Rubidium cesium ion adsorbent material, method for preparing same, and use thereof

Abstract

The present application relates to the field of adsorbing material, discloses a kind of rubidium cesium ion adsorbing material and its preparation method and application, the rubidium cesium ion adsorbing material includes framework and the organic sulfonate and / or organic sulfate modified metal ferricyanide adsorbent dispersed in the framework;The framework includes polyvinyl alcohol and crosslinked sodium alginate;The framework and the organic sulfonate and / or organic sulfate modified metal ferricyanide adsorbent are connected by amino-containing silane coupling agent.The rubidium cesium ion adsorbing material is not easy to fall off in long-term use process, metal ferricyanide adsorbent has high saturation adsorption capacity of rubidium and cesium and excellent stability.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of adsorbent materials, in particular, to a rubidium and cesium ion adsorbent material and a preparation method and application thereof. BACKGROUND

[0002] Rubidium and cesium are rare alkali metals with important economic value and application value in emerging industries, including biomedical research, solar cells, atomic clocks and electronic products. Rubidium and cesium are mainly extracted from ores or salt lakes or lithium. The rarity of rubidium and cesium and their specific industrial uses make it necessary to develop efficient processes to extract rubidium and cesium. Researchers use solvent extraction, precipitation, adsorption and hybrid membrane adsorption technology to recover Rb.

[0003] The adsorption method for extracting rubidium and cesium ions in the solution has the advantages of high recovery rate and simple operation. Metal ferricyanide adsorbent has good ion exchange performance and large adsorption capacity, but its powder particles are small and have poor mechanical strength, which cannot be directly applied to fixed bed and other conventional equipment for adsorption-desorption. Therefore, it is urgent to develop a granulated product with good mechanical strength and high adsorption capacity. SUMMARY

[0004] The purpose of the present application is to overcome the problems of poor stability of the existing granulated product with polyvinyl alcohol as the skeleton to wrap the adsorbent powder and agglomeration of the adsorbent powder, and to provide a rubidium and cesium ion adsorbent material. The organic sulfate and / or organic sulfonate modified metal ferricyanide adsorbent in the rubidium and cesium ion adsorbent material can be connected with the polyvinyl alcohol and cross-linked sodium alginate forming the skeleton through the amino-containing silane coupling agent. In the long-term use process, the metal ferricyanide adsorbent is not easy to fall off, and the organic sulfate and / or organic sulfonate modified metal ferricyanide adsorbent has excellent compatibility with the polyvinyl alcohol and cross-linked sodium alginate as the skeleton, so that the rubidium and cesium ion adsorbent material has excellent stability while maintaining high saturation adsorption capacity of rubidium and cesium.

[0005] In order to achieve the above-mentioned purpose, the first aspect of the present application provides a rubidium and cesium ion adsorbent material, wherein the rubidium and cesium ion adsorbent material comprises a skeleton and an organic sulfonate and / or organic sulfate modified metal ferricyanide adsorbent dispersed in the skeleton.

[0006] The skeleton comprises polyvinyl alcohol and cross-linked sodium alginate; the skeleton and the organic sulfonate and / or organic sulfate modified metal ferricyanide adsorbent are connected through an amino-containing silane coupling agent.

[0007] The second aspect of the present application provides a preparation method of a rubidium and cesium ion adsorbent material, wherein the preparation method comprises the following steps:

[0008] (1) mixing the metal ferric cyanide adsorbent with an aqueous organic sulfonate solution and / or an aqueous organic sulfate solution to modify the metal ferric cyanide adsorbent, thereby obtaining an organic sulfonate and / or organic sulfate modified metal ferric cyanide adsorbent;

[0009] (2) mixing the organic sulfonate and / or organic sulfate modified metal ferric cyanide adsorbent, an aqueous polyvinyl alcohol solution, and an aqueous sodium alginate solution, adjusting the pH value, and then adding an optional pore-forming agent and an amino-containing silane coupling agent to perform a coupling reaction;

[0010] (3) adding the product of step (2) into a solution of a polyvalent cation salt to obtain the rubidium and cesium ion adsorption material.

[0011] The third aspect of the present application provides a rubidium and cesium ion adsorption material prepared by the above preparation method.

[0012] The fourth aspect of the present application provides an application of the above rubidium and cesium ion adsorption material in the field of extracting rubidium and / or cesium.

[0013] Through the above technical solution, the rubidium and cesium ion adsorption material and the preparation method and application thereof provided by the present application have the following beneficial effects:

[0014] The organic sulfonate and / or organic sulfate modified metal ferric cyanide adsorbent in the rubidium and cesium ion adsorption material of the present application can be connected with the polyvinyl alcohol and cross-linked sodium alginate forming a skeleton through an amino-containing silane coupling agent. In the long-term use process, the metal ferric cyanide adsorbent is not easy to fall off, and the organic sulfonate and / or organic sulfate modified metal ferric cyanide adsorbent has excellent compatibility with the polyvinyl alcohol and cross-linked sodium alginate as the skeleton, so that the rubidium and cesium ion adsorption material has excellent stability while maintaining a high saturated adsorption capacity of rubidium and cesium.

[0015] The preparation method of the rubidium and cesium ion adsorption material provided by the present application performs a coupling reaction by using an organic sulfonate and / or organic sulfate modified metal ferric cyanide adsorbent, polyvinyl alcohol, cross-linked sodium alginate, and an amino-containing silane coupling agent. In the long-term use process, the metal ferric cyanide adsorbent is not easy to fall off, and the obtained rubidium and cesium ion adsorption material has a high saturated adsorption capacity and excellent stability. DETAILED DESCRIPTION

[0016] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The ranges and values should be interpreted as being approximate. The endpoints of the ranges and values are provided as exemplifications of the ranges and values. Other values within the ranges and values are neither practical nor are they to be excluded from the ranges or values. Each range and value given is intended to be a specific exemplification of a broader range or value. The disclosure is not to be limited to the specific ranges or values presented.

[0017] The first aspect of the present application provides a rubidium and cesium ion adsorption material, wherein the rubidium and cesium ion adsorption material comprises a skeleton, and an organic sulfonate and / or organic sulfate modified metal ferricyanide adsorbent dispersed in the skeleton;

[0018] The skeleton comprises polyvinyl alcohol and cross-linked sodium alginate; and the skeleton and the organic sulfonate and / or organic sulfate modified metal ferricyanide adsorbent are connected by an amino-containing silane coupling agent.

[0019] In the present application, the organic sulfonate and / or organic sulfate modified metal ferricyanide adsorbent in the rubidium and cesium ion adsorption material can be connected to the polyvinyl alcohol and cross-linked sodium alginate forming the skeleton through the amino-containing silane coupling agent. During long-term use, the metal ferricyanide adsorbent is not easy to fall off, and the organic sulfonate and / or organic sulfate modified metal ferricyanide adsorbent has excellent compatibility with the polyvinyl alcohol and cross-linked sodium alginate as the skeleton, so that the rubidium and cesium ion adsorption material has excellent stability while maintaining a high saturated adsorption capacity of rubidium and cesium.

[0020] According to the present application, the content of the polyvinyl alcohol is 5wt%-16wt%, the content of the cross-linked sodium alginate is 3wt%-8wt%, the content of the organic sulfonate and / or organic sulfate modified metal ferricyanide adsorbent is 25wt%-65wt%, and the content of the amino-containing silane coupling agent is 15wt%-65wt%, based on the total weight of the rubidium and cesium ion adsorption material.

[0021] In the present application, the sum of the contents of the polyvinyl alcohol, the cross-linked sodium alginate, the organic sulfonate and / or organic sulfate modified metal ferricyanide adsorbent, and the amino-containing silane coupling agent is 100wt%, based on the total weight of the rubidium and cesium ion adsorption material. When the content of each component in the rubidium and cesium ion adsorption material meets the above range, the strength of the adsorption material can be ensured, and the adsorption material can be prevented from breaking during adsorption-desorption, and the adsorption material can have a large adsorption capacity.

[0022] Further, the content of the polyvinyl alcohol is 8wt%-12wt%, the content of the cross-linked sodium alginate is 4wt%-6wt%, the content of the organic sulfonate and / or organic sulfate modified metal ferricyanide adsorbent is 30wt%-50wt%, and the content of the amino-containing silane coupling agent is 35wt%-55wt%, based on the total weight of the rubidium and cesium ion adsorption material.

[0023] In the present application, the organic sulfonate and / or organic sulfate can form a modified layer on the surface of the metal ferricyanide adsorbent. The modified layer can make the metal ferricyanide adsorbent have good compatibility with the polymer skeleton, and avoid the metal ferricyanide from agglomerating in the polymer.

[0024] According to the present application, the thickness of the modified layer formed by the organic sulfonate and / or organic sulfate in the metal ferricyanide adsorbent modified by the organic sulfonate and / or organic sulfate is 4-10 nm.

[0025] According to the present application, the organic sulfonate is sodium fatty acid methyl ester sulfonate (MES).

[0026] In the present application, the number of carbon atoms of the sodium fatty acid methyl ester sulfonate is not particularly limited, for example, the sodium fatty acid methyl ester sulfonate can be C12-C18 sodium fatty acid methyl ester sulfonate.

[0027] According to the present application, the organic sulfate is sodium fatty alcohol polyoxyethylene ether sulfate (AES).

[0028] According to the present application, the metal ferricyanide adsorbent is at least one selected from the group consisting of ferrocyanide iron, potassium cobalt cyanide, potassium nickel ferrocyanide, potassium titanium ferrocyanide, potassium copper ferrocyanide and potassium cadmium ferrocyanide.

[0029] Further, the metal ferricyanide adsorbent is ferrocyanide iron.

[0030] According to the present application, the amino-containing silane coupling agent is at least one selected from the group consisting of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, methylaminopropyltrimethoxysilane and 4-amino-3,3-dimethylbutyltrimethoxysilane.

[0031] In the present application, when the above-mentioned amino-containing silane coupling agent is selected, the polymer skeleton can be better cross-linked, so that the rubidium and cesium ion adsorption material is formed and has better strength, and is not damaged during use.

[0032] Further, the amino-containing silane coupling agent is at least one selected from the group consisting of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and 4-amino-3,3-dimethylbutyltrimethoxysilane.

[0033] According to the present application, the weight average molecular weight of the polyvinyl alcohol is 80-150 kg / mol.

[0034] In the present application, when the weight average molecular weight of the polyvinyl alcohol satisfies the above range, the strength of the rubidium and cesium ion adsorption material is higher.

[0035] Further, the weight average molecular weight of the polyvinyl alcohol is 80-110 thousand g / mol.

[0036] According to the present application, the alcoholysis degree of the polyvinyl alcohol is 85-98%.

[0037] In the present application, when the alcoholysis degree of the polyvinyl alcohol satisfies the above range, the mechanical strength and hydrophilicity of the adsorption material can be improved.

[0038] According to the present application, the average particle size of the rubidium and cesium ion adsorption material is 2-5 mm.

[0039] According to the present application, the porosity of the rubidium and cesium ion adsorption material is 75-85%.

[0040] In the present application, when the porosity of the rubidium and cesium ion adsorption material satisfies the above range, it indicates that the skeleton formed by the polyvinyl alcohol and the crosslinked sodium alginate has a network structure, which can reduce the mass transfer resistance, so that the rubidium and cesium ion adsorption material has a faster water mass transfer rate.

[0041] Further, the porosity of the rubidium and cesium ion adsorption material is 80-85%.

[0042] According to the present application, the contact angle of the rubidium and cesium ion adsorption material is 30-45°.

[0043] In the present application, when the contact angle of the rubidium and cesium ion adsorption material satisfies the above range, it indicates that the rubidium and cesium ion adsorption material has excellent hydrophilicity.

[0044] The second aspect of the present application provides a preparation method of a rubidium and cesium ion adsorption material, wherein the preparation method comprises the following steps:

[0045] (1) mixing and modifying a metal ferricyanide adsorbent with an aqueous organic sulfonate solution and / or an aqueous organic sulfate solution to obtain an organic sulfonate and / or organic sulfate modified metal ferricyanide adsorbent;

[0046] (2) mixing, adjusting pH value, and then adding an optional pore-forming agent and an amino-containing silane coupling agent for coupling reaction of the organic sulfonate and / or organic sulfate modified metal ferricyanide adsorbent, an aqueous polyvinyl alcohol solution, and an aqueous sodium alginate solution;

[0047] (3) adding the product of step (2) into a polyvalent cation salt solution to obtain the rubidium and cesium ion adsorption material.

[0048] In the present application, the metal ferricyanide adsorbent modified by organic sulfonate and / or organic sulfate, polyvinyl alcohol, cross-linked sodium alginate and amino-containing silane coupling agent are coupled to obtain a rubidium and cesium ion adsorption material, which has high saturated adsorption capacity and excellent stability because the metal ferricyanide adsorbent is not easy to fall off during long-term use.

[0049] According to the present application, the metal ferricyanide adsorbent is at least one selected from ferrocyanide iron, potassium cobalt cyanide, potassium nickel ferrocyanide, potassium titanium ferrocyanide, potassium copper ferrocyanide and potassium cadmium ferrocyanide.

[0050] Further, the metal ferricyanide adsorbent is ferrocyanide iron.

[0051] According to the present application, the organic sulfonate is sodium fatty acid methyl ester sulfonate.

[0052] According to the present application, the organic sulfate is sodium fatty alcohol polyoxyethylene ether sulfate.

[0053] According to the present application, the concentration of the aqueous solution of the organic sulfonate and the aqueous solution of the organic sulfate is independently 0.1 mg / L-1 mg / L.

[0054] According to the present application, the mass ratio of the metal ferricyanide adsorbent to the organic sulfonate and / or the organic sulfate is 1:0.1-1.

[0055] According to the present application, the modification conditions of the mixture include that the modification time is 1-4 h and the modification temperature is 25-40℃.

[0056] According to the present application, based on the total weight of the metal ferricyanide adsorbent modified by organic sulfonate and / or organic sulfate, polyvinyl alcohol, sodium alginate and amino-containing silane coupling agent, the content of the polyvinyl alcohol is 5wt%-16wt%, the content of the cross-linked sodium alginate is 3wt%-8wt%, the content of the metal ferricyanide adsorbent modified by organic sulfonate and / or organic sulfate is 25wt%-65wt%, and the content of the amino-containing silane coupling agent is 15wt%-65wt%.

[0057] In the present application, the sum of the content of the metal ferricyanide adsorbent modified by organic sulfonate and / or organic sulfate, the polyvinyl alcohol, the sodium alginate and the amino-containing silane coupling agent is 100wt%. When the content of each component meets the above range, the prepared rubidium and cesium ion adsorption material has both good strength and large adsorption capacity.

[0058] Further, the content of the polyvinyl alcohol is 8wt%-12wt%, the content of the crosslinked sodium alginate is 4wt%-6wt%, the content of the metal ferricyanide adsorbent modified by the organic sulfonate and / or organic sulfate is 30wt%-50wt%, and the content of the amino-containing silane coupling agent is 35wt%-55wt%, based on the total weight of the polyvinyl alcohol, the crosslinked sodium alginate, the metal ferricyanide adsorbent modified by the organic sulfonate and / or organic sulfate, and the amino-containing silane coupling agent.

[0059] According to the present application, the concentration of the polyvinyl alcohol aqueous solution is 10wt%-15wt%.

[0060] According to the present application, the amino-containing silane coupling agent is at least one selected from the group consisting of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, methylaminopropyltrimethoxysilane, and 4-amino-3,3-dimethylbutyltrimethoxysilane.

[0061] In the present application, when the above-mentioned amino-containing silane coupling agent is selected, the polymer skeleton can be better crosslinked, so that the rubidium and cesium ion adsorption material is formed and has better strength and is not broken during use

[0062] Further, the amino-containing silane coupling agent is at least one selected from the group consisting of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and 4-amino-3,3-dimethylbutyltrimethoxysilane.

[0063] According to the present application, the weight average molecular weight of the polyvinyl alcohol is 80-150 thousand g / mol.

[0064] In the present application, when the weight average molecular weight of the polyvinyl alcohol meets the above-mentioned range, the strength of the rubidium and cesium ion adsorption material is higher.

[0065] Further, the weight average molecular weight of the polyvinyl alcohol is 80-150 thousand g / mol.

[0066] According to the present application, the alcoholysis degree of the polyvinyl alcohol is 85%-98%.

[0067] In the present application, when the alcoholysis degree of the polyvinyl alcohol meets the above-mentioned range, the mechanical strength and hydrophilicity of the adsorption material can be improved.

[0068] In the present application, the pore-forming agent is hydrogen peroxide.

[0069] According to the application, the amount of the pore-forming agent is 1wt%-12wt% relative to the weight of the polyvinyl alcohol.

[0070] According to a preferred embodiment of the application, in step (2), after mixing, adjusting pH value of the organic sulfonate and / or organic sulfate modified metal ferricyanide adsorbent, polyvinyl alcohol aqueous solution and sodium alginate aqueous solution, adding amino-containing silane coupling agent to perform coupling reaction, after time T of the coupling reaction, adding the pore-forming agent; better pore-forming effect can be obtained. Preferably, the time T of the coupling reaction is ≥30min.

[0071] According to the application, in step (2), the pH value is 1-3.

[0072] According to the application, the conditions of the coupling reaction include: the coupling reaction temperature is 50-70℃, and the coupling reaction time is 50min-4h.

[0073] According to the application, in step (3), the multivalent cation salt solution is selected from at least one of CaCl2 aqueous solution, MgCl2 aqueous solution and CuCl2 aqueous solution.

[0074] Further, the multivalent cation salt solution is CaCl2 aqueous solution.

[0075] According to the application, the amount of the multivalent cation salt solution is such that the mass ratio of sodium alginate to the multivalent cation salt is 1:1-4.

[0076] According to the application, the concentration of the multivalent cation salt solution is 1wt%-4wt%.

[0077] According to the application, the product of step (2) is dropped into the multivalent cation salt solution at a speed of 1-2mL / min.

[0078] In the application, step (1) comprises: mixing the metal ferricyanide adsorbent with organic sulfonate aqueous solution and / or organic sulfate aqueous solution to modify, centrifuging and drying to obtain the organic sulfonate and / or organic sulfate modified metal ferricyanide adsorbent.

[0079] The third aspect of the application provides a rubidium and cesium ion adsorption material prepared by the above preparation method.

[0080] The fourth aspect of the application provides an application of the above rubidium and cesium ion adsorption material in the field of extracting rubidium and / or cesium.

[0081] The application will be described in detail through examples below.

[0082] In the following examples and comparative examples, the performances involved are obtained by the following methods:

[0083] Dynamic adsorption-desorption cycle method of rubidium cesium ion adsorbent: The obtained rubidium cesium ion adsorbent (4 g) was loaded into a glass column and acid washed (acid washing was performed at 30°C using 400 mL of 0.5 M hydrochloric acid, and the flow rate of the hydrochloric acid was 2 mL / min), and then 400 mL of rubidium carbonate solution (Rb + with a concentration of 200 ppm, pH = 10) or 400 mL of cesium carbonate solution (Cs 2+ with a concentration of 50 ppm, pH = 7.6) was pumped into the column at a flow rate of 2 mL / min using a peristaltic pump to perform a dynamic adsorption-desorption cycle for 24 h. Then, 0.5 M hydrochloric acid (200 mL) was pumped into the column at a flow rate of 2 mL / min using a peristaltic pump to desorb the rubidium ions or cesium ions in the particles for 24 h. Then, deionized water was used to wash the column to neutralization, which was one cycle.

[0084] Saturation adsorption capacity of rubidium and cesium ions: The change in adsorption capacity with time was monitored during a dynamic adsorption-desorption cycle, and the saturation adsorption capacity Q was calculated according to the following formula:

[0085]

[0086] wherein Q is the saturation adsorption capacity, in mg / g, which reflects the adsorption amount of the rubidium cesium ion adsorbent when adsorption reaches equilibrium; C0 and C are the ion concentrations in the solution at the start and at the saturation of adsorption, respectively, in mg / L; V is the volume of the rubidium carbonate solution or the cesium carbonate solution, in L; and M is the mass of the rubidium cesium ion adsorbent, in g.

[0087] Concentration of rubidium ions and cesium ions: Ion chromatography (ICS-1100, DIONEX, America) was used to determine the ion concentration.

[0088] Contact angle of rubidium cesium ion adsorbent: The contact angle was measured using a DSA100 surface contact angle measuring instrument produced by KRUSS, Germany.

[0089] Porosity of rubidium cesium ion adsorbent: The porosity was measured using a porosity tester.

[0090] Mass loss ratio of rubidium cesium ion adsorbent: The mass loss ratio was determined by weighing the mass of the adsorbent before use (i.e., the initial mass) and the mass of the adsorbent after 30 adsorption-desorption cycles, and the ratio of the lost mass to the initial mass was the mass loss ratio.

[0091] The content of polyvinyl alcohol, crosslinked sodium alginate, organic sulfonate and / or organic sulfate modified metal ferricyanide adsorbent, and amino-containing silane coupling agent in the rubidium cesium ion adsorbent was calculated according to the feeding ratio of the corresponding raw materials.

[0092] Average particle diameter of the rubidium cesium ion adsorbent material, thickness of the modified layer: The thickness of the modified layer formed by the organic sulfonate and / or organic sulfate, the average particle diameter of the rubidium cesium ion adsorbent material were characterized by a scanning electron microscope (SEM, S-4800).

[0093] Weight average molecular weight of polyvinyl alcohol: Measured by gel permeation chromatography (GPC).

[0094] Polyvinyl alcohol A: alcoholysis degree of 88%, weight average molecular weight of 89000 g / mol.

[0095] Polyvinyl alcohol B: alcoholysis degree of 95%, weight average molecular weight of 12000 g / mol.

[0096] In the following examples and comparative examples, the room temperature is 25°C.

[0097] Other raw materials used in the preparation examples, examples and comparative examples are commercially available.

[0098] Preparation Example 1

[0099] The ferrous ferricyanide was dispersed in an aqueous solution, and an aqueous AES solution (in which the concentration of AES was 0.1 wt%) was added and mixed so that the mass usage ratio of the adsorbent powder and AES was 1:0.1, and mixed for modification at room temperature for 2 h.

[0100] The above mixed solution was centrifuged, and the solid phase material was dried to obtain the organic sulfate modified metal ferricyanide adsorbent A. The water content thereof was 0.5 wt%.

[0101] Preparation Example 2

[0102] The ferrous ferricyanide was dispersed in an aqueous solution, and an aqueous AES solution (in which the concentration of AES was 0.1 wt%) was added and mixed so that the mass usage ratio of the adsorbent powder and AES was 1:0.5, and mixed for modification at room temperature for 2 h.

[0103] The above mixed solution was centrifuged, and the solid phase material was dried to obtain the organic sulfate modified metal ferricyanide adsorbent B. The water content thereof was 0.5 wt%.

[0104] Preparation Example 3

[0105] The ferrous ferricyanide was dispersed in an aqueous solution, and an aqueous AES solution (in which the concentration of AES was 0.1 wt%) was added and mixed so that the mass usage ratio of the adsorbent powder and AES was 1:1, and mixed for modification at room temperature for 2 h.

[0106] The above mixed solution was centrifuged, and the solid phase material was dried to obtain the organic sulfate modified metal ferricyanide adsorbent C. The water content thereof was 0.5 wt%.

[0107] Preparation Example 4

[0108] An organic sulfonate-modified metal ferricyanide adsorbent D was prepared according to the method of Preparation Example 1, except that the aqueous AES solution was replaced with an aqueous MES solution. The water content of the organic sulfonate-modified metal ferricyanide adsorbent D was 0.5 wt%.

[0109] Example 1

[0110] (1) An aqueous solution of 15 wt% polyvinyl alcohol A, the organic sulfonate-modified metal ferricyanide adsorbent A, and an aqueous solution of sodium alginate (1 wt%) were mixed and stirred until uniform. After adjusting the pH to 1 with 0.1 M HC1, the mixture was stirred uniformly at 70°C, and γ-aminopropyltrimethoxysilane was added. The content of the polyvinyl alcohol was 8.7 wt%, the content of the crosslinked sodium alginate was 4.4 wt%, the content of the organic sulfonate-modified metal ferricyanide adsorbent was 34.7 wt%, and the content of the amino-containing silane coupling agent was 52.2 wt%, based on the total weight of the organic sulfonate-modified metal ferricyanide adsorbent, the polyvinyl alcohol, the sodium alginate, and the amino-containing silane coupling agent. The coupling was performed at 70°C for 2 h, and 1 mL of a 1 wt% H2O2 solution was added at 30 min of the coupling reaction (the amount of the pore-forming agent was 6.7 wt% relative to the weight of the polyvinyl alcohol).

[0111] (2) The product obtained in step (1) was loaded into a syringe pump, and was dropped into a 4 wt% aqueous CaCl2 solution at a rate of 1 mL / min, and was dried to obtain a rubidium-caesium ion adsorbing material having a particle size of 3 mm.

[0112] Example 2

[0113] (1) An aqueous solution of 15 wt% polyvinyl alcohol A, the organic sulfonate-modified metal ferricyanide adsorbent B, and an aqueous solution of sodium alginate (1 wt%) were mixed and stirred until uniform. After adjusting the pH to 1 with 0.1 M HC1, the mixture was stirred uniformly at 70°C, and γ-aminopropyltrimethoxysilane was added. The content of the polyvinyl alcohol was 11.8 wt%, the content of the crosslinked sodium alginate was 5.9 wt%, the content of the organic sulfonate-modified metal ferricyanide adsorbent was 47.1 wt%, and the content of the amino-containing silane coupling agent was 35.2 wt%, based on the total weight of the organic sulfonate-modified metal ferricyanide adsorbent, the polyvinyl alcohol, the sodium alginate, and the amino-containing silane coupling agent. The coupling was performed at 70°C for 2 h, and 1 mL of a 1 wt% H2O2 solution was added at 30 min of the coupling reaction (the amount of the pore-forming agent was 6.7 wt% relative to the weight of the polyvinyl alcohol).

[0114] (2) The product obtained in step (1) is loaded into a syringe pump and dripped into a 4wt% CaCl2 aqueous solution at a rate of 1 mL / min, and dried to obtain a rubidium-caesium ion adsorbent material with a particle size of 3 mm.

[0115] Example 3

[0116] (1) A 15wt% polyvinyl alcohol A aqueous solution, an organic sulphate modified metal ferricyanide adsorbent C and a sodium alginate aqueous solution (1wt%) are mixed and stirred uniformly, and then 0.1M HCl is added to adjust the pH to 1. Then, γ-aminopropyltrimethoxysilane is added, and the content of the polyvinyl alcohol is 6.9wt% based on the total weight of the organic sulphate modified metal ferricyanide adsorbent, the crosslinked sodium alginate and the amino-containing silane coupling agent, the content of the crosslinked sodium alginate is 3.5wt%, the content of the organic sulphate modified metal ferricyanide adsorbent is 27.5wt%, and the content of the amino-containing silane coupling agent is 62.1wt%. The coupling is carried out at 70°C for 2h, and 1 mL of a 1wt% H2O2 solution is added at 30min (the amount of the pore-forming agent is 6.7wt% based on the weight of the polyvinyl alcohol).

[0117] (2) The product obtained in step (1) is loaded into a syringe pump and dripped into a 4wt% CaCl2 aqueous solution at a rate of 1 mL / min, and dried to obtain a rubidium-caesium ion adsorbent material with a particle size of 3 mm.

[0118] Example 4

[0119] A rubidium-caesium ion adsorbent material is prepared according to the method of Example 1, except that the organic sulphate modified metal ferricyanide adsorbent A is replaced by an organic sulphonic acid modified metal ferricyanide adsorbent D.

[0120] Example 5

[0121] A rubidium-caesium ion adsorbent material is prepared according to the method of Example 1, except that the γ-aminopropyltrimethoxysilane is replaced by γ-aminopropyltriethoxysilane.

[0122] Example 6

[0123] A rubidium-caesium ion adsorbent material is prepared according to the method of Example 1, except that the γ-aminopropyltrimethoxysilane is replaced by 4-amino-3,3-dimethylbutyltrimethoxysilane.

[0124] Example 7

[0125] (1) A 15 wt% aqueous solution of polyvinyl alcohol A, an organic sulfate-modified metal ferricyanide adsorbent A, and an aqueous solution of sodium alginate (1 wt%) were mixed and stirred uniformly, and then adjusted to pH 1 with 0.1 M HC1. After stirring uniformly at 70°C, γ-aminopropyltrimethoxysilane was added. The content of the polyvinyl alcohol was 15.4 wt%, the content of the crosslinked sodium alginate was 7.7 wt%, the content of the organic sulfate-modified metal ferricyanide adsorbent was 61.5 wt%, and the content of the amino-containing silane coupling agent was 15.4 wt%, based on the total weight of the organic sulfate-modified metal ferricyanide adsorbent, the polyvinyl alcohol, the sodium alginate, and the amino-containing silane coupling agent. The coupling was performed at 70°C for 2 h, and 1 mL of a 1 wt% H2O2 solution was added at 30 min after the start of the coupling reaction (the amount of the pore former was 6.7 wt% relative to the weight of the polyvinyl alcohol).

[0126] (2) The product obtained in step (1) was loaded into a syringe pump, and dropped into a 4 wt% aqueous CaCl2 solution at a rate of 1 mL / min. After drying, a rubidium-caesium ion adsorbent material having a particle size of 3 mm was obtained.

[0127] Example 8

[0128] (1) A 9 wt% aqueous solution of polyvinyl alcohol B, an organic sulfate-modified metal ferricyanide adsorbent A, and an aqueous solution of sodium alginate (1 wt%) were mixed and stirred uniformly, and then adjusted to pH 1 with 0.1 M HC1. After stirring uniformly at 70°C, γ-aminopropyltrimethoxysilane was added. The content of the polyvinyl alcohol was 8.7 wt%, the content of the crosslinked sodium alginate was 4.4 wt%, the content of the organic sulfate-modified metal ferricyanide adsorbent was 34.7 wt%, and the content of the amino-containing silane coupling agent was 52.2 wt%, based on the total weight of the organic sulfate-modified metal ferricyanide adsorbent, the polyvinyl alcohol, the sodium alginate, and the amino-containing silane coupling agent. The coupling was performed at 70°C for 2 h, and 1 mL of a 1 wt% H2O2 solution was added at 30 min after the start of the coupling reaction (the amount of the pore former was 11.1 wt% relative to the weight of the polyvinyl alcohol).

[0129] (2) The product obtained in step (1) was loaded into a syringe pump, and dropped into a 4 wt% aqueous CaCl2 solution at a rate of 1 mL / min. After drying, a rubidium-caesium ion adsorbent material having a particle size of 3 mm was obtained.

[0130] Example 9

[0131] A rubidium-caesium ion adsorbent material was prepared according to the method of Example 1, except that the content of polyvinyl alcohol was 15.2 wt%, the content of cross-linked sodium alginate was 7.6 wt%, the content of organic sulfate-modified metal ferricyanide adsorbent was 75.7 wt%, and the content of amino-containing silane coupling agent was 1.5 wt%.

[0132] Example 10

[0133] (1) A 15 wt% aqueous solution of polyvinyl alcohol A, organic sulfate-modified metal ferricyanide adsorbent A, and an aqueous solution of sodium alginate (1 wt%) were mixed and stirred uniformly. After adjusting the pH to 1 with 0.1 M HC1, stirring was performed uniformly at 70°C, and γ-aminopropyltrimethoxysilane was added, 1 mL of a 1 wt% solution of H2O2 was added (the amount of pore-forming agent was 6.7 wt% relative to the weight of the polyvinyl alcohol), and coupling was performed at 70°C for 2 h; based on the total weight of the organic sulfate-modified metal ferricyanide adsorbent, polyvinyl alcohol, sodium alginate, and amino-containing silane coupling agent, the content of polyvinyl alcohol was 8.7 wt%, the content of cross-linked sodium alginate was 4.4 wt%, the content of organic sulfate-modified metal ferricyanide adsorbent was 34.7 wt%, and the content of amino-containing silane coupling agent was 52.2 wt%.

[0134] (2) The product obtained in step (1) was loaded into a syringe pump, and was dropped into a 4 wt% aqueous solution of CaCl2 at a rate of 1 mL / min, and was dried to obtain a rubidium-caesium ion adsorbent material with a particle size of 3 mm.

[0135] Example 11

[0136] A rubidium-caesium ion adsorbent material was prepared according to the method of Example 1, except that no H2O2 solution was added.

[0137] Comparative Example 1

[0138] A rubidium-caesium ion adsorbent material was prepared according to the method of Example 1, except that the organic sulfate-modified metal ferricyanide adsorbent A was replaced with iron ferrocyanide. Based on the total weight of the iron ferrocyanide, polyvinyl alcohol, sodium alginate, and amino-containing silane coupling agent, the content of polyvinyl alcohol was 8.7 wt%, the content of cross-linked sodium alginate was 4.4 wt%, the content of iron ferrocyanide was 34.7 wt%, and the content of amino-containing silane coupling agent was 52.2 wt%.

[0139] Comparative Example 2

[0140] The rubidium and cesium ion adsorbing material was prepared according to the method of Example 1, except that the silane coupling agent containing amino was not added. The content of the polyvinyl alcohol was 18.2 wt%, the content of the crosslinked sodium alginate was 9.1 wt%, and the content of the organic sulfate modified metal ferricyanide adsorbent was 72.7 wt% based on the total weight of the organic sulfate modified metal ferricyanide adsorbent, polyvinyl alcohol and sodium alginate.

[0141] Comparative Example 3

[0142] The rubidium and cesium ion adsorbing material was prepared according to the method of Example 1, except that the sodium alginate was not added.

[0143] In the present application, the content of the organic sulfonate and / or organic sulfate modified metal ferricyanide adsorbent, polyvinyl alcohol, sodium alginate and silane coupling agent containing amino in the rubidium and cesium ion adsorbing material of the examples and comparative examples is shown in Table 1. The thickness of the modified layer, porosity, contact angle, saturated rubidium ion adsorption capacity Q Rb , saturated cesium ion adsorption capacity Q Cs and mass loss ratio of the rubidium and cesium ion adsorbing material of the examples and comparative examples are shown in Table 2.

[0144] Table 1

[0145]

[0146]

[0147] Table 2

[0148]

[0149] It can be seen from the results that the rubidium and cesium ion adsorbing material of the examples has a rubidium ion adsorption capacity greater than or equal to 10.2 mg / g, a saturated cesium ion adsorption capacity greater than or equal to 5 mg / g, and a mass loss ratio less than or equal to 2.1 wt% after 30 times of adsorption and acid washing desorption. It is shown that the rubidium and cesium ion adsorbing material prepared by the scheme of the present application has good saturated rubidium ion and cesium ion adsorption capacity, and the structure of the rubidium and cesium ion adsorbing material is stable, the metal ferricyanide adsorbent is not easy to fall off from the skeleton during long-term use, and the rubidium and cesium ion adsorbing material has good acid resistance. Comparative Example 3 does not add sodium alginate, and the polyvinyl alcohol has poor formability in CaCl2 aqueous solution.

[0150] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A rubidium-cesium ion adsorption material, characterized in that: The rubidium and cesium ion adsorption material includes a skeleton and a metal ferrocyanide adsorbent modified by an organic sulfonate and / or an organic sulfate dispersed in the skeleton; The skeleton comprises polyvinyl alcohol and cross-linked sodium alginate; The skeleton is connected to the metal ferrocyanide adsorbent modified by the organic sulfonate and / or organic sulfate via an amino-containing silane coupling agent; Based on the total weight of the rubidium and cesium ion adsorption material, the content of the polyvinyl alcohol is 5wt%-16wt%, the content of the cross-linked sodium alginate is 3wt%-8wt%, the content of the metal ferrocyanide adsorbent modified by the organic sulfonate and / or organic sulfate is 25wt%-65wt%, and the content of the amino-containing silane coupling agent is 15wt%-65wt%.

2. The rubidium-cesium ion adsorbent according to claim 1, wherein Based on the total weight of the rubidium and cesium ion adsorption material, the content of the polyvinyl alcohol is 8wt%-12wt%, the content of the cross-linked sodium alginate is 4wt%-6wt%, the content of the metal ferrocyanide adsorbent modified by the organic sulfonate and / or organic sulfate is 30wt%-50wt%, and the content of the amino-containing silane coupling agent is 35wt%-55wt%.

3. The rubidium-cesium ion adsorbent according to claim 1 or 2, wherein: The thickness of the modified layer formed by the organic sulfonate and / or organic sulfate in the metal ferrocyanide adsorbent modified by the organic sulfonate and / or organic sulfate is 4-10 nm; and / or, the organic sulfonate is sodium fatty acid methyl ester sulfonate; And / or, the organic sulfate is sodium fatty alcohol polyoxyethylene ether sulfate; And / or, the metal ferrocyanide adsorbent is selected from at least one of ferric ferrocyanide, potassium nickel ferrocyanide, potassium titanium ferrocyanide, potassium copper ferrocyanide and potassium cadmium ferrocyanide.

4. The rubidium-cesium ion adsorbent according to claim 1 or 2, wherein: The amino-containing silane coupling agent is selected from at least one of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, methylaminopropyltrimethoxysilane and 4-amino-3,3-dimethylbutyltrimethoxysilane; and / or, the weight average molecular weight of the polyvinyl alcohol is 80,000-150,000 g / mol; And / or, the alcoholysis degree of the polyvinyl alcohol is 85-98%.

5. The rubidium-cesium ion adsorbent according to claim 1 or 2, wherein: The average particle size of the rubidium-cesium ion adsorption material is 2-5 mm; and / or, the porosity of the rubidium-cesium ion adsorption material is 75-85%; And / or, the contact angle of the rubidium-cesium ion adsorption material is 30-45°.

6. The rubidium-cesium ion adsorbent material according to claim 5, wherein The porosity of the rubidium-cesium ion adsorption material is 80-85%.

7. A method for preparing a rubidium-cesium ion adsorption material, characterized in that: The preparation method comprises the following steps: (1) mixing and modifying a metal ferrocyanide adsorbent with an organic sulfonate aqueous solution and / or an organic sulfate aqueous solution to obtain an organic sulfonate and / or organic sulfate modified metal ferrocyanide adsorbent; (2) mixing a metal ferrocyanide adsorbent modified with an organic sulfonate and / or organic sulfate, a polyvinyl alcohol aqueous solution, and a sodium alginate aqueous solution, adjusting the pH value, adding an optional pore-forming agent, and adding an amino-containing silane coupling agent to carry out a coupling reaction; (3) adding the product of step (2) to a polyvalent cation salt solution to obtain the rubidium and cesium ion adsorption material; Based on the total weight of the organic sulfonate and / or organic sulfate modified metal ferrocyanide adsorbent, polyvinyl alcohol, sodium alginate and amino-containing silane coupling agent, the content of the polyvinyl alcohol is 5wt%-16wt%, the content of the sodium alginate is 3wt%-8wt%, the content of the organic sulfonate and / or organic sulfate modified metal ferrocyanide adsorbent is 25wt%-65wt%, and the content of the amino-containing silane coupling agent is 15wt%-65wt%.

8. The preparation method according to claim 7, wherein The metal ferrocyanide adsorbent is selected from at least one of ferric ferrocyanide, potassium nickel ferrocyanide, potassium titanium ferrocyanide, potassium copper ferrocyanide and potassium cadmium ferrocyanide; and / or, the organic sulfonate is sodium fatty acid methyl ester sulfonate; And / or, the organic sulfate is sodium fatty alcohol polyoxyethylene ether sulfate; and / or, the concentrations of the organic sulfonate aqueous solution and the organic sulfate aqueous solution are each independently 0.1 mg / L-1 mg / L; and / or, the mass ratio of the metal ferrocyanide adsorbent to the organic sulfonate and / or organic sulfate is 1:0.1-1; And / or, the mixed modification conditions include: modification time of 1-4 hours, modification temperature of 25-40°C.

9. The preparation method according to claim 7, wherein The concentration of the polyvinyl alcohol aqueous solution is 10 wt %-15 wt %.

10. The preparation method according to claim 7, wherein Based on the total weight of the organic sulfonate and / or organic sulfate modified metal ferrocyanide adsorbent, polyvinyl alcohol, sodium alginate and amino-containing silane coupling agent, the content of the polyvinyl alcohol is 8wt%-12wt%, the content of the sodium alginate is 4wt%-6wt%, the content of the organic sulfonate and / or organic sulfate modified metal ferrocyanide adsorbent is 30wt%-50wt%, and the content of the amino-containing silane coupling agent is 35wt%-55wt%; And / or, the amino-containing silane coupling agent is selected from at least one of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, methylaminopropyltrimethoxysilane and 4-amino-3,3-dimethylbutyltrimethoxysilane; and / or, the weight average molecular weight of the polyvinyl alcohol is 80,000-150,000 g / mol; and / or, the alcoholysis degree of the polyvinyl alcohol is 85-98%; And / or, relative to the weight of polyvinyl alcohol, the amount of the pore-forming agent is 1 wt%-12 wt%.

11. The preparation method according to claim 7 or 8, wherein In step (2), the pH value is 1-3; And / or, the coupling reaction conditions include: coupling reaction temperature of 50-70° C., coupling reaction time of 50 min-4 h.

12. The preparation method according to claim 7 or 8, wherein In step (3), the polyvalent cation salt solution is selected from at least one of a CaCl2 aqueous solution, a MgCl2 aqueous solution, and a CuCl2 aqueous solution; and / or, the amount of the multivalent cation salt solution used is such that the mass ratio of sodium alginate to the multivalent cation salt is 1:1-4; and / or, the concentration of the multivalent cation salt solution is 1 wt%-4 wt%; and / or, the product of step (2) is dripped into the multivalent cation salt solution at a rate of 1-2 mL / min.

13. A rubidium and cesium ion adsorption material prepared by the preparation method according to any one of claims 7 to 12.

14. Use of the rubidium and cesium ion adsorption material according to any one of claims 1 to 6 and 13 in the field of extracting rubidium and / or cesium.

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