Synthesis method and application of beta-cyclodextrin aluminum citrate ion imprinted material

Abstract

This invention discloses a method for synthesizing β-cyclodextrin / aluminum citrate ion-imprinted materials and their applications. The synthesis method includes the following steps: S1, β-cyclodextrin, citric acid, and potassium dihydrogen phosphate are poured into a bottle containing deionized water, mixed uniformly, and reacted in a water bath to synthesize a β-cyclodextrin / citric acid precursor; S2, aluminum sulfate octadecyl sulfate, ethylene glycol dimethacrylate, and ammonium persulfate are sequentially poured into a bottle, and reacted in a water bath to synthesize a crude product of β-cyclodextrin / aluminum citrate ion polymer; S3, the crude product in the bottle is dried; S4, the crude product is washed with deionized water, filtered, dried, and modified by grinding with ethanol; S5, the product is soaked in sodium hydroxide solution, washed with deionized water to a neutral pH value, and dried to obtain the β-cyclodextrin / aluminum citrate ion-imprinted material. The synthesis process of this invention is simple, and the β-cyclodextrin source is simple and the cost is low. The prepared product has significantly improved mechanical strength and acid resistance, and has the characteristics of appropriate strength and stable adsorption under acidic conditions.

Description

Technical Field

[0001] This invention belongs to the fields of mineral materials and environmental protection technology, specifically relating to a method for synthesizing β-cyclodextrin aluminum citrate ion-imprinted materials and their applications. Background Technology

[0002] Rare earth elements, as non-renewable resources, have relatively small overall reserves. However, due to their magnetic, optical, and catalytic properties, they are widely used in new energy, superconductors, and information technology fields. The purity of rare earth products directly affects their value. Ion-adsorption rare earth ores have advantages over other rare earth minerals, such as ease of mining, extraction, and low cost. Currently, mature processing technologies exist for ion-adsorption rare earth ores, but the problem of excessively high impurity content still exists, particularly for Al. 3+ and rare earth ions (Re 3+ Because they have similar properties, impurities Al are present in the subsequent rare earth extraction and separation process. 3+ With Re 3+ Competitive extraction reduces the rare earth content, leading to rare earth loss. Therefore, it is necessary to develop a method to selectively remove Al impurities from rare earth mother liquor. 3+ The technology for achieving efficient recovery of rare earth ores through ion adsorption is of great importance.

[0003] Currently, the removal of Al from rare earth mother liquor 3+ The main methods include precipitation, extraction, and adsorption. Currently, ammonium bicarbonate precipitation is primarily used industrially, but this process generates large amounts of ammonia nitrogen wastewater, causing secondary pollution. Furthermore, aluminum extractants are currently scarce and prone to emulsification reactions. Adsorption, due to its green and environmentally friendly characteristics, is considered the most promising method. The core of adsorption is the adsorbent material. Researchers have developed various adsorbent materials for the selective removal of Al from complex rare earth solutions. 3+ Examples of suitable materials include ion exchange resins, hydrogels, activated carbon, and ion-imprinted materials. The selectivity of ion exchange resins is primarily determined by the ion charge, hydration radius, and solution environment (pH, concentration), making it difficult to distinguish ions with similar charges and radii. Hydrogels trap ions through pores in their hydrophilic network or adsorb ions via weak bonds (hydrogen bonds, van der Waals forces), but their dynamic cross-linked network is susceptible to swelling, leading to deformation of recognition sites, and the random distribution of functional groups makes high-precision recognition difficult. Activated carbon's selectivity is determined by pore size distribution (micropores trap small molecules) and the weak ionization of surface functional groups (such as carboxyl groups), but its surface chemical modification is limited, lacking directional recognition sites. Ion-imprinted materials form specific binding sites through the directional interaction between template ions and functional monomers, exhibiting specific recognition of target ions. Therefore, due to their high selectivity, they have attracted considerable attention in the field of rare earth separation.

[0004] Scholars have successfully prepared aluminum ion-imprinted materials for rare earth separation. B. Özkahraman et al. synthesized an ion-imprinted biosorbent [Al(III)-IP] using epichlorohydrin as a crosslinking agent and chitosan as a functional monomer. Their research found that Al(III)-IP and non-imprinted materials have different effects on the separation of aluminum ions. 3+ The adsorption capacities for Al were 48 mg / g and 12 mg / g, respectively, and their adsorption for Al... 3+ The selectivity coefficient was 4.4. Li et al. used acrylic acid as a functional monomer, aluminum sulfate octadecylhydrate as a template ion, and EGDMA as a crosslinking agent to react under certain conditions to generate a product which was then loaded onto hydrochloric acid-activated silica gel to obtain aluminum ion imprinted material (IIP-Al). IIP-Al showed a high selectivity for Al. 3+ The maximum adsorption capacity can reach 106 mg / g, in combination with Nd 3+ In mixed solutions, its selectivity coefficient can reach up to 17.76; Behisht et al. synthesized Aluminum(III) using methacrylic acid as a monomer and divinylbenzene as a crosslinking agent, and found that it exhibited high selectivity for Al at pH 4.5. 3+ The adsorption capacity can reach up to 165.1 µmol·g. −1 However, the selectivity of ion-imprinted materials under low pH conditions remains a challenge in existing literature. Furthermore, due to the similar chemical properties of rare earth elements and aluminum, they precipitate together at pH values ​​exceeding 4.3. Therefore, a method for selectively precipitating Al in rare earth mother liquor at low pH conditions has been developed. 3+ Materials with highly selective adsorption properties are an urgent problem to be solved.

[0005] β-Cyclodextrin (β-CD), as a low-cost natural polymer, stands out among many adsorbents due to its excellent biocompatibility, non-toxicity, and low water solubility. Currently, some researchers have used β-CD to prepare ion-imprinted materials. Nchoe et al. encapsulated 1,5'-diphenylcarbazine (DPC) ligands in β-CD and then added crosslinking agents ethylene glycol dimethacrylate (EGDMA) and 4-vinylpyridine (4-VP) to obtain chromium ion-imprinted materials, achieving a maximum adsorption capacity of 15.61 mg / g for Cr(VI), but its regenerability was poor. Fan et al. used glutaraldehyde as a crosslinking agent and employed a sol-gel method to prepare hydrogel beads with β-CD, finding that they could adsorb Cu... 2+The adsorption capacity can reach up to 822 mg / g, exhibiting good regeneration performance, but the method is relatively complex and the selectivity coefficient is lower compared to other ion-imprinted materials. Researchers have found that crosslinking natural, non-toxic, highly reactive, and readily available citric acid (CA) with β-CD to form β-CD / CA polymers can not only solve the problem of low water solubility of β-CD and change its chemical properties without collapsing its hydrophobic cavity structure, but also add carboxyl and ester groups to enhance the material's performance. He et al. systematically reviewed previous research on the synthesis mechanism and application of β-CD / CA complexes formed by crosslinking CA and β-CD. Currently, β-CD / CA has not been used to prepare ion-imprinted materials. Therefore, developing a new, simple, and highly selective β-cyclodextrin-based adsorbent material would be beneficial in attracting more scholars to focus on β-cyclodextrin research.

[0006] Currently, the synthesis of aluminum ion imprinted materials has the following shortcomings: 1) The preparation process of ion imprinted materials is complex and the amount of crosslinking agent used is large, which limits their large-scale industrial application; 2) Ion imprinted materials have a large saturated adsorption capacity, but low mechanical strength and low selective adsorption performance.

[0007] Therefore, a method for synthesizing β-cyclodextrin aluminum citrate ion imprinted materials with simple process, high mechanical strength, and high selectivity, and its application, is urgently needed. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this invention provides a method for synthesizing β-cyclodextrin-citric acid aluminum ion imprinted materials and their applications. The process is simple, low-cost, and produces no secondary pollution. It also exhibits a strong selective ability to remove aluminum ions from solutions and good cycle stability, making it a promising method for aluminum ion removal.

[0009] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0010] The first objective of this invention is to provide a method for synthesizing β-cyclodextrin / aluminum citrate ion-imprinted materials, comprising the following steps:

[0011] S1. Pour β-cyclodextrin, citric acid and potassium dihydrogen phosphate into a bottle containing deionized water solution, mix evenly, and heat in a water bath to synthesize the precursor β-cyclodextrin / citric acid.

[0012] S2. Add aluminum sulfate octadecyl water, ethylene glycol dimethacrylate and ammonium persulfate into the bottle in sequence, heat in a water bath to react, and dry the crude product in the bottle after the reaction is completed.

[0013] S3. Wash the crude product with deionized water, filter and dry it, then grind and modify it with ethanol to obtain β-cyclodextrin / aluminum citrate ion polymer material.

[0014] S4, using 0.25 mol·L -1 Soaking in sodium hydroxide solution removes aluminum ions from the β-cyclodextrin / aluminum citrate polymer material;

[0015] S5. Wash with deionized water to adjust the pH of the β-cyclodextrin / aluminum citrate polymer material to neutral. After drying, obtain the β-cyclodextrin / aluminum citrate imprinted material.

[0016] Preferably, in step S1, the mass ratio of β-cyclodextrin, citric acid, and potassium dihydrogen phosphate is 4:(1-12):1;

[0017] In step S1, the water bath reaction involves placing the bottle in a water bath constant temperature shaker and stirring it. The temperature of the constant temperature shaker is 70-120°C, and the water bath time is 0.5-5 hours.

[0018] Preferably, in step S2, the mass ratio of aluminum sulfate octahydrate, ethylene glycol dimethacrylate, and ammonium persulfate is (1-3):(0.2-0.7):(0.1-0.3).

[0019] In step S2, the water bath reaction involves placing the bottle in a water bath constant temperature shaker and stirring. The temperature of the constant temperature shaker is 110-160°C, and the water bath time is 10-60 minutes.

[0020] In step S2, the drying temperature is 120–160°C and the drying time is 45–105 min.

[0021] Preferably, the soaking time in sodium hydroxide solution in step S4 is 6 to 8 hours.

[0022] Preferably, the drying temperature in step S5 is 80-90°C and the drying time is 6-12 hours.

[0023] The second objective of this invention is to provide an application of β-cyclodextrin-citric acid aluminum ion imprinted material for the selective removal of aluminum ions from rare earth elements, comprising the following steps:

[0024] S6. Prepare an aluminum ion solution of a certain concentration using aluminum sulfate;

[0025] S7. Measure the aluminum ion solution, adjust the pH value to 2.5~4 with sulfuric acid or sodium hydroxide, add the β-cyclodextrin / citric acid aluminum ion imprinting material to the aluminum ion solution, shake to mix and react, filter to separate and obtain the supernatant.

[0026] S8. Detect the aluminum ion concentration in the supernatant and calculate the removal rate and adsorption amount of aluminum ions by the β-cyclodextrin / aluminum citrate imprinted material.

[0027] S9. Measure out the mixed solution of aluminum ions and rare earth ions, add the β-cyclodextrin / aluminum citrate imprinted material to the mixed solution of aluminum ions and rare earth ions, shake to mix and react, filter to separate and obtain the supernatant.

[0028] S10. Detect the concentration of aluminum ions and rare earth ions in the supernatant, and calculate the selectivity coefficient of the β-cyclodextrin / aluminum citrate imprinted material for aluminum ions.

[0029] Preferably, the concentration of the aluminum ion solution in step S6 is 10 mg / L to 500 mg / L.

[0030] Preferably, in step S7, the mass ratio of β-cyclodextrin / aluminum citrate ion imprinting material to aluminum ions is (60~250):(0.5~25).

[0031] In step S7, the mixing reaction is carried out in a constant temperature shaking chamber at a reaction temperature of 25°C for a reaction time of 0.5 to 26 hours.

[0032] Preferably, in step S9, the rare earth ions in the aluminum ion and rare earth ion mixed solution are at least one of lanthanum, yttrium, and erbium.

[0033] Preferably, in step S9, the concentration of rare earth ions in the mixed solution of aluminum ions and rare earth ions is 100 mg / L and the concentration of aluminum ions is 20 mg / L; the mass ratio of β-cyclodextrin / aluminum citrate imprinted material to aluminum ions is 100:1.

[0034] In step S9, the mixing reaction is carried out in a constant temperature shaking chamber at a temperature of 25°C for a time of 0.5 to 26 hours.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) This invention uses β-cyclodextrin as raw material to synthesize the precursor β-cyclodextrin / citric acid through esterification reaction, and uses β-cyclodextrin / citric acid to synthesize aluminum ion imprinted material with strong selectivity to aluminum ions through water bath method. The synthesis process is simple, and the source of β-cyclodextrin is simple and the cost is low.

[0037] (2) Compared with other methods, the β-cyclodextrin-based ion-imprinted materials prepared by this invention have significantly improved mechanical strength and acid resistance, and have the characteristics of appropriate strength and stable adsorption under acidic conditions.

[0038] (3) The β-cyclodextrin / aluminum citrate ion imprinted material prepared in this invention still has a high removal rate and selectivity for aluminum ions in the solution after multiple cycles of reuse, and the material loss rate is extremely low, and it has good chemical stability.

[0039] (4) The process of this invention is green and environmentally friendly, with significant environmental and economic benefits, and is suitable for industrial production. Attached Figure Description

[0040] Figure 1 This invention provides examples of β-cyclodextrin / aluminum citrate ion-imprinted materials with different β-cyclodextrin / aluminum citrate mass ratios for Al. 3+ Curves showing adsorption capacity and selectivity coefficient;

[0041] Figure 2 Example 2 of this invention illustrates the effect of β-cyclodextrin / citric acid aluminum ion imprinted materials on Al at different β-cyclodextrin / citric acid synthesis temperatures. 3+ Curves showing adsorption capacity and selectivity coefficient;

[0042] Figure 3 Example 3 of this invention describes the effect of β-cyclodextrin / citric acid aluminum ion imprinted materials on Al under different β-cyclodextrin / citric acid synthesis times. 3+ Curves showing adsorption capacity and selectivity coefficient;

[0043] Figure 4 Example 4 of this invention illustrates the effect of β-cyclodextrin / aluminum citrate ion-imprinted materials on Al under different water bath times. 3+ Curves showing adsorption capacity and selectivity coefficient;

[0044] Figure 5 Example 5 of this invention illustrates the effect of β-cyclodextrin / aluminum citrate ion-imprinted materials on Al under different curing times. 3+ Curves showing adsorption capacity and selectivity coefficient;

[0045] Figure 6 Example 6 of this invention illustrates the effect of β-cyclodextrin / aluminum citrate ion-imprinted materials on Al at different curing temperatures. 3+ Curves showing adsorption capacity and selectivity coefficient;

[0046] Figure 7 Example 7 of this invention illustrates the effect of β-cyclodextrin / aluminum citrate ion-imprinted materials on Al under different pH conditions. 3+ A graph showing the adsorption capacity and removal rate;

[0047] Figure 8 Examples 8 of this invention illustrate the effects of different amounts of β-cyclodextrin / aluminum citrate ion-imprinted materials on Al. 3+ A graph showing the adsorption capacity and removal rate;

[0048] Figure 9 Example 9 of this invention illustrates the effect of β-cyclodextrin / aluminum citrate ion-imprinted materials on Al under different oscillation times. 3+ A graph showing the adsorption capacity and removal rate;

[0049] Figure 10 Example 10 of this invention illustrates the effect of β-cyclodextrin / aluminum citrate ion-imprinted materials on Al at different initial concentrations. 3+ Adsorption capacity curve;

[0050] Figure 11 This invention provides an example of the effect of β-cyclodextrin / aluminum citrate ion-imprinted material on Al under different cycle numbers in Example 11 of the present invention. 3+ Curves showing adsorption capacity and selectivity coefficient;

[0051] Figure 12 This is a schematic diagram of the synthesis method of the present invention. Detailed Implementation

[0052] The preferred embodiments of the present invention will be described below with reference to the accompanying drawings. It should be understood that the preferred embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0053] Example 1

[0054] like Figure 12 As shown, a certain mass ratio of β-cyclodextrin:citric acid (4:1, 3:1, 2:1, 1:1, 1:2, 1:3) and 0.75g KH2PO4 were successively added to a conical flask containing 30ml of deionized water and reacted in a water bath at 100℃ for 3 hours to form a clear and transparent solution. 1g of aluminum sulfate, 3mmol of EGDMA, and 1mmol of ammonium persulfate were then added sequentially to the conical flask containing the precursor. The conical flask was then placed back into a magnetic stirrer and reacted in a water bath for 30 minutes. After stirring, the mixture in the conical flask was poured into a petri dish and placed in a forced-air drying oven at 140℃ for 75 minutes. After the incubation time, the forced-air drying oven was turned off, and the petri dish was left in the oven to cool to room temperature. After washing the product several times with deionized water, the solid product was collected by centrifugation and dried in a vacuum drying oven. After constant weight, it was ground into powder and then reacted with 0.25mol·L⁻¹. -1 Aluminum ions were eluted from the β-cyclodextrin / aluminum citrate ion polymer by washing with NaOH solution for 6 hours. Solid-liquid separation was performed using a centrifuge, and the sample was washed with deionized water until neutral, then dried in an oven at 80℃ to obtain the β-cyclodextrin / aluminum citrate ion imprinted material. 0.1 g of the β-cyclodextrin / aluminum citrate ion imprinted material was added to 50 mL of a mixed solution of 20 mg / L aluminum ions and 100 mg / L lanthanum ions (pH adjusted to 4 with sulfuric acid or sodium hydroxide). The solution was shaken in a constant temperature shaking incubator for 20 h, filtered, and the supernatant was obtained. The concentrations of aluminum and lanthanum ions in the supernatant were detected by ICP, and the adsorption capacity and selectivity of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions were calculated. Figure 1This embodiment uses β-cyclodextrin / citric acid aluminum ion-imprinted materials with different β-cyclodextrin / citric acid mass ratios to support the effects of Al 3+ A graph showing the adsorption capacity and selectivity coefficient.

[0055] Depend on Figure 1 It can be seen that β-cyclodextrin / aluminum citrate ion-imprinted materials have a significant effect on Al 3+ The adsorption capacity and selectivity coefficient reached their peaks at a β-cyclodextrin / citric acid mass ratio of 2:1, with the selectivity coefficient exceeding 70.

[0056] Example 2

[0057] like Figure 12 As shown, 3g of β-cyclodextrin, 1.5g of citric acid, and 0.75g of KH₂PO₄ were successively added to a conical flask containing 30ml of deionized water and reacted in a water bath at 70℃, 80℃, 90℃, 100℃, 110℃, and 120℃ for 3 hours, respectively, to form a clear and transparent solution. 1g of aluminum sulfate, 3mmol of EGDMA, and 1mmol of ammonium persulfate were then added sequentially to the conical flask containing the precursor. The conical flask was then placed back into a magnetic stirrer and reacted in a water bath for 30 minutes. After stirring, the mixture in the conical flask was poured into a petri dish and placed in a forced-air drying oven at 140℃ for 75 minutes. After the incubation time, the forced-air drying oven was turned off, and the petri dish was left in the drying oven to cool to room temperature. After washing the product several times with deionized water, the solid product was collected by centrifugation and dried in a vacuum drying oven. After constant weight, it was ground into powder and then treated with 0.25mol·L⁻¹. -1 Aluminum ions were eluted from the β-cyclodextrin / aluminum citrate ion polymer by washing with NaOH solution for 6 hours. Solid-liquid separation was performed using a centrifuge, and the sample was washed with deionized water until neutral, then dried in an oven at 80℃ to obtain the β-cyclodextrin / aluminum citrate ion imprinted material. 0.1 g of the β-cyclodextrin / aluminum citrate ion imprinted material was added to 50 mL of a mixed solution of 20 mg / L aluminum ions and 100 mg / L lanthanum ions (pH adjusted to 4 with sulfuric acid or sodium hydroxide). The solution was shaken in a constant temperature shaking incubator for 20 h, filtered, and the supernatant was obtained. The concentrations of aluminum and lanthanum ions in the supernatant were detected by ICP, and the adsorption capacity and selectivity of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions were calculated. Figure 2 This embodiment illustrates the effect of β-cyclodextrin / citric acid aluminum ion-imprinted materials on Al at different β-cyclodextrin / citric acid synthesis temperatures. 3+ A graph showing the adsorption capacity and selectivity coefficient.

[0058] Depend on Figure 2 It can be seen that β-cyclodextrin / aluminum citrate ion-imprinted materials have a significant effect on Al 3+The adsorption capacity and selectivity coefficients reached their peak at 100℃, with the adsorption capacity exceeding 4.5 mg / g.

[0059] Example 3

[0060] like Figure 12 As shown, 3g of β-cyclodextrin, 1.5g of citric acid, and 0.75g of KH₂PO₄ were successively added to a conical flask containing 30ml of deionized water and reacted in a water bath at 100℃ for 0.5h, 1h, 2h, 3h, 4h, and 5h, respectively, to form a clear and transparent solution. 1g of aluminum sulfate, 3mmol of EGDMA, and 1mmol of ammonium persulfate were then added sequentially to the conical flask containing the precursor. The conical flask was then placed back into a magnetic stirrer and reacted in a water bath for 30 minutes. After stirring, the mixture in the conical flask was poured into a petri dish and placed in a forced-air drying oven at 140℃ for 75 minutes. After the incubation time, the forced-air drying oven was turned off, and the petri dish was left in the drying oven to cool to room temperature. After washing the product several times with deionized water, the solid product was collected by centrifugation and dried in a vacuum drying oven. After constant weight, it was ground into powder and then processed with 0.25mol·L⁻¹. -1 Aluminum ions were eluted from the β-cyclodextrin / aluminum citrate ion polymer by washing with NaOH solution for 6 hours. Solid-liquid separation was performed using a centrifuge, and the sample was washed with deionized water until neutral, then dried in an oven at 80℃ to obtain the β-cyclodextrin / aluminum citrate ion imprinted material. 0.1 g of the β-cyclodextrin / aluminum citrate ion imprinted material was added to 50 mL of a mixed solution of 20 mg / L aluminum ions and 100 mg / L lanthanum ions (pH adjusted to 4 with sulfuric acid or sodium hydroxide). The solution was shaken in a constant temperature shaking incubator for 20 h, filtered, and the supernatant was obtained. The concentrations of aluminum and lanthanum ions in the supernatant were detected by ICP, and the adsorption capacity and selectivity of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions were calculated. Figure 3 This embodiment illustrates the effect of β-cyclodextrin / citric acid aluminum ion-imprinted materials on Al under different β-cyclodextrin / citric acid synthesis times. 3+ A graph showing the adsorption capacity and selectivity coefficient.

[0061] Depend on Figure 3 It can be seen that β-cyclodextrin / aluminum citrate ion-imprinted materials have a significant effect on Al 3+ The adsorption capacity and selectivity coefficient reached their peaks at a synthesis time of 3 hours, with the selectivity coefficient reaching over 72.

[0062] Example 4

[0063] like Figure 12As shown, 3g of β-cyclodextrin, 1.5g of citric acid, and 0.75g of KH₂PO₄ were successively added to an Erlenmeyer flask containing 30ml of deionized water and reacted in a water bath at 100℃ for 3 hours to form a clear and transparent solution. 1g of aluminum sulfate, 3mmol of EGDMA, and 1mmol of ammonium persulfate were then added sequentially to the Erlenmeyer flask containing the precursor. The Erlenmeyer flask was then placed back into a magnetic stirrer and reacted in a water bath for 10min, 20min, 30min, 40min, 50min, and 60min, respectively. After stirring, the mixture in the Erlenmeyer flask was poured into a petri dish and placed in a forced-air drying oven at 140℃ for 75min. After the incubation period, the forced-air drying oven was turned off, and the petri dish was left in the oven to cool to room temperature. After washing the product several times with deionized water, the solid product was collected by centrifugation and dried in a vacuum drying oven. After constant weight, it was ground into powder and then processed with 0.25mol·L⁻¹. -1 Aluminum ions were eluted from the β-cyclodextrin / aluminum citrate ion polymer by washing with NaOH solution for 6 hours. Solid-liquid separation was performed using a centrifuge, and the sample was washed with deionized water until neutral, then dried in an oven at 80℃ to obtain the β-cyclodextrin / aluminum citrate ion imprinted material. 0.1 g of the β-cyclodextrin / aluminum citrate ion imprinted material was added to 50 mL of a mixed solution of 20 mg / L aluminum ions and 100 mg / L lanthanum ions (pH adjusted to 4 with sulfuric acid or sodium hydroxide). The solution was shaken in a constant temperature shaking incubator for 20 h, filtered, and the supernatant was obtained. The concentrations of aluminum and lanthanum ions in the supernatant were detected by ICP, and the adsorption capacity and selectivity of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions were calculated. Figure 4 This embodiment illustrates the effect of β-cyclodextrin / aluminum citrate ion-imprinted materials on Al under different water bath times. 3+ A graph showing the adsorption capacity and selectivity coefficient.

[0064] Depend on Figure 4 It can be seen that β-cyclodextrin / aluminum citrate ion-imprinted materials have a significant effect on Al 3+ The adsorption capacity and selectivity coefficient reached their peaks when the water bath time was 30 min, with the adsorption capacity reaching over 4.6 mg / g.

[0065] Example 5

[0066] like Figure 12As shown, 3g of β-cyclodextrin, 1.5g of citric acid, and 0.75g of KH₂PO₄ were successively added to an Erlenmeyer flask containing 30ml of deionized water and reacted in a water bath at 100℃ for 3 hours to form a clear and transparent solution. 1g of aluminum sulfate, 3mmol of EGDMA, and 1mmol of ammonium persulfate were then added sequentially to the Erlenmeyer flask containing the precursor. The Erlenmeyer flask was then placed back into a magnetic stirrer and reacted in a water bath for 30 minutes. After stirring, the mixture in the Erlenmeyer flask was poured into a petri dish and placed in a forced-air drying oven. The dish was incubated at 140℃ for 45min, 60min, 75min, 90min, and 105min, respectively. After the incubation time, the forced-air drying oven was turned off, and the petri dish was left in the oven to cool to room temperature. After washing the product several times with deionized water, the solid product was collected by centrifugation and dried in a vacuum drying oven. After constant weight, it was ground into powder and then processed with 0.25mol·L⁻¹. -1 Aluminum ions were eluted from the β-cyclodextrin / aluminum citrate ion polymer by washing with NaOH solution for 6 hours. Solid-liquid separation was performed using a centrifuge, and the sample was washed with deionized water until neutral, then dried in an oven at 80℃ to obtain the β-cyclodextrin / aluminum citrate ion imprinted material. 0.1 g of the β-cyclodextrin / aluminum citrate ion imprinted material was added to 50 mL of a mixed solution of 20 mg / L aluminum ions and 100 mg / L lanthanum ions (pH adjusted to 4 with sulfuric acid or sodium hydroxide). The solution was shaken in a constant temperature shaking incubator for 20 h, filtered, and the supernatant was obtained. The concentrations of aluminum and lanthanum ions in the supernatant were detected by ICP, and the adsorption capacity and selectivity of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions were calculated. Figure 5 This embodiment illustrates the effect of β-cyclodextrin / aluminum citrate ion-imprinted materials on Al under different curing times. 3+ A graph showing the adsorption capacity and selectivity coefficient.

[0067] Depend on Figure 5 It can be seen that β-cyclodextrin / aluminum citrate ion-imprinted materials have a significant effect on Al 3+ The adsorption capacity and selectivity coefficient reached their peaks at a curing time of 75 min, with the adsorption capacity reaching over 4.6 mg / g.

[0068] Example 6

[0069] like Figure 12As shown, 3g of β-cyclodextrin, 1.5g of citric acid, and 0.75g of KH₂PO₄ were successively added to an Erlenmeyer flask containing 30ml of deionized water and reacted in a water bath at 100℃ for 3 hours to form a clear and transparent solution. 1g of aluminum sulfate, 3mmol of EGDMA, and 1mmol of ammonium persulfate were then added sequentially to the Erlenmeyer flask containing the precursor. The Erlenmeyer flask was then placed back into a magnetic stirrer and reacted in a water bath for 30 minutes. After stirring, the mixture in the Erlenmeyer flask was poured into a petri dish and placed in a forced-air drying oven. The dish was incubated at 110℃, 120℃, 130℃, 140℃, 150℃, and 160℃ for 75 minutes each. After the incubation time, the forced-air drying oven was turned off, and the petri dish was left in the oven to cool to room temperature. After washing the product several times with deionized water, the solid product was collected by centrifugation and dried in a vacuum drying oven. After constant weight, it was ground into powder and then processed with 0.25mol·L⁻¹. -1 Aluminum ions were eluted from the β-cyclodextrin / aluminum citrate ion polymer by washing with NaOH solution for 6 hours. Solid-liquid separation was performed using a centrifuge, and the sample was washed with deionized water until neutral, then dried in an oven at 80℃ to obtain the β-cyclodextrin / aluminum citrate ion imprinted material. 0.1 g of the β-cyclodextrin / aluminum citrate ion imprinted material was added to 50 mL of a mixed solution of 20 mg / L aluminum ions and 100 mg / L lanthanum ions (pH adjusted to 4 with sulfuric acid or sodium hydroxide). The solution was shaken in a constant temperature shaking incubator for 20 h, filtered, and the supernatant was obtained. The concentrations of aluminum and lanthanum ions in the supernatant were detected by ICP, and the adsorption capacity and selectivity of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions were calculated. Figure 6 This embodiment illustrates the effect of β-cyclodextrin / aluminum citrate ion-imprinted materials on Al at different curing temperatures. 3+ A graph showing the adsorption capacity and selectivity coefficient.

[0070] Depend on Figure 6 It can be seen that β-cyclodextrin / aluminum citrate ion-imprinted materials have a significant effect on Al 3+ The adsorption capacity and selectivity coefficient reached their peak at a curing temperature of 150℃, with the selectivity coefficient exceeding 300.

[0071] Example 7

[0072] like Figure 12As shown, 3g of β-cyclodextrin, 1.5g of citric acid, and 0.75g of KH₂PO₄ were successively added to an Erlenmeyer flask containing 30ml of deionized water and reacted in a water bath at 100℃ for 3 hours to form a clear and transparent solution. 1g of aluminum sulfate, 3mmol of EGDMA, and 1mmol of ammonium persulfate were then added sequentially to the Erlenmeyer flask containing the precursor. The Erlenmeyer flask was then placed back into a magnetic stirrer and reacted in a water bath for 30 minutes. After stirring, the mixture in the Erlenmeyer flask was poured into a petri dish and placed in a forced-air drying oven at 150℃ for 75 minutes. After the incubation period, the forced-air drying oven was turned off, and the petri dish was left inside to cool to room temperature. After washing the product several times with deionized water, the solid product was collected by centrifugation and dried in a vacuum drying oven. After constant weight, it was ground into powder and then processed with 0.25mol·L⁻¹. -1 Aluminum ions were eluted from the β-cyclodextrin / aluminum citrate ion polymer by washing with NaOH solution for 6 hours. Solid-liquid separation was performed using a centrifuge, and the sample was washed with deionized water until neutral, then dried in an oven at 80℃ to obtain the β-cyclodextrin / aluminum citrate ion imprinted material. 0.1 g of the β-cyclodextrin / aluminum citrate ion imprinted material was added to 50 mL of a mixed solution containing 20 mg / L aluminum ions and 100 mg / L lanthanum ions, with the pH adjusted to 2, 2.5, 3, 3.5, or 4 using sulfuric acid or sodium hydroxide. The solution was shaken in a constant temperature shaker for 20 hours, filtered, and the supernatant was obtained. The concentrations of aluminum and lanthanum ions in the supernatant were detected by ICP, and the adsorption capacity and selectivity of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions were calculated. Figure 7 This embodiment demonstrates the effect of β-cyclodextrin / aluminum citrate ion-imprinted materials on Al at different pH values. 3+ A graph showing the adsorption capacity and removal rate.

[0073] Depend on Figure 7 It can be seen that, with increasing pH, the effect of β-cyclodextrin / aluminum citrate ion-imprinted materials on Al 3+ The adsorption capacity and removal rate reached their peak at pH 4, with the removal rate exceeding 79%.

[0074] Example 8

[0075] like Figure 12As shown, 3g of β-cyclodextrin, 1.5g of citric acid, and 0.75g of KH₂PO₄ were successively added to an Erlenmeyer flask containing 30ml of deionized water and reacted in a water bath at 100℃ for 3 hours to form a clear and transparent solution. 1g of aluminum sulfate, 3mmol of EGDMA, and 1mmol of ammonium persulfate were then added sequentially to the Erlenmeyer flask containing the precursor. The Erlenmeyer flask was then placed back into a magnetic stirrer and reacted in a water bath for 30 minutes. After stirring, the mixture in the Erlenmeyer flask was poured into a petri dish and placed in a forced-air drying oven at 150℃ for 75 minutes. After the incubation period, the forced-air drying oven was turned off, and the petri dish was left inside to cool to room temperature. After washing the product several times with deionized water, the solid product was collected by centrifugation and dried in a vacuum drying oven. After constant weight, it was ground into powder and then processed with 0.25mol·L⁻¹. -1 Aluminum ions in the β-cyclodextrin / aluminum citrate ion-polymer material were eluted by washing with NaOH solution for 6 hours. Solid-liquid separation was performed using a centrifuge, and the sample was washed with deionized water until neutral, then dried in an oven at 80℃ to obtain the β-cyclodextrin / aluminum citrate ion-imprinted material. 0.06, 0.08, 0.1, 0.15, 0.5, and 0.25 g of the β-cyclodextrin / aluminum citrate ion-imprinted material were added to 50 mL of a mixed solution of 20 mg / L aluminum ions and 100 mg / L lanthanum ions (pH adjusted to 4 with sulfuric acid or sodium hydroxide), respectively. The solution was shaken in a constant temperature shaking incubator for 20 h, filtered, and the supernatant was obtained. The concentrations of aluminum and lanthanum ions in the supernatant were detected by ICP, and the adsorption capacity and selectivity of the β-cyclodextrin / aluminum citrate ion-imprinted material for aluminum ions were calculated. Figure 8 This embodiment illustrates the effect of different amounts of β-cyclodextrin / aluminum citrate ion-imprinted materials on Al 3+ A graph showing the adsorption capacity and removal rate.

[0076] Depend on Figure 8 It can be seen that β-cyclodextrin / aluminum citrate ion-imprinted materials have a significant effect on Al 3+ The adsorption capacity and removal rate reached their peak at a dosage of 0.1g, with the removal rate exceeding 85%.

[0077] Example 9

[0078] like Figure 12As shown, 3g of β-cyclodextrin, 1.5g of citric acid, and 0.75g of KH₂PO₄ were successively added to an Erlenmeyer flask containing 30ml of deionized water and reacted in a water bath at 100℃ for 3 hours to form a clear and transparent solution. 1g of aluminum sulfate, 3mmol of EGDMA, and 1mmol of ammonium persulfate were then added sequentially to the Erlenmeyer flask containing the precursor. The Erlenmeyer flask was then placed back into a magnetic stirrer and reacted in a water bath for 30 minutes. After stirring, the mixture in the Erlenmeyer flask was poured into a petri dish and placed in a forced-air drying oven at 150℃ for 75 minutes. After the incubation period, the forced-air drying oven was turned off, and the petri dish was left inside to cool to room temperature. After washing the product several times with deionized water, the solid product was collected by centrifugation and dried in a vacuum drying oven. After constant weight, it was ground into powder and then processed with 0.25mol·L⁻¹. -1 Aluminum ions were eluted from the β-cyclodextrin / aluminum citrate ion polymer by washing with NaOH solution for 6 hours. Solid-liquid separation was performed using a centrifuge, and the sample was washed with deionized water until neutral, then dried in an oven at 80℃ to obtain the β-cyclodextrin / aluminum citrate ion imprinted material. 0.1 g of the β-cyclodextrin / aluminum citrate ion imprinted material was added to 50 mL of a mixed solution of 20 mg / L aluminum ions and 100 mg / L lanthanum ions (pH adjusted to 4 with sulfuric acid or sodium hydroxide). The solution was shaken in a constant temperature shaking incubator for 0.5 h, 2 h, 8 h, 16 h, 20 h, 24 h, and 26 h, respectively. The supernatant was obtained by filtration, and the concentrations of aluminum and lanthanum ions in the supernatant were detected by ICP. The adsorption capacity and selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions were calculated. Figure 9 This embodiment illustrates the effect of β-cyclodextrin / aluminum citrate ion-imprinted materials on Al under different oscillation times. 3+ A graph showing the adsorption capacity and removal rate.

[0079] Depend on Figure 9 It can be seen that the β-cyclodextrin / aluminum citrate ion-imprinted material Al 3+ The adsorption capacity and removal rate reached their peak after 20 hours of shaking, with the removal rate exceeding 78%.

[0080] Example 10

[0081] like Figure 12As shown, 3g of β-cyclodextrin, 1.5g of citric acid, and 0.75g of KH₂PO₄ were successively added to an Erlenmeyer flask containing 30ml of deionized water and reacted in a water bath at 100℃ for 3 hours to form a clear and transparent solution. 1g of aluminum sulfate, 3mmol of EGDMA, and 1mmol of ammonium persulfate were then added sequentially to the Erlenmeyer flask containing the precursor. The Erlenmeyer flask was then placed back into a magnetic stirrer and reacted in a water bath for 30 minutes. After stirring, the mixture in the Erlenmeyer flask was poured into a petri dish and placed in a forced-air drying oven at 150℃ for 75 minutes. After the incubation period, the forced-air drying oven was turned off, and the petri dish was left inside to cool to room temperature. After washing the product several times with deionized water, the solid product was collected by centrifugation and dried in a vacuum drying oven. After constant weight, it was ground into powder and then processed with 0.25mol·L⁻¹. -1 Aluminum ions were eluted from the β-cyclodextrin / aluminum citrate ion polymer by washing with NaOH solution for 6 hours. Solid-liquid separation was performed using a centrifuge, and the sample was washed with deionized water until neutral, then dried in an oven at 80℃ to obtain the β-cyclodextrin / aluminum citrate ion imprinted material. 0.1 g of the β-cyclodextrin / aluminum citrate ion imprinted material was added to 50 mL of solutions containing 10 mg / L, 20 mg / L, 60 mg / L, 100 mg / L, 200 mg / L, 300 mg / L, 400 mg / L, and 500 mg / L aluminum ions, respectively, with the pH adjusted to 4 using sulfuric acid or sodium hydroxide. The solutions were shaken in a constant temperature shaking incubator for 20 hours, filtered, and the supernatant was obtained. The concentrations of aluminum and lanthanum ions in the supernatant were detected by ICP, and the adsorption capacity and selectivity of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions were calculated. Figure 10 This embodiment illustrates the effect of β-cyclodextrin / aluminum citrate ion-imprinted materials on Al at different initial concentrations. 3+ Adsorption capacity curve.

[0082] Depend on Figure 10 It can be seen that β-cyclodextrin / aluminum citrate ion-imprinted materials have a significant effect on Al 3+ The adsorption capacity and removal rate reached their peak at an initial concentration of 300 mg / L, with the adsorption capacity exceeding 28 mg / g.

[0083] Example 11

[0084] like Figure 12As shown, 3g of β-cyclodextrin, 1.5g of citric acid, and 0.75g of KH₂PO₄ were successively added to an Erlenmeyer flask containing 30ml of deionized water and reacted in a water bath at 100℃ for 3 hours to form a clear and transparent solution. 1g of aluminum sulfate, 3mmol of EGDMA, and 1mmol of ammonium persulfate were then added sequentially to the Erlenmeyer flask containing the precursor. The Erlenmeyer flask was then placed back into a magnetic stirrer and reacted in a water bath for 30 minutes. After stirring, the mixture in the Erlenmeyer flask was poured into a petri dish and placed in a forced-air drying oven at 150℃ for 75 minutes. After the incubation period, the forced-air drying oven was turned off, and the petri dish was left inside to cool to room temperature. After washing the product several times with deionized water, the solid product was collected by centrifugation and dried in a vacuum drying oven. After constant weight, it was ground into powder and then processed with 0.25mol·L⁻¹. -1 Aluminum ions in the β-cyclodextrin / aluminum citrate ion-polymerized material were eluted by washing with NaOH solution for 6 hours. Solid-liquid separation was performed using a centrifuge, followed by washing with deionized water until neutral, and then drying in an oven at 80°C to obtain the β-cyclodextrin / aluminum citrate ion-imprinted material. 0.1 g of the β-cyclodextrin / aluminum citrate ion-imprinted material was added to 50 mL of a mixed solution of 20 mg / L aluminum ions and 100 mg / L lanthanum ions (pH adjusted to 4 with sulfuric acid or sodium hydroxide). The solution was shaken in a constant temperature shaking incubator for 20 hours. The supernatant and the adsorbed β-cyclodextrin / aluminum citrate ion-imprinted material were obtained by filtration. The adsorbed β-cyclodextrin / aluminum citrate ion-imprinted material was eluted again with 0.25 mol / L NaOH solution, followed by solid-liquid separation using a centrifuge and washing with deionized water. The sample was washed until neutral and then dried in an oven at 80°C. 0.1 g of β-cyclodextrin / aluminum citrate ion imprinted material was added to 50 mL of a mixed solution of 20 mg / L aluminum ions and 100 mg / L lanthanum ions, with the pH adjusted to 4 using sulfuric acid or sodium hydroxide. The solution was shaken in a constant temperature shaker for 20 h. The supernatant was obtained by filtration. The concentrations of aluminum ions and lanthanum ions in the supernatant were detected by ICP. The adsorption capacity and selectivity of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions were calculated after each cycle. Figure 11 This embodiment demonstrates the effect of β-cyclodextrin / aluminum citrate ion-imprinted material on Al under cyclic experiments. 3+ A graph showing the adsorption capacity and selectivity coefficient.

[0085] Depend on Figure 11 It can be seen that β-cyclodextrin / aluminum citrate ion-imprinted materials have a significant effect on Al 3+ The selectivity coefficients are all higher than 110.

[0086] Example 12

[0087] like Figure 12As shown, 3g of β-cyclodextrin, 1.5g of citric acid, and 0.75g of KH₂PO₄ were successively added to an Erlenmeyer flask containing 30ml of deionized water and reacted in a water bath at 100℃ for 3 hours to form a clear and transparent solution. 1g of aluminum sulfate, 3mmol of EGDMA, and 1mmol of ammonium persulfate were then added sequentially to the Erlenmeyer flask containing the precursor. The Erlenmeyer flask was then placed back into a magnetic stirrer and reacted in a water bath for 30 minutes. After stirring, the mixture in the Erlenmeyer flask was poured into a petri dish and placed in a forced-air drying oven at 150℃ for 75 minutes. After the incubation period, the forced-air drying oven was turned off, and the petri dish was left inside to cool to room temperature. After washing the product several times with deionized water, the solid product was collected by centrifugation and dried in a vacuum drying oven. After constant weight, it was ground into powder and then processed with 0.25mol·L⁻¹. -1 Aluminum ions in the β-cyclodextrin / aluminum citrate ion-polymer material were eluted by washing with NaOH solution for 6 hours. Solid-liquid separation was performed using a centrifuge, and the sample was washed with deionized water until neutral. It was then dried in an oven at 80℃ to obtain the β-cyclodextrin / aluminum citrate ion-imprinted material. 0.1 g of the β-cyclodextrin / aluminum citrate ion-imprinted material was added to 50 mL of water. 100 mg / L of lanthanum ions, 100 mg / L of yttrium ions, and erbium ions were added to a 20 mg / L aluminum ion solution to form a mixed solution. The pH of the mixed solution was adjusted to 4 using sulfuric acid or sodium hydroxide. The solution was shaken in a constant temperature shaking incubator for 20 h, and the supernatant was obtained by filtration. The concentrations of aluminum and lanthanum ions in the supernatant were detected by ICP, and the adsorption capacity and selectivity coefficient of the β-cyclodextrin / aluminum citrate ion-imprinted material for aluminum ions were calculated (results are shown in Table 1).

[0088] Table 1: Effects of β-cyclodextrin / aluminum citrate ion-imprinted materials on Al at initial concentrations 3+ Adsorption capacity and removal rate.

[0089]

[0090] Table 1 shows that β-cyclodextrin / aluminum citrate ion-imprinted materials in Al 3+ :La 3+ Al 3+ Y 3+ And Al 3+ Er 3+ The selectivity coefficients were 150.38, 10.64 and 33.92, respectively, with the selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material reaching its maximum when aluminum and lanthanum ions were mixed.

[0091] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for synthesizing a β-cyclodextrin / aluminum citrate ion-imprinted material, characterized in that, Includes the following steps: S1. Pour β-cyclodextrin, citric acid, and potassium dihydrogen phosphate into a bottle containing deionized water solution, mix evenly, and heat in a water bath to synthesize the β-cyclodextrin / citric acid precursor; the mass ratio of β-cyclodextrin, citric acid, and potassium dihydrogen phosphate is 4:(1~12):1, and the mass ratio of this mixture to deionized water is (3.75~12):30; the water bath reaction is carried out by placing the bottle in a water bath constant temperature shaker and stirring, the temperature of the constant temperature shaker is 70~120℃, and the water bath time is 0.5~5h; S2. Aluminum sulfate octadecyl water, ethylene glycol dimethacrylate, and ammonium persulfate are sequentially added to a bottle containing the precursor. The mixture is heated in a water bath to react. After the reaction is complete, the crude product in the bottle is dried. The mass ratio of aluminum sulfate octadecyl water, ethylene glycol dimethacrylate, and ammonium persulfate is (1-3):(0.2-0.7):(0.1-0.3). The water bath reaction is carried out by placing the bottle in a water bath constant temperature shaker and stirring. The temperature of the constant temperature shaker is 110-160℃, and the water bath time is 10-60 min. The drying temperature is 120-160℃, and the drying time is 45-105 min. S3. Wash the crude product with deionized water, filter and dry it, then grind and modify it with ethanol to obtain β-cyclodextrin / aluminum citrate ion polymer material. S4, using 0.25 mol·L -1 Soaking in sodium hydroxide solution removes aluminum ions from the β-cyclodextrin / aluminum citrate polymer material; S5. Wash with deionized water to adjust the pH of the β-cyclodextrin / aluminum citrate polymer material to neutral. After drying, obtain the β-cyclodextrin / aluminum citrate imprinted material.

2. The method for synthesizing a β-cyclodextrin / aluminum citrate ion-imprinted material according to claim 1, characterized in that, In step S4, the sodium hydroxide solution soaking time is 6 to 8 hours.

3. The method for synthesizing a β-cyclodextrin / aluminum citrate ion-imprinted material according to claim 1, characterized in that, In step S5, the drying temperature is 80–90°C and the drying time is 6–12 hours.

4. The application of the β-cyclodextrin / aluminum citrate ion-imprinted material prepared by the synthesis method according to any one of claims 1-3 for the selective removal of aluminum ions from rare earth elements, characterized in that, Includes the following steps: S6. Prepare an aluminum ion solution of a certain concentration using aluminum sulfate; S7. Measure the aluminum ion solution, adjust the pH value to 3~4 with sulfuric acid or sodium hydroxide, add the β-cyclodextrin / citric acid aluminum ion imprinting material to the aluminum ion solution, shake to mix and react, filter to separate and obtain the supernatant. S8. Detect the aluminum ion concentration in the supernatant and calculate the removal rate and adsorption amount of aluminum ions by the β-cyclodextrin / aluminum citrate imprinted material. S9. Measure out a mixed solution of aluminum ions and rare earth ions, adjust the pH value to 3~4 with sulfuric acid or sodium hydroxide, add β-cyclodextrin / aluminum citrate imprinted material to the mixed solution of aluminum ions and rare earth ions, shake to mix and react, filter to separate and obtain the supernatant. S10. Detect the concentration of aluminum ions and rare earth ions in the supernatant, and calculate the selectivity coefficient of the β-cyclodextrin / aluminum citrate imprinted material for aluminum ions.

5. The application of the β-cyclodextrin / aluminum citrate ion-imprinted material according to claim 4 for the selective removal of aluminum ions from rare earth elements, characterized in that... In step S6, the concentration of the aluminum ion solution is 10 mg / L to 500 mg / L.

6. The application of the β-cyclodextrin / aluminum citrate ion-imprinted material according to claim 4 for the selective removal of aluminum ions from rare earth elements, characterized in that... In step S7, the mass ratio of β-cyclodextrin / aluminum citrate ion imprinting material to aluminum ions is (60~250):(0.5~25). In step S7, the mixing reaction is carried out in a constant temperature shaking chamber at a reaction temperature of 25°C for a reaction time of 0.5 to 26 hours.

7. The application of the β-cyclodextrin / aluminum citrate ion-imprinted material according to claim 6 for the selective removal of aluminum ions from rare earth elements, characterized in that... In step S9, the rare earth ions in the mixed solution of aluminum ions and rare earth ions are at least one of lanthanum, yttrium, and erbium.

8. The application of the β-cyclodextrin / aluminum citrate ion-imprinted material according to claim 7 for the selective removal of aluminum ions from rare earth elements, characterized in that... In step S9, the concentration of rare earth ions in the mixed solution of aluminum ions and rare earth ions is 100 mg / L, and the concentration of aluminum ions is 20 mg / L; the mass ratio of β-cyclodextrin / aluminum citrate imprinted material to aluminum ions is 100:

1. In step S9, the mixing reaction is carried out in a constant temperature shaking chamber at a temperature of 25°C for a time of 0.5 to 26 hours.

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