Functionalized hierarchical pore adsorption chelating resin as well as preparation method and application thereof

Abstract

The invention relates to the field of resin synthesis, in particular to functionalized hierarchical pore adsorption chelating resin as well as a preparation method and application thereof. According to the functionalized hierarchical pore adsorption chelating resin, the particle size is 0.65-1.2 mm, the specific surface area is 550-1500 m < 2 > / g, the pore volume is 0.4-1.8 cm < 3 > / g, the proportion of micropores is 15-35%, the proportion of mesopores is 25-40%, and the proportion of macropores is 25-60%. Micropores, mesopores and macropores of the functionalized hierarchical pore adsorption chelating resin are uniformly distributed, the particle size is moderate, the specific surface area and pore volume are relatively large, and the functionalized hierarchical pore adsorption chelating resin has relatively large adsorption capacity on copper ions, nickel ions and lead ions.

Description

Technical Field

[0001] The invention relates to the field of resin synthesis, and in particular to a functionalized multi-level pore adsorption chelating resin and a preparation method and application thereof. Background Art

[0002] Chelating resin is a kind of cross-linked functional polymer material that can form multi-coordinated complexes with metal ions. The mechanism of metal ion adsorption by chelating resin is that the functional atoms on the resin react with the metal ions to form a stable structure similar to a small molecule chelate, while the adsorption mechanism of ion exchange resin is electrostatic action. Therefore, compared with ion exchange resin, chelating resin has stronger binding force with metal ions and higher selectivity, and can be widely used in various industries, including the recovery and separation of metal ions, the splitting of amino acids, hydrometallurgy, pollution prevention and control, etc.

[0003] The chelating resin is composed of a cross-linked polymer (such as styrene / divinylbenzene resin) as a skeleton, connected with special functional groups, and has the advantages of high selectivity and strong binding force with the adsorbate. Patent CN 115490867A discloses an adsorption resin and its preparation method and application. The adsorption resin uses a styrene-divinylbenzene macroporous resin containing carboxyl groups as a carrier, immobilizes an adsorption ligand, and the adsorption ligand is polyethyleneimine. The polyethyleneimine and the carboxyl group undergo an amidation reaction and are immobilized on the carrier. The carboxyl group is obtained by carboxylation modification of the styrene-divinylbenzene macroporous resin; the application field of the resin is the field of blood purification technology, which plays a role in the treatment and regulation of endotoxins, cytokines and coagulation function in sepsis patients. Patent CN 116253816A discloses a preparation method of a chelating resin, the steps of which include: placing an amino resin in a swelling solution for swelling treatment, adding acrylic acid, propylene sulfonic acid, acrylate, propylene sulfonate, acrylate or propylene sulfonate for addition reaction, and washing with a detergent after the reaction is completed to obtain a chelating resin. Although the chelating resin is environmentally friendly and has low energy consumption, its exchange capacity and Cu 2+ The adsorption capacity is still not ideal.

[0004] In addition, in some special industrial production, a resin with selectivity for a certain metal and a large adsorption capacity is required to improve the production efficiency and reduce the production cost. Therefore, the development of a functionalized chelating resin that can be mass-produced, has high selectivity for the target adsorbent, and has a high adsorption capacity is of great significance to industrial production and scientific and technological development. Summary of the invention

[0005] In order to solve the above-mentioned technical problems, the purpose of the present invention is to propose a functionalized multi-level pore adsorption chelating resin and its preparation method and application. The prepared functionalized multi-level pore adsorption chelating resin has uniform pore size distribution, moderate particle size, large specific surface area and pore volume, and has good selectivity, adsorption performance and high desorption regeneration rate for heavy metal ions.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0007] The first aspect of the present invention provides a functionalized multi-level porous adsorption chelating resin, wherein the particle size of the chelating resin is 0.65-1.2 mm, and the specific surface area is 550-1500 m 2 / g, pore volume 0.4-1.8cm 3 / g.

[0008] In some embodiments, the micropores of the chelating resin account for 15-35%, the mesopores account for 25-40%, and the macropores account for 25-60%.

[0009] The second aspect of the present invention provides a method for preparing a functionalized multi-level porous adsorption chelating resin, comprising the following preparation steps:

[0010] (1) Styrene, divinylbenzene and vinyl acetic acid are uniformly mixed, an initiator is added thereto, and the mixture is stirred until the initiator is completely dissolved, and then the mixture is poured into pure water, and the mixture is reacted for 6-10 hours under stirring and heating conditions, and then separated, washed and dried to obtain a white solid;

[0011] (2) at room temperature, adding the white solid obtained in step (1) to C2H4Cl2, stirring and swelling for 10-14 hours, then adding p-dichlorobenzyl and anhydrous tin tetrachloride thereto in sequence, stirring for 25-40 minutes, reacting at 75-85°C for 20-24 hours, separating, washing, and drying to obtain a multi-level porous adsorption resin;

[0012] (3) Add the multi-level porous adsorption resin and the coupling agent obtained in step (2) into toluene and mix them evenly, then add the functional monomer, heat to 100-120° C. and react for 1-4 hours, then cool to room temperature, separate, wash and dry to obtain a functionalized multi-level porous adsorption chelating resin.

[0013] In some embodiments, the molar ratio of styrene, divinylbenzene and vinyl acetic acid is 1:(0.01-0.02):(0.05-0.15).

[0014] In some embodiments, the heating temperature in step (1) is 85-95°C.

[0015] Preferably, the heating temperature in step (1) is 90°C.

[0016] In some embodiments, the mass ratio of the white solid, p-benzyl dichloride and anhydrous tin tetrachloride in step (2) is 1:(0.9-1.1):(0.9-1.1).

[0017] Preferably, in step (2), the mass ratio of the white solid, p-benzyl dichloride and anhydrous tin tetrachloride is 1:1.05:1.05.

[0018] In some embodiments, the preparation steps of the functional monomer are:

[0019] Mix hydroxylamine hydrochloride, DL-aminocaprolactam and toluene evenly, react at 85-95° C. for 2-4 hours with stirring, separate and dry to obtain a functional monomer.

[0020] In some embodiments, the molar ratio of hydroxylamine hydrochloride to DL-aminocaprolactam is (1-1.3):1.

[0021] Preferably, the molar ratio of hydroxylamine hydrochloride to DL-aminocaprolactam is 1.15:1.

[0022] In some embodiments, the amount of the functional monomer in step (3) is 10-20 wt % of the multi-level porous adsorption resin.

[0023] Preferably, the amount of the functional monomer used in step (3) is 15 wt % of the multi-level porous adsorption resin.

[0024] The third aspect of the present invention provides an application of a functionalized multi-level porous adsorption chelating resin in the adsorption field.

[0025] The invention firstly uses styrene, divinylbenzene and vinylacetic acid as raw materials to synthesize carboxylation resin through process control, then uses hydroxylamine hydrochloride and DL-aminocaprolactam as raw materials to synthesize a hydroxamic acid functional monomer, and introduces the functional monomer into the carboxylation resin to prepare a multi-level porous adsorption chelating resin with hydroxamic acid functional groups and amide functional groups, which has high adsorption performance for different heavy metals.

[0026] Hydroxamic acid compounds are used in the field of heavy metal ion adsorption due to their unique skeleton structure and excellent coordination performance. The functional monomer synthesized in the present invention belongs to a hydroxamic acid compound, in which the hydrophobic group can effectively reduce the interfacial tension between the resin and the heavy metal ions, and the hydroxamic acid functional group can also improve the adsorption performance of the chelating resin for heavy metal ions.

[0027] The present invention prepares monomer molecules such as styrene, divinylbenzene and vinylacetic acid into multi-level porous adsorption resin by polycondensation reaction, and introduces aminohydroxamic acid functional monomer and carboxylic acid group into multi-level porous adsorption resin by amidation reaction, generates double hydrophobic group, multi-level porous adsorption chelating resin, its functional group is evenly distributed, chelating capacity is large, hydroxamic acid functional group and acylamino functional group therein chelate with metal ion to form cyclic complex, selectively chelates specific metal ion from solution system containing heavy metal. This is because nitrogen and oxygen atoms in these two functional groups can coordinate with metal ion to form stable chelate structure as adsorption active sites, and hydroxamic acid functional group and acylamino functional group are both soft bases, and have significant binding performance and selective adsorption to soft acids such as heavy metal ions. In addition, the carboxyl group on the chelating resin can further adsorb heavy metal ions, and improve the adsorption kinetics speed of the chelating resin. The multi-level pore adsorption chelating resin of the present invention has uniform pore size distribution, moderate particle size, large specific surface area and pore volume, can selectively adsorb specific heavy metal ions, has large adsorption capacity, and has high desorption regeneration rate.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] 1. The present invention prepares a multi-level porous adsorption resin from monomer molecules such as styrene, divinylbenzene and vinylacetic acid through a condensation reaction, and introduces an aminohydroxamic acid functional monomer and a carboxylic acid group into the multi-level porous adsorption resin through an amidation reaction to generate a double hydrophobic group, multi-level porous adsorption chelating resin. The multi-level porous adsorption chelating resin can not only selectively adsorb specific heavy metal ions and has a large adsorption capacity, but also has a high desorption regeneration rate.

[0030] 2. The present invention synthesizes hydroxamic acid functional monomers through process control, wherein the hydrophobic groups can effectively reduce the interfacial tension between the resin and the heavy metal ions, and the hydroxamic acid functional groups can also improve the adsorption performance of the chelating resin for heavy metal ions. DETAILED DESCRIPTION

[0031] Now describe in detail various exemplary embodiments of the present invention, this detailed description should not be considered as limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics and embodiments of the present invention. It should be understood that the terms described in the present invention are only for describing a particular embodiment, and are not used to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper limit and the lower limit of the range is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the range.

[0032] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. Various modifications and variations may be made to the specific embodiments of the present invention specification without departing from the scope or spirit of the present invention, which will be apparent to those skilled in the art. Other embodiments obtained from the present invention specification will be apparent to the technician. The present application specification and examples are exemplary only.

[0033] The words “include,” “including,” “have,” or “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0034] The initiator used in the present invention is initiator TPO; the coupling agent used is N,N-carbonyldiimidazole.

[0035] Preparation Example 1

[0036] 1.15 mol of hydroxylamine hydrochloride, 1 mol of DL-aminocaprolactam and 500 mL of toluene were mixed evenly, reacted at a stirring speed of 150 r / min and 90° C. for 3 h, filtered, and dried at 60° C. to constant weight to obtain a functional monomer.

[0037] Preparation Example 2

[0038] 0.9 mol of hydroxylamine hydrochloride, 1 mol of DL-aminocaprolactam and 500 mL of toluene were mixed evenly, reacted at a stirring speed of 150 r / min and 90° C. for 3 h, filtered, and dried at 60° C. to constant weight to obtain a functional monomer.

[0039] Preparation Example 3

[0040] 1.15 mol of hydroxylamine hydrochloride, 1 mol of DL-aminocaprolactam and 500 mL of toluene were mixed evenly, reacted at a stirring speed of 150 r / min and 80° C. for 3 h, filtered, and dried at 60° C. to constant weight to obtain a functional monomer.

[0041] Example 1

[0042] A method for preparing a functionalized multi-level porous adsorption chelating resin comprises the following preparation steps:

[0043] (1) 1 mol of styrene, 0.01 mol of divinylbenzene and 0.05 mol of vinyl acetic acid were uniformly mixed, 0.03 mol of initiator was added thereto, and the mixture was stirred at a stirring speed of 200 r / min until the initiator was completely dissolved, and then poured into 250 mL of pure water, reacted at 200 r / min and 85° C. for 10 h, filtered, washed with pure water 3 times, and dried at 65° C. to constant weight to obtain a white solid;

[0044] (2) At room temperature, 60 g of the white solid obtained in step (1) was added to 500 mL of C2H4Cl2, stirred and swollen for 10 h, and then 54 g of p-dichlorobenzyl and 54 g of anhydrous tin tetrachloride were added thereto in sequence, stirred for 25 min, reacted at 75°C for 24 h, filtered, washed with pure water 3 times, and dried at 65°C to constant weight to obtain a multi-level porous adsorption resin;

[0045] (3) 50 g of the multi-level porous adsorption resin obtained in step (2) and 10 g of the coupling agent are added to 200 mL of toluene and mixed evenly, and then 5 g of the functional monomer is added, and the temperature is raised to 100 ° C. to react for 4 hours, followed by cooling to room temperature, filtering, washing with anhydrous ethanol and pure water for 3 times respectively, and drying at 65 ° C. to constant weight to obtain a functionalized multi-level porous adsorption chelating resin.

[0046] The functional monomer used was obtained from Preparation Example 1.

[0047] Example 2

[0048] A method for preparing a functionalized multi-level porous adsorption chelating resin comprises the following preparation steps:

[0049] (1) 1 mol of styrene, 0.02 mol of divinylbenzene and 0.15 mol of vinyl acetic acid were uniformly mixed, 0.04 mol of initiator was added thereto, and the mixture was stirred at a stirring speed of 200 r / min until the initiator was completely dissolved, and then poured into 250 mL of pure water, reacted at 200 r / min and 95° C. for 6 h, filtered, washed with pure water 3 times, and dried at 65° C. to constant weight to obtain a white solid;

[0050] (2) At room temperature, 60 g of the white solid obtained in step (1) was added to 500 mL of C2H4Cl2, and the mixture was stirred and swollen for 14 h. Then, 66 g of p-dichlorobenzyl and 66 g of anhydrous tin tetrachloride were added thereto in sequence, and the mixture was stirred for 40 min. The mixture was reacted at 85°C for 20 h, filtered, washed with pure water for 3 times, and dried at 65°C to constant weight to obtain a multi-level porous adsorption resin;

[0051] (3) 50 g of the multi-level porous adsorption resin obtained in step (2) and 16 g of the coupling agent are added to 200 mL of toluene and mixed evenly, and then 10 g of the functional monomer is added, and the temperature is raised to 120° C. for reaction for 1 hour, followed by cooling to room temperature, filtering, washing with anhydrous ethanol and pure water for 3 times respectively, and drying at 65° C. to constant weight to obtain a functionalized multi-level porous adsorption chelating resin.

[0052] The functional monomer used was obtained from Preparation Example 1.

[0053] Example 3

[0054] A method for preparing a functionalized multi-level porous adsorption chelating resin comprises the following preparation steps:

[0055] (1) 1 mol of styrene, 0.015 mol of divinylbenzene and 0.1 mol of vinyl acetic acid were uniformly mixed, 0.04 mol of initiator was added thereto, and the mixture was stirred at a stirring speed of 200 r / min until the initiator was completely dissolved, and then poured into 250 mL of pure water, reacted at 200 r / min and 90° C. for 12 h, filtered, washed with pure water 3 times, and dried at 65° C. to constant weight to obtain a white solid;

[0056] (2) At room temperature, 60 g of the white solid obtained in step (1) was added to 500 mL of C2H4Cl2, and the mixture was stirred and swollen for 12 h. Then, 63 g of p-dichlorobenzyl and 63 g of anhydrous tin tetrachloride were added thereto in sequence, and the mixture was stirred for 35 min. The mixture was reacted at 80°C for 22 h, filtered, washed with pure water for 3 times, and dried at 65°C to constant weight to obtain a multi-level porous adsorption resin;

[0057] (3) 50 g of the multi-level porous adsorption resin obtained in step (2) and 14 g of the coupling agent were added to 200 mL of toluene and mixed evenly, and then 7.5 g of the functional monomer was added, and the mixture was heated to 110° C. and reacted for 2.5 h. The mixture was then cooled to room temperature, filtered, washed with anhydrous ethanol and pure water for 3 times each, and dried at 65° C. to constant weight to obtain a functionalized multi-level porous adsorption chelating resin.

[0058] The functional monomer used was obtained from Preparation Example 1.

[0059] Example 4

[0060] A method for preparing a functionalized multi-level porous adsorption chelating resin, the specific implementation method is the same as that of Example 3, except that the functional monomer used is obtained from Preparation Example 2.

[0061] Example 5

[0062] A method for preparing a functionalized multi-level porous adsorption chelating resin, the specific implementation method is the same as that of Example 3, except that the functional monomer used is obtained from Preparation Example 3.

[0063] Comparative Example 1

[0064] A method for preparing a multi-stage porous adsorption chelating resin comprises the following preparation steps:

[0065] (1) 1 mol of styrene, 0.015 mol of divinylbenzene and 0.1 mol of vinyl acetic acid were uniformly mixed, 0.04 mol of initiator was added thereto, and the mixture was stirred at a stirring speed of 200 r / min until the initiator was completely dissolved, and then poured into 250 mL of pure water, reacted at 200 r / min and 90° C. for 12 h, filtered, washed with pure water 3 times, and dried at 65° C. to constant weight to obtain a white solid;

[0066] (2) At room temperature, 60 g of the white solid obtained in step (1) was added to 500 mL of C2H4Cl2, stirred and swollen for 12 h, and then 63 g of p-dichlorobenzyl and 63 g of anhydrous tin tetrachloride were added thereto in sequence, stirred for 35 min, reacted at 80°C for 22 h, filtered, washed with pure water 3 times, and dried at 65°C to constant weight to obtain a multi-level porous chelating resin.

[0067] Comparative Example 2

[0068] A method for preparing a functionalized multi-level porous adsorption chelating resin comprises the following preparation steps:

[0069] (1) 1 mol of styrene and 0.015 mol of divinylbenzene were uniformly mixed, 0.04 mol of initiator was added thereto, and the mixture was stirred at a stirring speed of 200 r / min until the initiator was completely dissolved, then poured into 250 mL of pure water, reacted at 200 r / min and 90° C. for 12 h, filtered, washed with pure water 3 times, and dried at 65° C. to constant weight to obtain a white solid;

[0070] (2) At room temperature, 60 g of the white solid obtained in step (1) was added to 500 mL of C2H4Cl2, and the mixture was stirred and swollen for 12 h. Then, 63 g of p-dichlorobenzyl and 63 g of anhydrous tin tetrachloride were added thereto in sequence, and the mixture was stirred for 35 min. The mixture was reacted at 80° C. for 22 h, filtered, washed with pure water for 3 times, and dried at 65° C. to constant weight to obtain a multi-level porous chelating resin.

[0071] (3) 50 g of the multi-level porous adsorption resin obtained in step (2) and 14 g of the coupling agent were added to 200 mL of toluene and mixed evenly, and then 7.5 g of the functional monomer was added, and the mixture was heated to 110° C. and reacted for 2.5 h. The mixture was then cooled to room temperature, filtered, washed with anhydrous ethanol and pure water for 3 times each, and dried at 65° C. to constant weight to obtain a functionalized multi-level porous adsorption chelating resin.

[0072] The functional monomer used was obtained from Preparation Example 1.

[0073] Performance test of chelating resin

[0074] 1. Determination of the grafting rate of the functional monomer on the chelating resin in the embodiment: The grafting rate of the functional monomer on the functionalized multi-level porous adsorption chelating resin was titrated and calculated using the cation exchange resin exchange capacity determination method in the national standard GB / T8144-2008.

[0075] The grafting process of the present invention is that the carboxyl group in the multi-level porous adsorption chelating resin reacts with the amino group in the functional monomer at a molar ratio of 1:1. The functional monomer in the present invention is 2,6-diaminohexyl hydroxamic acid. Therefore, the amount of the functional monomer in the solution before and after grafting is recorded as n0 and n1 respectively, the amount of the carboxyl group in the functionalized multi-level porous adsorption chelating resin is recorded as n2, and the grafting rate is calculated according to the following formula: G=100%*(n0-n1) / n2.

[0076] Calculation method of mass concentration of functional monomer: firstly prepare the functional monomer obtained in each preparation example with pure water to be a 1g / L standard solution, take 1mL, 2mL, 3mL, 5mL, 7mL, 8mL of the standard solution in a 50mL volumetric flask, add 5mL of anhydrous ethanol and 10mL of 0.365g / L HCl solution in sequence, shake well, then add 2mL of 1wt% ferric chloride solution, mix and shake well, make up to 50mL with pure water, let stand for 30min, obtain the solution to be tested, take the blank sample as the reference solution, measure the absorbance of functional monomers of different concentrations at a wavelength of 503nm with an ultraviolet spectrophotometer, and draw a standard working curve for each preparation example;

[0077] Calculate the amount of functional monomer substance n0 in the solution before grafting in each example, then take 1 mL of the solution after grafting in each example and dissolve it in 100 mL of pure water to prepare a test solution, measure the absorbance at a wavelength of 503 nm, and calculate the amount of functional monomer substance n1 in the solution after grafting;

[0078] The amount of carboxyl substance on the chelating resin is determined by back titration and recorded as n2.

[0079] The specific test results are shown in Table 1.

[0080] Table 1

[0081] serial number Example 1 Example 2 Example 3 Example 4 Example 5 Grafting rate (%) 65.2 66.1 66.7 62.2 60.8

[0082] It can be seen from Table 1 that the grafting rate of the functional monomers in Examples 1-3 is relatively high; compared with Example 3, the preparation steps of the functional monomers used in Examples 4 and 5 have changed, which may change the yield and structure of the functional monomers and reduce the grafting rate of the amino and carboxyl groups in the functional monomers.

[0083] Based on the grafting rate data, the functionalized multi-level porous adsorption chelating resin prepared in Example 3 was selected to carry out the following test experiments.

[0084] 2. Performance test of chelating resin:

[0085] 2.1 Pore diameter ratio, specific surface area and pore volume

[0086] The pore size ratio, specific surface area and pore volume of the chelating resin in Example 3 were measured using ASAP2020 according to the BET method. Specific test data are shown in Table 2.

[0087] 2.2 Determination of heavy metal adsorption capacity of chelating resin

[0088] The chelating resin in Example 3, Comparative Examples 1 and 2 was subjected to a static adsorption experiment to measure the heavy metal adsorption capacity: 10 g of a wet-based functionalized multi-level pore adsorption chelating resin (water content of 50 wt%) was added to 50 mL of a copper sulfate aqueous solution (100 mg / mL), a nickel sulfate aqueous solution (50 mg / mL) and a lead sulfate aqueous solution (100 mg / mL) at pH = 5, respectively, and the mixture was shaken at 150 r / min for 30 min. The heavy metal ion adsorption capacity of the functionalized multi-level pore adsorption chelating resin was obtained by the following calculation formula: Q = V (C0 - Ce) / m, wherein Q is the equilibrium adsorption capacity (mg / g); C0 and Ce are the initial concentration of metal ions in the solution and the concentration when equilibrium is reached (mg / L), respectively; V is the volume of the solution (L); and m is the mass (g) of the wet-based functionalized multi-level pore adsorption chelating resin;

[0089] Among them, the copper ion concentration of the copper sulfate aqueous solution when it reaches adsorption equilibrium is determined by the sodium diethyldithiocarbamate spectrophotometry in the national standard GB / T7474-87; the nickel ion concentration of the nickel sulfate aqueous solution when it reaches adsorption equilibrium is determined by the dimethylglyoxime spectrophotometry in the national standard GB 11910-89; the lead ion concentration of the lead sulfate aqueous solution when it reaches adsorption equilibrium is determined by the dithizone spectrophotometry in the national standard GB / T 7470-87. Specific test data are shown in Table 3.

[0090] Table 2

[0091]

[0092] Table 3

[0093]

[0094] As shown in Tables 2 and 3, the functionalized multi-stage pore adsorption resin micropore, mesopore and macropore prepared in Example 3 are evenly distributed, and particle diameter is moderate, with larger specific surface area, pore volume, and copper ion, nickel ion and lead ion are all provided with larger adsorption capacity, compared to Example 3, functional monomer is not added in the resin preparation process in Comparative Example 1, vinyl acetate is not used in step (1) in Comparative Example 2, so that the structure of the resin changes, the number of functional groups is reduced, and the chelating effect of metal ions is significantly reduced. The above is only a preferred embodiment of the present invention, and is not to limit the present application in any form, although the present application discloses as above with a preferred embodiment, but is not to limit the present application, any technician familiar with the profession, within the scope of not departing from the technical solution of the present application, utilizing the technical contents disclosed above to make some changes or modifications are all equal to equivalent implementation cases, but as long as it is not departing from the technical solution content of the present invention, any simple modification, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention, all still belong to the scope of the technical solution.

Claims

1. A functionalized multi-level porous adsorption chelating resin, characterized in that: The particle size of the chelating resin is 0.65-1.2 mm, and the specific surface area is 550-1500 m 2 / g, pore volume 0.4-1.8cm 3 / g.

2. The functionalized multi-stage porous adsorption chelating resin according to claim 1, characterized in that: The micropores of the chelating resin account for 15-35%, the mesopores account for 25-40%, and the macropores account for 25-60%.

3. A method for preparing the functionalized multi-level porous adsorption chelating resin according to claim 1 or 2, characterized in that: The method comprises the following preparation steps: (1) Styrene, divinylbenzene and vinyl acetic acid are uniformly mixed, an initiator is added thereto, and the mixture is stirred until the initiator is completely dissolved, and then the mixture is poured into pure water, and the mixture is reacted for 6-10 hours under stirring and heating conditions, and then separated, washed and dried to obtain a white solid; (2) at room temperature, adding the white solid obtained in step (1) to C2H4Cl2, stirring and swelling for 10-14 hours, then adding p-dichlorobenzyl and anhydrous tin tetrachloride thereto in sequence, stirring for 25-40 minutes, reacting at 75-85°C for 20-24 hours, separating, washing, and drying to obtain a multi-level porous adsorption resin; (3) Add the multi-level porous adsorption resin and the coupling agent obtained in step (2) into toluene and mix them evenly, then add the functional monomer, heat to 100-120° C. and react for 1-4 hours, then cool to room temperature, separate, wash and dry to obtain a functionalized multi-level porous adsorption chelating resin.

4. The method for preparing a chelating resin according to claim 3, wherein The molar ratio of styrene, divinylbenzene and vinyl acetic acid is 1:(0.01-0.02):(0.05-0.15).

5. The method for preparing a chelating resin according to claim 3, wherein The heating temperature in step (1) is 85-95°C.

6. The method for preparing a chelating resin according to claim 3, wherein: In the step (2), the mass ratio of the white solid, p-benzyl dichloride and anhydrous tin tetrachloride is 1:(0.9-1.1):(0.9-1.1).

7. The method for preparing a chelating resin according to claim 3, wherein: The preparation steps of the functional monomer are: Mix hydroxylamine hydrochloride, DL-aminocaprolactam and toluene evenly, react at 85-95° C. for 2-4 hours with stirring, separate and dry to obtain a functional monomer.

8. The method for preparing a chelating resin according to claim 7, wherein: The molar ratio of the hydroxylamine hydrochloride to DL-aminocaprolactam is (1-1.3):

1.

9. The method for preparing a chelating resin according to claim 7, wherein: The amount of the functional monomer used in step (3) is 10-20 wt % of the multi-level porous adsorption resin.

10. Use of the functionalized multi-level pore adsorption chelating resin according to claim 1 or 2 or the functionalized multi-level pore adsorption chelating resin prepared by the preparation method according to any one of claims 3 to 9 in the field of adsorption.

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