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

Abstract

The invention discloses a synthesis method and application of a beta-cyclodextrin aluminum citrate ion imprinting material, and the synthesis method comprises the following steps: S1, pouring beta-cyclodextrin, citric acid and monopotassium phosphate into a bottle filled with a deionized water solution, uniformly mixing, and carrying out water bath heating reaction to synthesize a beta-cyclodextrin / citric acid precursor; s2, sequentially pouring aluminum sulfate octadecahydrate, ethylene glycol dimethacrylate and ammonium persulfate into a bottle, and performing water bath heating reaction to synthesize a crude product of a beta-cyclodextrin / aluminum citrate ionic polymer; s3, drying the crude product in the bottle; s4, washing the crude product with deionized water, filtering and drying, and grinding and modifying with ethanol; and S5, soaking in a sodium hydroxide solution, washing with deionized water until the pH value is neutral, and drying to obtain the beta-cyclodextrin / aluminum citrate ion imprinted material. The synthesis process and process are simple, and the beta-cyclodextrin is simple in source and low in cost. The mechanical strength and the acid resistance of the prepared product are greatly improved, and the prepared product has the characteristics of proper strength, stable adsorption under an acidic condition and the like.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of mineral materials and environmental protection, and particularly relates to a synthesis method of a beta-cyclodextrin aluminum citrate ion imprinted material and application thereof. BACKGROUND

[0002] Rare earth is a non-renewable resource with relatively small overall reserves, but due to its magnetic, optical and catalytic properties, it can be widely used in new energy, superconductor and information technology fields. The purity of rare earth products directly affects its value. Ion-adsorbed rare earth ore has the advantages of easy mining, easy extraction and low cost compared with other rare earth ores. At present, there is a mature technology for ion-adsorbed rare earth ore, but there is still a problem of too high impurity content. Among them, Al 3+ and rare earth ions (Re 3+ ) have similar properties, and in the subsequent rare earth extraction and separation process, impurity Al 3+ competes with Re 3+ for extraction, reducing the extraction content of rare earth and causing loss of rare earth. Therefore, it is important to develop a technology that can selectively remove impurity Al 3+ from rare earth mother liquor to realize efficient recovery of ion-adsorbed rare earth ore.

[0003] At present, the methods for removing Al 3+ from rare earth mother liquor mainly include precipitation, extraction and adsorption. At present, ammonium bicarbonate precipitation is mainly used in industry, but a large amount of ammonia-nitrogen wastewater is generated in the precipitation process, causing secondary pollution. At present, there are still few aluminum extractants and emulsification reactions occur. The adsorption method is considered to be the most promising method due to its green and environmental protection characteristics. The core of the adsorption method is the adsorption material. At present, researchers have developed a variety of adsorption materials for selectively removing Al 3+ from complex rare earth solutions, such as ion exchange resins, hydrogels, activated carbon and ion imprinted materials. The selectivity of ion exchange resins is mainly determined by the ion charge number, hydration radius and solution environment (pH, concentration), so it is difficult to distinguish ions with similar charge and radius; hydrogels adsorb ions through the pores in the hydrophilic network or weak bonds (hydrogen bonds, van der Waals forces), but the dynamic cross-linked network is easily affected by swelling, causing the recognition site to deform, and the functional groups are randomly distributed, making it difficult to achieve high-precision recognition; the selectivity of activated carbon is determined by the pore size distribution (micropores trap small molecules) and the weak ionization of surface functional groups (such as carboxyl groups), but the surface chemical modification is limited and lacks directional recognition sites; ion imprinted materials form specific binding sites through the directional interaction of template ions and functional monomers, which have the effect of specific recognition of target ions, so they are concerned in the field of rare earth separation due to their high selectivity.

[0004] Now there are scholars successfully prepared aluminum ion imprinted material for rare earth separation field, B. Özkahraman et al. used epichlorohydrin as crosslinking agent with chitosan as functional monomer to synthesize ion imprinted biosorbent [Al(III)-IP], research found that Al(III)-IP and non-imprinted material for Al 3+ The adsorption capacity is 48mg / g and 12mg / g, respectively, and the selectivity coefficient for Al 3+ Is 4.4; Li et al. used acrylic acid as functional monomer, aluminum sulfate octadecahydrate as template ion and EGDMA as crosslinking agent to react under certain conditions to generate product loaded with hydrochloric acid activated silica gel to get aluminum ion imprinted material (IIP-Al), the maximum adsorption capacity of IIP-Al for Al 3+ Can reach 106mg / g, and the selectivity coefficient in the mixed solution of Nd 3+ Can be as high as 17.76; Behisht et al. synthesized Aluminum(III) by using methacrylic acid as monomer and divinyl benzene as crosslinking agent, and found that its adsorption capacity for Al 3+ Can be as high as 165.1 µmol·g −1 But in the existing literature, the selectivity performance of ion imprinted material under low pH value is still a difficulty, and because the chemical properties of rare earth elements and aluminum element are similar, they will precipitate together when the pH value is more than 4.3, so it is urgent to develop a material with high selectivity adsorption performance for Al 3+ In rare earth mother liquor under low pH value.

[0005] β-cyclodextrin (β-CD) as a kind of low-cost natural polymer, has good biocompatibility, harmless and low water solubility and other properties, in many adsorbents stand out. At present, scholars have used β-CD for the preparation of ion imprinted material, Nchoe et al. Encapsulated 1,5'-diphenyl carbazide (DPC) ligand in β-CD and then added crosslinking agent ethylene glycol dimethyl acrylate (EGDMA) and 4-vinyl pyridine (4-VP) to get chromium ion imprinted material, and its maximum adsorption capacity for Cr(VI) reached 15.61mg / g, but its regeneration performance is poor; Fan et al. Prepared hydrogel beads with β-CD by sol-gel method with glutaraldehyde as crosslinking agent, and found that it can adsorb Cu 2+The adsorption capacity of the material can be up to 822 mg / g, and the material has good regeneration performance, but the method is relatively complex and the selectivity coefficient is lower than that of other ion imprinting materials. Researchers found that the cross-linking of natural non-toxic, strong reactivity and easy-to-obtain citric acid (CA) and beta-CD can not only solve the problem of low water solubility of beta-CD, change the chemical properties of beta-CD, and the hydrophobic cavity structure of beta-CD will not be collapsed, but also add carboxyl and ester groups to enhance the performance of the material. He et al. systematically combed the synthesis mechanism and application research of beta-CD / CA complex formed by cross-linking of CA and beta-CD. So far, beta-CD / CA has not been used to prepare ion imprinting materials, so developing a new method of beta-cyclodextrin-based adsorption material with simple method and high selective adsorption performance is conducive to attracting more scholars to pay attention to the research of beta-cyclodextrin.

[0006] At present, the synthesis of aluminum ion imprinting material has the following shortcomings: 1) the preparation process of ion imprinting material is complex, and the amount of crosslinking agent is large, which limits its large-scale industrial application; 2) the saturated adsorption capacity of ion imprinting material is large, but the mechanical strength is low, and the selective adsorption performance is low.

[0007] Therefore, a synthesis method of beta-cyclodextrin aluminum citrate ion imprinting material with simple process, high mechanical strength and high selectivity and its application are urgently needed. SUMMARY

[0008] In order to solve the defects in the prior art, the present application provides a synthesis method of beta-cyclodextrin aluminum citrate ion imprinting material and its application, which has the advantages of simple process, low cost, no secondary pollution, high selectivity for removing aluminum ions in solution, good cycle stability and wide application prospect.

[0009] In order to solve the above technical problems, the present application provides the following technical solutions:

[0010] The first object of the present application provides a synthesis method of beta-cyclodextrin aluminum citrate ion imprinting material, comprising the following steps:

[0011] S1, beta-cyclodextrin, citric acid and potassium dihydrogen phosphate are poured into a bottle containing deionized water solution, uniformly mixed, and the precursor beta-cyclodextrin / citric acid is synthesized by water bath heating reaction;

[0012] S2, aluminum sulfate octadecahydrate, ethylene glycol dimethyl acrylate and ammonium persulfate are poured into the bottle in turn, and the crude product in the bottle is dried after water bath heating reaction;

[0013] S3, the crude product is washed with deionized water, dried and filtered, and then modified with ethanol to obtain beta-cyclodextrin aluminum citrate ion polymer material.

[0014] S4, soaking with 0.25 mol·L -1 of sodium hydroxide solution to remove aluminum ions in the β-cyclodextrin / aluminum citrate ion polymer material;

[0015] S5, washing with deionized water, adjusting the pH value of the β-cyclodextrin / aluminum citrate ion polymer material from which the aluminum ions have been removed to neutral, and after drying, obtaining a β-cyclodextrin / aluminum citrate ion imprinted material.

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

[0017] The water bath reaction in step S1 is to place the bottle in a water bath constant temperature oscillator for stirring, the temperature of the constant temperature oscillator is 70-120℃, and the water bath time is 0.5-5h.

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

[0019] The water bath reaction in step S2 is to place the bottle in a water bath constant temperature oscillator for stirring, the temperature of the constant temperature oscillator is 110-160℃, and the water bath time is 10-60min;

[0020] The drying temperature in step S2 is 120-160℃, and the drying time is 45-105min.

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

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

[0023] The second object of the present application provides an application of a β-cyclodextrin aluminum citrate ion imprinted material for selectively removing aluminum ions in rare earth, comprising the following steps:

[0024] S6, aluminum sulfate is prepared into an aluminum ion solution with a certain concentration;

[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 / aluminum citrate ion imprinted material into the aluminum ion solution, shake and mix the reaction, and filter and separate to obtain a supernatant;

[0026] S8, detect the aluminum ion concentration in the supernatant, and calculate the removal rate and adsorption capacity of the β-cyclodextrin / aluminum citrate ion imprinted material to aluminum ions;

[0027] S9, measure the mixed solution of aluminum ions and rare earth ions, add the beta-cyclodextrin / aluminum citrate ion imprinting material into the mixed solution of aluminum ions and rare earth ions, shake and mix the reaction, and filter and separate to obtain the supernatant;

[0028] S10, detect the aluminum ion concentration and rare earth ions in the supernatant, and calculate the selectivity coefficient of the beta-cyclodextrin / aluminum citrate ion imprinting material to aluminum ions.

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

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

[0031] The mixing reaction in step S7 is carried out in a constant-temperature shaking incubator, the reaction temperature is 25 DEG C, and the reaction time is 0.5 to 26 h.

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

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

[0034] The mixing reaction in step S9 is carried out in a constant-temperature shaking incubator, the reaction temperature is 25 DEG C, and the reaction time is 0.5 to 26 h.

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

[0036] (1) The present application uses beta-cyclodextrin as a raw material, synthesizes a precursor beta-cyclodextrin / citric acid through an esterification reaction, and synthesizes an aluminum ion imprinting material with strong selectivity to aluminum ions through a water bath method, and the synthesis process is simple, and the source of beta-cyclodextrin is simple and the cost is low.

[0037] (2) Compared with the beta-cyclodextrin-based ion imprinting material prepared by other methods, the mechanical strength and acid resistance are greatly improved, and the material has appropriate strength and can be stably adsorbed under acidic conditions.

[0038] (3) The beta-cyclodextrin / aluminum citrate aluminum ion imprinting material prepared by the present application still has high removal rate and selectivity to aluminum ions in the solution after being used for multiple cycles, and the material loss rate is extremely low, and the material has good chemical stability.

[0039] (4) The process of the present invention is green and environmentally friendly, with significant environmental and economic benefits, and is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 The β-cyclodextrin / aluminum citrate ion imprinting material under different β-cyclodextrin / aluminum citrate mass ratios in Example 1 of the present invention is shown in FIG. 3+ Graph of adsorption capacity and selectivity coefficient;

[0041] Figure 2 The β-cyclodextrin / aluminum citrate ion imprinted material has an effect on the Al content of the β-cyclodextrin / aluminum citrate ion imprinted material at different β-cyclodextrin / citric acid synthesis temperatures in Example 2 of the present invention. 3+ Graph of adsorption capacity and selectivity coefficient;

[0042] Figure 3 The β-cyclodextrin / aluminum citrate ion imprinting material has the following characteristics: 3+ Graph of adsorption capacity and selectivity coefficient;

[0043] Figure 4 The results of the β-cyclodextrin / aluminum citrate ion imprinting material on Al under different water bath times in Example 4 of the present invention are shown in FIG. 3+ Graph of adsorption capacity and selectivity coefficient;

[0044] Figure 5 The β-cyclodextrin / aluminum citrate ion imprinting material is used to imprint Al at different curing times in Example 5 of the present invention. 3+ Graph of adsorption capacity and selectivity coefficient;

[0045] Figure 6 The β-cyclodextrin / aluminum citrate ion imprinting material is used to imprint Al at different curing temperatures in Example 6 of the present invention. 3+ Graph of adsorption capacity and selectivity coefficient;

[0046] Figure 7 The β-cyclodextrin / aluminum citrate ion imprinting material is used to imprint Al under different pH conditions in Example 7 of the present invention. 3+ Graph of adsorption capacity and removal rate;

[0047] Figure 8 The results of Example 8 of the present invention show that different amounts of β-cyclodextrin / aluminum citrate ion imprinting materials are used to imprint Al 3+ Graph of adsorption capacity and removal rate;

[0048] Figure 9 The β-cyclodextrin / aluminum citrate ion imprinting material is used to imprint Al at different oscillation times in Example 9 of the present invention. 3+ Graph of adsorption capacity and removal rate;

[0049] Figure 10 The results of the β-cyclodextrin / aluminum citrate ion imprinting material on Al at different initial concentrations in Example 10 of the present invention are shown in FIG. 3+ Curve graph of adsorption amount;

[0050] Figure 11 The β-cyclodextrin / aluminum citrate ion imprinting material is used to imprint Al at different cycle times in Example 11 of the present invention. 3+ Graph of adsorption capacity and selectivity coefficient;

[0051] Figure 12 Schematic diagram of the synthesis method of the present invention. DETAILED DESCRIPTION

[0052] The preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood that the preferred embodiments described herein are only used to illustrate and explain the present invention, and are not used 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 placed in 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 poured into the conical flask containing the precursor in sequence, and the conical flask was placed back in 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, and kept warm at 140℃ for 75 minutes. After the holding time was over, the forced air drying oven was turned off and the petri dish was left in the drying oven to cool to room temperature. The product was washed several times with deionized water, and the solid product was collected by solid-liquid separation using a centrifuge and dried in a vacuum drying oven. After constant weight, it was ground into powder and then precipitated with 0.25mol·L -1 The aluminum ions in the β-cyclodextrin / aluminum citrate ion polymer material were eluted by alkaline washing with NaOH solution for 6 hours. A centrifuge was used for solid-liquid separation, and the sample was washed with deionized water until neutral, and then dried in an 80°C oven to obtain a β-cyclodextrin / aluminum citrate ion imprinted material. 0.1g of β-cyclodextrin / aluminum citrate ion imprinted material was added to 50mL of a mixed solution of 20mg / L aluminum ions and 100mg / L lanthanum ions, the pH of which was adjusted to 4 with sulfuric acid or sodium hydroxide. The mixture was shaken in a constant temperature shaker for 20h, and the supernatant was separated by filtration. The concentrations of aluminum ions 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. Figure 1The β-cyclodextrin / aluminum citrate ion imprinting materials with different β-cyclodextrin / citric acid mass ratios in this embodiment are shown in FIG. 3+ Graph of adsorption capacity and selectivity coefficient.

[0055] Depend on Figure 1 It can be seen that the β-cyclodextrin / aluminum citrate ion imprinting material has a great effect on Al 3+ The adsorption capacity and selectivity coefficient reached peak values ​​when the mass ratio of β-cyclodextrin to citric acid was 2:1, and the selectivity coefficient reached above 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 placed in a conical flask filled with 30ml of deionized water, and reacted in a water bath at 70℃, 80℃, 90℃, 100℃, 110℃ and 120℃ for 3 hours to form a clear and transparent solution. 1g of aluminum sulfate, 3mmol of EGDMA and 1mmol of ammonium persulfate were poured into the conical flask containing the precursor in sequence, and the conical flask was placed back in 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 blast drying oven, and kept warm at 140℃ for 75 minutes. After the insulation time was over, the blast 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 solid-liquid separation using a centrifuge and placed in a vacuum drying oven for drying. After constant weight, it was ground into powder and then precipitated with 0.25mol·L -1 The aluminum ions in the β-cyclodextrin / aluminum citrate ion polymer material were eluted by alkaline washing with NaOH solution for 6 hours. A centrifuge was used for solid-liquid separation, and the sample was washed with deionized water until neutral, and then dried in an 80°C oven to obtain a β-cyclodextrin / aluminum citrate ion imprinted material. 0.1g of β-cyclodextrin / aluminum citrate ion imprinted material was added to 50mL of a mixed solution of 20mg / L aluminum ions and 100mg / L lanthanum ions, the pH of which was adjusted to 4 with sulfuric acid or sodium hydroxide. The mixture was shaken in a constant temperature shaker for 20h, and the supernatant was separated by filtration. The concentrations of aluminum ions 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. Figure 2 The β-cyclodextrin / aluminum citrate ion imprinting material has an effect on the Al content at different β-cyclodextrin / citric acid synthesis temperatures in this embodiment. 3+ Graph of adsorption capacity and selectivity coefficient.

[0058] Depend on Figure 2 It can be seen that the β-cyclodextrin / aluminum citrate ion imprinting material has a great effect on Al 3+The adsorption capacity and selectivity coefficient reached peak values ​​at a temperature of 100°C, 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 placed in a conical flask filled with 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 poured into the conical flask containing the precursor in sequence, and the conical flask was placed back in a magnetic stirrer for a water bath reaction for 30 minutes. After stirring, the mixture in the conical flask was poured into a Petri dish and placed in a blast drying oven, and kept warm at 140℃ for 75 minutes. After the insulation time was over, the blast 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 solid-liquid separation using a centrifuge and placed in a vacuum drying oven for drying. After constant weight, it was ground into powder and then precipitated with 0.25mol·L -1 The aluminum ions in the β-cyclodextrin / aluminum citrate ion polymer material were eluted by alkaline washing with NaOH solution for 6 hours. A centrifuge was used for solid-liquid separation, and the sample was washed with deionized water until neutral, and then dried in an 80°C oven to obtain a β-cyclodextrin / aluminum citrate ion imprinted material. 0.1g of β-cyclodextrin / aluminum citrate ion imprinted material was added to 50mL of a mixed solution of 20mg / L aluminum ions and 100mg / L lanthanum ions, the pH of which was adjusted to 4 with sulfuric acid or sodium hydroxide. The mixture was shaken in a constant temperature shaker for 20h, and the supernatant was separated by filtration. The concentrations of aluminum ions 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. Figure 3 The β-cyclodextrin / aluminum citrate ion imprinting material has different β-cyclodextrin / citric acid synthesis time in this embodiment. 3+ Graph of adsorption capacity and selectivity coefficient.

[0061] Depend on Figure 3 It can be seen that the β-cyclodextrin / aluminum citrate ion imprinting material has a great effect on Al 3+ The adsorption capacity and selectivity coefficient reached peak values ​​when the synthesis time was 3 h, and the selectivity coefficient reached above 72.

[0062] Example 4

[0063] like Figure 12As shown, 3 g of β-cyclodextrin, 1.5 g of citric acid and 0.75 g of KH2PO4 were sequentially added into a conical flask containing 30 ml of deionized water, and reacted in a water bath at 100°C for 3 hours to form a clear and transparent solution. 1 g of aluminum sulfate, 3 mmol of EGDMA and 1 mmol of ammonium persulfate were sequentially poured into the conical flask containing the precursor, and the conical flask was placed in a magnetic stirrer and reacted in a water bath for 10 min, 20 min, 30 min, 40 min, 50 min and 60 min, respectively. After the stirring was completed, the mixture in the conical flask was poured into a culture dish and placed in a forced air drying oven, and incubated at 140°C for 75 minutes. After the incubation time was over, the forced air drying oven was turned off and the culture dish was left in the drying oven to cool to room temperature. After the product was washed several times with deionized water, the solid product was collected by centrifugal solid-liquid separation, and was placed in a vacuum drying oven for drying. After the constant weight was reached, it was ground into a powder, and then eluted with 0.25 mol·L -1 of NaOH solution for 6 hours to elute the aluminum ions in the β-cyclodextrin / aluminum citrate ion imprinted material. The sample was washed to neutral with deionized water, and then dried 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 of aluminum ions and 100 mg / L of lanthanum ions with the pH value adjusted to 4 with sulfuric acid or sodium hydroxide, and was shaken in a constant temperature shaking incubator for 20 h. The supernatant was separated by filtration, and the concentrations of aluminum ions and lanthanum ions in the supernatant were detected by ICP to calculate the adsorption capacity and selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions. Figure 4 The adsorption capacity and selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for Al 3+ at different water bath times in this embodiment are shown in the following graph.

[0064] As can be seen from Figure 4 the graph, the adsorption capacity and selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for Al 3+ reach a peak when the water bath time is 30 min, and the adsorption capacity is more than 4.6 mg / g.

[0065] Example 5

[0066] As Figure 12As shown, 3 g of β-cyclodextrin, 1.5 g of citric acid and 0.75 g of KH2PO4 were sequentially added into a conical flask containing 30 ml of deionized water, and reacted in a water bath at 100°C for 3 hours to form a clear and transparent solution. 1 g of aluminum sulfate, 3 mmol of EGDMA and 1 mmol of ammonium persulfate were sequentially poured into the conical flask containing the precursor, and the conical flask was placed into a magnetic stirrer for water bath reaction for 30 minutes. After completion of stirring, the mixture in the conical flask was poured into a culture dish and placed into a forced air drying oven, and was incubated at 140°C for 45 min, 60 min, 75 min, 90 min and 105 min, respectively. After the incubation time ended, the forced air drying oven was turned off and the culture dish was left in the drying oven to cool to room temperature. After washing the product with deionized water several times, the solid product was collected by centrifugation and was placed into a vacuum drying oven for drying. After constant weight, the product was ground into powder, and then washed with 0.25 mol·L-1 NaOH solution for 6 hours to elute the aluminum ions in the β-cyclodextrin / aluminum citrate ion imprinted material. The sample was washed with deionized water to neutral, and then dried 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 into 50 mL of a mixed solution of 20 mg / L aluminum ions and 100 mg / L lanthanum ions with pH adjusted to 4 by sulfuric acid or sodium hydroxide, and was shaken in a constant temperature shaking incubator for 20 h. The supernatant was separated by filtration, and the concentrations of aluminum ions and lanthanum ions in the supernatant were detected by ICP to calculate the adsorption amount and selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions. -1 As shown in FIG. 2, the adsorption amount and selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions reached a peak value when the solidification time was 75 min, and the adsorption amount was more than 4.6 mg / g. Figure 5 As shown in FIG. 2, the adsorption amount and selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions reached a peak value when the solidification time was 75 min, and the adsorption amount was more than 4.6 mg / g. 3+ As shown in FIG. 2, the adsorption amount and selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions reached a peak value when the solidification time was 75 min, and the adsorption amount was more than 4.6 mg / g.

[0067] As shown in FIG. 2, the adsorption amount and selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions reached a peak value when the solidification time was 75 min, and the adsorption amount was more than 4.6 mg / g. Figure 5 As shown in FIG. 2, the adsorption amount and selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions reached a peak value when the solidification time was 75 min, and the adsorption amount was more than 4.6 mg / g. 3+ As shown in FIG. 2, the adsorption amount and selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions reached a peak value when the solidification time was 75 min, and the adsorption amount was more than 4.6 mg / g.

[0068] Example 6

[0069] As shown in FIG. 2, the adsorption amount and selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions reached a peak value when the solidification time was 75 min, and the adsorption amount was more than 4.6 mg / g. Figure 12As shown, 3g of β-cyclodextrin, 1.5g of citric acid, and 0.75g of KH2PO4 were placed in a conical flask containing 30ml of deionized water and reacted in a water bath at 100°C 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 to the conical flask containing the precursors. The conical flask was then placed back in 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, where it was kept at 110°C, 120°C, 130°C, 140°C, 150°C, and 160°C for 75 minutes. After the holding time was complete, the forced air drying oven was turned off and the Petri dish was left in the drying oven to cool to room temperature. The product was washed several times with deionized water, and the solid product was collected by solid-liquid separation using a centrifuge and dried in a vacuum drying oven. After constant weight, it was ground into a powder and then precipitated with 0.25mol·L -1 The aluminum ions in the β-cyclodextrin / aluminum citrate ion polymer material were eluted by alkaline washing with NaOH solution for 6 hours. A centrifuge was used for solid-liquid separation, and the sample was washed with deionized water until neutral, and then dried in an 80°C oven to obtain a β-cyclodextrin / aluminum citrate ion imprinted material. 0.1g of β-cyclodextrin / aluminum citrate ion imprinted material was added to 50mL of a mixed solution of 20mg / L aluminum ions and 100mg / L lanthanum ions, the pH of which was adjusted to 4 with sulfuric acid or sodium hydroxide. The mixture was shaken in a constant temperature shaker for 20h, and the supernatant was separated by filtration. The concentrations of aluminum ions 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. Figure 6 The β-cyclodextrin / aluminum citrate ion imprinting material is used to imprint Al at different curing temperatures in this embodiment. 3+ Graph of adsorption capacity and selectivity coefficient.

[0070] Depend on Figure 6 It can be seen that the β-cyclodextrin / aluminum citrate ion imprinting material has a great effect on Al 3+ The adsorption capacity and selectivity coefficient reached peak values ​​at a curing temperature of 150°C, and the selectivity coefficient reached over 300.

[0071] Example 7

[0072] like Figure 12As shown, 3g of β-cyclodextrin, 1.5g of citric acid and 0.75g of KH2PO4 were placed in a conical flask filled with 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 poured into the conical flask containing the precursor in sequence, and the conical flask was placed back in a magnetic stirrer for water bath reaction for 30 minutes. After stirring, the mixture in the conical flask was poured into a Petri dish and placed in a blast drying oven, and kept warm at 150℃ for 75 minutes. After the insulation time was over, the blast 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 solid-liquid separation using a centrifuge, and placed in a vacuum drying oven for drying. After constant weight, it was ground into powder, and then 0.25mol·L -1 The aluminum ions in the β-cyclodextrin / aluminum citrate ion polymer material were eluted by alkaline washing with NaOH solution for 6 hours. A centrifuge was used for solid-liquid separation, and the sample was washed with deionized water until neutral, then dried in an 80°C oven 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, the pH values ​​of which were adjusted to 2, 2.5, 3, 3.5, or 4 using sulfuric acid or sodium hydroxide. The mixture was shaken in a constant temperature shaker for 20 hours, and the supernatant was filtered and separated. The aluminum and lanthanum ion concentrations 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. Figure 7 The β-cyclodextrin / aluminum citrate ion imprinting material has an effect on Al 3+ Graph of adsorption capacity and removal rate.

[0073] Depend on Figure 7 It can be seen that with the increase of pH, the β-cyclodextrin / aluminum citrate ion imprinted material has a greater effect on the Al 3+ The adsorption capacity and removal rate reached their peak values ​​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 placed in a conical flask filled with 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 poured into the conical flask containing the precursor in sequence, and the conical flask was placed back in a magnetic stirrer for water bath reaction for 30 minutes. After stirring, the mixture in the conical flask was poured into a Petri dish and placed in a blast drying oven, and kept warm at 150℃ for 75 minutes. After the insulation time was over, the blast 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 solid-liquid separation using a centrifuge, and placed in a vacuum drying oven for drying. After constant weight, it was ground into powder, and then 0.25mol·L -1 The aluminum ions in the β-cyclodextrin / aluminum citrate polymer were eluted by alkaline washing with a NaOH solution for 6 hours. A centrifuge was used for solid-liquid separation, and the sample was washed with deionized water until neutral and then dried in an 80°C oven to obtain the β-cyclodextrin / aluminum citrate imprinted material. 0.06, 0.08, 0.1, 0.15, 0.5, and 0.25 g of the β-cyclodextrin / aluminum citrate imprinted material were added to 50 mL of a mixed solution of 20 mg / L aluminum ions and 100 mg / L lanthanum ions adjusted to pH 4 with sulfuric acid or sodium hydroxide. The mixture was shaken in a constant temperature shaker for 20 hours, and the supernatant was filtered and separated. The aluminum and lanthanum ion concentrations in the supernatant were determined by ICP. The adsorption capacity and selectivity coefficient of the β-cyclodextrin / aluminum citrate imprinted material for aluminum ions were calculated. Figure 8 The different amounts of β-cyclodextrin / aluminum citrate ion imprinting materials used in this example are 3+ Graph of adsorption capacity and removal rate.

[0076] Depend on Figure 8 It can be seen that the β-cyclodextrin / aluminum citrate ion imprinting material has a great effect on Al 3+ The adsorption capacity and removal rate reached peak values ​​when the dosage was 0.1 g, and the removal rate reached more than 85%.

[0077] Example 9

[0078] like Figure 12As shown, 3 g of β-cyclodextrin, 1.5 g of citric acid and 0.75 g of KH2PO4 were sequentially added into a conical flask containing 30 ml of deionized water, and reacted in a water bath at 100°C for 3 hours to form a clear and transparent solution. 1 g of aluminum sulfate, 3 mmol of EGDMA and 1 mmol of ammonium persulfate were sequentially poured into the conical flask containing the precursor, and the conical flask was placed into a magnetic stirrer for water bath reaction for 30 minutes. After completion of stirring, the mixture in the conical flask was poured into a culture dish and placed into a forced air drying oven, and incubated at 150°C for 75 minutes. After the incubation time ended, the forced air drying oven was turned off and the culture dish was left in the drying oven to cool to room temperature. After washing the product with deionized water several times, the solid product was collected by centrifugal solid-liquid separation, and was placed into a vacuum drying oven for drying. After constant weight, it was ground into powder, and then washed with 0.25 mol·L -1 of NaOH solution for 6 hours to elute the aluminum ions in the β-cyclodextrin / aluminum citrate ion imprinted material. The sample was washed to neutral with deionized water, and then dried 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 of aluminum ions and 100 mg / L of lanthanum ions with the pH value adjusted to 4 with sulfuric acid or sodium hydroxide, and 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 separated by filtration, and the concentrations of aluminum ions and lanthanum ions in the supernatant were detected by ICP to calculate the adsorption amount and selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions. Figure 9 The adsorption amount and removal rate of the β-cyclodextrin / aluminum citrate ion imprinted material for Al 3+ under different shaking times in this embodiment are shown in the following graph.

[0079] It can be seen from Figure 9 that the adsorption amount and removal rate of the β-cyclodextrin / aluminum citrate ion imprinted material for Al 3+ reach a peak at a shaking time of 20 hours, and the removal rate is more than 78%.

[0080] Example 10

[0081] As Figure 12As shown, 3 g of β-cyclodextrin, 1.5 g of citric acid and 0.75 g of KH2PO4 were sequentially added into a conical flask containing 30 ml of deionized water, and reacted in a water bath at 100°C for 3 hours to form a clear and transparent solution. 1 g of aluminum sulfate, 3 mmol of EGDMA and 1 mmol of ammonium persulfate were sequentially poured into the conical flask containing the precursor, and the conical flask was placed into a magnetic stirrer for water bath reaction for 30 minutes. After completion of stirring, the mixture in the conical flask was poured into a culture dish and placed into a forced air drying oven, and incubated at 150°C for 75 minutes. After the incubation time ended, the forced air drying oven was turned off and the culture dish was left in the drying oven to cool to room temperature. After washing the product with deionized water several times, the solid product was collected by centrifugal solid-liquid separation, and was placed into a vacuum drying oven for drying. After constant weight, it was ground into powder, and then washed with 0.25 mol·L -1 of NaOH solution for 6 hours to elute the aluminum ions in the β-cyclodextrin / aluminum citrate ion imprinted material. Centrifugal solid-liquid separation was used, the sample was washed with deionized water until neutral, and then dried 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 into 50 mL of a solution of aluminum ions at 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, respectively, with the pH value adjusted to 4 using sulfuric acid or sodium hydroxide, and was shaken in a constant temperature shaking box for 20 hours. The supernatant was obtained by filtration separation, and the concentrations of aluminum ions and lanthanum ions in the supernatant were detected by ICP to calculate the adsorption amount and selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions. Figure 10 The curve graph of the adsorption amount of the β-cyclodextrin / aluminum citrate ion imprinted material for Al 3+ at different initial concentrations in this embodiment.

[0082] As can be seen from Figure 10 , the adsorption amount and removal rate of the β-cyclodextrin / aluminum citrate ion imprinted material for Al 3+ reach a peak at an initial concentration of 300 mg / L, and the adsorption amount is more than 28 mg / g.

[0083] Example 11

[0084] As Figure 12As shown, 3 g of β-cyclodextrin, 1.5 g of citric acid and 0.75 g of KH2PO4 were sequentially added into a conical flask containing 30 ml of deionized water, and reacted in a water bath at 100°C for 3 hours to form a clear and transparent solution. 1 g of aluminum sulfate, 3 mmol of EGDMA and 1 mmol of ammonium persulfate were sequentially added into the conical flask containing the precursor, and the conical flask was placed into a magnetic stirrer for water bath reaction for 30 minutes. After completion of stirring, the mixture in the conical flask was poured into a culture dish and placed into a forced air drying oven, and incubated at 150°C for 75 minutes. After the incubation time ended, the forced air drying oven was turned off and the culture dish was left in the drying oven to cool to room temperature. After washing the product with deionized water several times, the solid product was collected by solid-liquid separation using a centrifuge, and was placed into a vacuum drying oven for drying. After constant weight, the product was ground into powder, and then eluted with 0.25 mol / L NaOH solution for 6 hours to elute the aluminum ions in the β-cyclodextrin / aluminum citrate ion imprinted material. The sample was washed to neutral with deionized water, and then dried 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 into 50 mL of a mixed solution of 20 mg / L aluminum ions and 100 mg / L lanthanum ions with the pH value adjusted to 4 using sulfuric acid or sodium hydroxide, and was shaken in a constant temperature shaking incubator for 20 h. The supernatant and the β-cyclodextrin / aluminum citrate ion imprinted material after adsorption were separated by filtration, and the β-cyclodextrin / aluminum citrate ion imprinted material after adsorption was eluted again using 0.25 mol / L NaOH solution. The sample was washed to neutral with deionized water, and then dried in an oven at 80°C. 0.1 g of the β-cyclodextrin / aluminum citrate ion imprinted material was added into 50 mL of a mixed solution of 20 mg / L aluminum ions and 100 mg / L lanthanum ions with the pH value adjusted to 4 using sulfuric acid or sodium hydroxide, and was shaken in a constant temperature shaking incubator for 20 h. The supernatant was separated by filtration, and the concentrations of aluminum ions and lanthanum ions in the supernatant were detected by ICP. The adsorption amount and the selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions after each cycle were calculated. -1 The curve of the adsorption amount and the selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions in the cyclic experiment in this embodiment is shown in FIG. 1. Figure 11 The curve of the adsorption amount and the selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions in the cyclic experiment in this embodiment is shown in FIG. 1. 3+ The curve of the adsorption amount and the selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions in the cyclic experiment in this embodiment is shown in FIG. 1.

[0085] As can be seen from FIG. 1, the selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for Al Figure 11 3+ is higher than 110.

[0086] Example 12

[0087] As shown in FIG. 2, the curve of the adsorption amount and the selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for Al Figure 12 ​As shown, 3 g of β-cyclodextrin, 1.5 g of citric acid and 0.75 g of KH2PO4 were sequentially added into a conical flask containing 30 ml of deionized water, and reacted in a water bath at 100°C for 3 hours to form a clear and transparent solution. 1 g of aluminum sulfate, 3 mmol of EGDMA and 1 mmol of ammonium persulfate were sequentially poured into the conical flask containing the precursor, and the conical flask was placed into a magnetic stirrer for water bath reaction for 30 minutes. After completion of stirring, the mixture in the conical flask was poured into a culture dish and placed into a forced air drying oven, and incubated at 150°C for 75 minutes. After the incubation time ended, the forced air drying oven was turned off and the culture dish was left in the drying oven to cool to room temperature. After washing the product with deionized water several times, the solid product was collected by centrifugal solid-liquid separation, and placed into a vacuum drying oven for drying. After constant weight, it was ground into powder, and then washed with 0.25 mol·L -1 of NaOH solution for 6 hours to elute the aluminum ions in the β-cyclodextrin / aluminum citrate ion polymer material. Solid-liquid separation was performed by a centrifuge, the sample was washed with deionized water until neutral, and then dried 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 formed by adding 20 mg / L of aluminum ion solution, 100 mg / L of lanthanum ion, 100 mg / L of yttrium ion and erbium ion, respectively, and adjusting the pH of the mixed solution to 4 with sulfuric acid or sodium hydroxide. Shake in a constant temperature shaking incubator for 20 h, filter to separate the supernatant, and detect the concentrations of aluminum ions and lanthanum ions in the supernatant by ICP to calculate the adsorption amount and selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material to aluminum ions (see Table 1).

[0088] Table 1: Adsorption amount and removal rate of β-cyclodextrin / aluminum citrate ion imprinted material to Al 3+ at initial concentration.

[0089]

[0090] As shown in Table 1, the β-cyclodextrin / aluminum citrate ion imprinted material has a selectivity coefficient of 150.38, 10.64 and 33.92 to Al 3+ : La 3+ , Al 3+ : Y 3+ and Al 3+ : Er 3+ , respectively, and the selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material reaches the maximum when aluminum and lanthanum ions are mixed.

[0091] Finally, it should be noted that the above only describes the preferred embodiments of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art will appreciate that the technical solutions described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalent ones. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for synthesizing a β-cyclodextrin aluminum citrate ion imprinted material, characterized in that: The following steps are involved: 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 react to synthesize a β-cyclodextrin / citric acid precursor; S2. Pour aluminum sulfate 18hydrate, ethylene glycol dimethacrylate, and ammonium persulfate into the bottle containing the precursor in sequence, heat in a water bath for reaction, and dry the crude product in the bottle after the reaction is completed; S3, washing the crude product with deionized water, filtering and drying, and then grinding and modifying with ethanol to obtain a β-cyclodextrin / aluminum citrate ionomer material; S4, use 0.25 mol·L -1 Sodium hydroxide solution is used to remove aluminum ions from the β-cyclodextrin / aluminum citrate ion polymer material; S5. Wash with deionized water to adjust the pH value of the β-cyclodextrin / aluminum citrate ion polymer material from which aluminum ions have been removed to neutral. After drying, a β-cyclodextrin / aluminum citrate ion imprinted material is obtained.

2. The method for synthesizing a β-cyclodextrin / aluminum citrate ion imprinted material according to claim 1, characterized in that: In step S1, the mass ratio of β-cyclodextrin, citric acid and potassium dihydrogen phosphate is 4: (1-12): 1, and the mass ratio of the mixture to deionized water is (3.75-12): 30; The water bath reaction in step S1 is performed by placing the bottle in a water bath constant temperature oscillator for stirring, wherein the temperature of the constant temperature oscillator is 70-120° C. and the water bath time is 0.5-5 h.

3. The method for synthesizing a β-cyclodextrin / aluminum citrate ion imprinted material according to claim 1, characterized in that: In step S2, the mass ratio of aluminum sulfate 18hydrate, ethylene glycol dimethacrylate and ammonium persulfate is (1-3): (0.2-0.7): (0.1-0.3); The water bath reaction in step S2 is to place the bottle in a water bath constant temperature oscillator for stirring, the temperature of the constant temperature oscillator is 110-160° C., and the water bath time is 10-60 min; In step S2, the drying temperature is 120-160° C., and the drying time is 45-105 minutes.

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

5. 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.

6. Use of the β-cyclodextrin / aluminum citrate ion imprinted material prepared by the synthesis method according to any one of claims 1 to 5 for selectively removing aluminum ions from rare earth elements, characterized in that: The following steps are involved: S6, preparing aluminum sulfate into an aluminum ion solution of a certain concentration; S7, measuring the aluminum ion solution, adjusting the pH value to 2.5-4 with sulfuric acid or sodium hydroxide, adding the β-cyclodextrin / aluminum citrate ion imprinting material to the aluminum ion solution, shaking and mixing, and filtering to obtain a supernatant; S8. Detecting the aluminum ion concentration in the supernatant and calculating the aluminum ion removal rate and adsorption amount of the β-cyclodextrin / aluminum citrate ion imprinted material; S9, measuring a mixed solution of aluminum ions and rare earth ions, adding the β-cyclodextrin / aluminum citrate ion imprinting material to the mixed solution of aluminum ions and rare earth ions, shaking the mixed solution for reaction, and filtering to obtain a supernatant; S10. Detect the concentrations of aluminum ions and rare earth ions in the supernatant, and calculate the selectivity coefficient of the β-cyclodextrin / aluminum citrate ion imprinted material for aluminum ions.

7. Use of the β-cyclodextrin / aluminum citrate ion imprinted material according to claim 6 for selectively removing aluminum ions from rare earth elements, characterized in that: The concentration of the aluminum ion solution in step S6 is 10 mg / L to 500 mg / L.

8. Use of the β-cyclodextrin / aluminum citrate ion imprinted material according to claim 6 for selectively removing aluminum ions from rare earth elements, characterized in that: In step S7, the mass ratio of the β-cyclodextrin / aluminum citrate ion imprinting material to the aluminum ion is (60-250): (0.5-25); The mixing reaction in step S7 is carried out in a constant temperature shaking box at a reaction temperature of 25° C. and a reaction time of 0.5 to 26 h.

9. Use of the β-cyclodextrin / aluminum citrate ion imprinted material according to claim 8 for selectively removing aluminum ions from rare earth elements, characterized in that: The rare earth ions in the mixed solution of aluminum ions and rare earth ions in step S9 are at least one of lanthanum, yttrium and erbium.

10. Use of the β-cyclodextrin / aluminum citrate ion imprinted material according to claim 8 for selectively removing aluminum ions from rare earth elements, characterized in that: In the step S9, the rare earth ion concentration in the mixed solution of aluminum ions and rare earth ions is 100 mg / L, and the aluminum ion concentration is 20 mg / L; the mass ratio of the β-cyclodextrin / aluminum citrate ion imprinting material to the aluminum ion is 100:1; The mixing reaction in step S9 is carried out in a constant temperature shaking box at a reaction temperature of 25° C. and a reaction time of 0.5 to 26 h.

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