to come into close contact with the surface adsorption sites and achieve rapid adsorption.

[0137] Figure 2 This chart compares the adsorption capacity retention rates of samples from Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3 after ten adsorption cycles, compared to their initial adsorption capacity retention rates. Comparing Example 1 and Comparative Example 1 reveals that the solid bubble adsorbent prepared in this invention exhibits a higher capacity retention rate than the powder adsorbent. However, comparing Example 1, Comparative Example 2, and Comparative Example 3 shows that untreated samples from Comparative Example 2 and Comparative Example 3 exhibit relatively poor cycling performance. This is because the Prussian blue grown in situ on the matrix gradually detaches during the cycling experiment and cannot participate in later adsorption stages. Based on the synergistic treatment of hydroxylation and silanization, stable in-situ growth of Prussian blue can be achieved in the sample of Example 1, exhibiting excellent cycling stability and facilitating long-term cyclic use.

[0138] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for producing a solid bubble-type rubidium, cesium and thallium adsorbent, characterized by, The method comprises: S1: activating the solid bubbles with an alkaline solution; S2: reacting the activated solid bubbles of step S1 with a silanization reagent to obtain modified solid bubbles; S3: the modified solid bubble is immersed in a solution containing [Fe(CN)6] 3- After reaction, a rubidium-caesium-thallium adsorbent with the solid bubble surface complexed with Prussian blue or Prussian blue analogues is obtained.

2. The production method according to claim 1, characterized by, In step S1, the alkaline solution is a sodium hydroxide or potassium hydroxide aqueous solution with a concentration of 0.5-5 mol / L.

3. The method of claim 1, wherein, The solid bubbles are one or more of hollow glass beads, hollow glass microspheres, fly ash floating beads, ceramic bubbles, the density of the solid bubbles is 0.10-0.90 g / cm 3 , the particle size is 10-1000 μm, and the compressive strength is 1 MPa-200 MPa.

4. The method of claim 1, wherein, In step S1, the specific steps of the activation treatment are to place the solid bubbles in the strong alkali solution at a solid-liquid ratio of 10-100 g / L and stir.

5. The preparation method according to claim 1, characterized in that, In step S2, the silanization reagent is one or more of 3-aminopropyltriethoxysilane, bis-[3-(trimethoxysilyl)propyl]ethylenediamine, and 3-mercaptopropyltrimethoxysilane. And / or, the mass ratio of the solid bubbles to the silanization reagent is 1:0.5-4.

6. The method of claim 1, wherein, In step S2, the reaction is specifically mixing the solid bubbles and the silanization reagent in a solvent and reacting at a temperature of 40-80℃ for 2-12 h.

7. The preparation method according to claim 1, characterized in that, In step S3, the mass ratio of the solid gas bubbles to the solution containing [Fe(CN)6] 3- is 1-5:50, and the concentration of [Fe(CN)6] 3- is 0.1-0.4 mol / L.

8. The method of claim 1, wherein, In step S3, the metal ion in the transition metal salt is at least one of Fe 2+ , Mn 2+ , Co 2+ , Ni 2+ , Cu 2+ , and Zn 2+ ; the concentration of the transition metal salt solution is 0.1-0.4 mol / L.

9. A solid bubble-type rubidium-caesium-thallium adsorbent, characterized in that, The solid bubble type rubidium cesium thallium adsorbent is prepared by the preparation method of any one of claims 1-8.

10. Application of a solid bubble type rubidium cesium thallium adsorbent in nuclear waste treatment, salt lake extraction, and electronic waste resource treatment.

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