A resin-based filter material, its preparation method and application

Abstract

The present invention relates to the field of filter material technology, and in particular to a resin-based filter material, its preparation method, and application. The resin-based filter material is based on a cation exchange resin and loaded with a CTF / CuS composite photocatalyst. The CTF accounts for 8.71-12.04% of the total mass of the filter material, and nano-CuS accounts for 4.16-7.68% of the total mass of the filter material. The resin-based filter material is used in antibiotic wastewater treatment. The resin-based filter material produced by the present invention can efficiently remove aminoglycoside antibiotics from water bodies, has high cyclic stability, and can still achieve a kanamycin removal rate of over 97.5% after secondary use.

Description

Technical Field

[0001] The present invention relates to the technical field of filter materials, and in particular to a resin-based filter material and a preparation method and application thereof. Background Art

[0002] Ion exchange resins are insoluble polymer compounds with active groups that exchange ions, a network structure, and a network structure. They are commonly used in water treatment, the food industry (such as sugar, monosodium glutamate, and wine), the pharmaceutical industry, synthetic chemistry and petrochemical industries, and air purification (such as removing acidic and alkaline gases, VOCs, and butane). Ion exchange resins can be divided into gel-type and macroporous types based on their pore structure. Resins with physical pores are called macroporous resins. They can also be divided into styrene-based resins and acrylic-based resins based on their matrix type. They are further divided into cationic resins and anionic resins. Cationic resins are further divided into strong acid and weak acid types, while anionic resins are divided into strong basic and weak basic types, or even medium-strong acid and medium-strong basic types.

[0003] Ion exchange resins work by exchanging their chemically active groups with ions in solution, thereby removing or separating ions. For example, strong-base anion exchange resins contain strongly basic groups that adsorb and bind to anions in solution, producing an anion exchange reaction. After a period of use, the resin typically requires regeneration using a chemical agent such as a strong base (such as NaOH) to restore its exchange capacity.

[0004] Since ion exchange resins have excellent adsorption properties, they are easily contaminated by organic matter and colloids in water bodies, resulting in a decrease in exchange capacity and difficulty in regeneration. At the same time, traditional ion exchange resins usually only use a single ion exchange effect to adsorb and remove impurities and pollutants in wastewater, which is difficult to meet the needs of complex water treatment. In order to solve the above problems, various functional ion exchange resin-based composite materials have emerged in an endless stream, and have become one of the research hotspots in the field of filtration materials. For example, the invention patent with application number CN201710003826.7 discloses a nuclear-grade ion exchange resin-based composite material and a preparation method thereof, which is a loaded catalyst obtained by assembling a platinum precursor, a silicon source, an aluminum source and a nuclear-grade ion exchange resin. The carrier is a nuclear-grade ion exchange resin, and the active load is a core-shell structure composite. The core is nano-platinum particles, and the shell is a platinum-silicon-aluminum molecular sieve composite of a porous silicon-aluminum molecular sieve. Through the synergistic effect of the three, it is beneficial to simultaneously exert the ion exchange effect of the ion exchange resin and the element exchange effect of the precious metal platinum nanocatalyst, thereby improving the removal and purification efficiency and recycling regeneration capacity. This composite material is effective for 24 Na + The decontamination efficiency can reach 92.7%, and the decontamination rate of the composite material is greater than 88.9% after 10 cycles.129 I - The decontamination efficiency reaches 96.7%, and the decontamination rate of the composite material is greater than 91.8% after 10 cycles. For example, the invention patent with application number CN202010664155.0 discloses an ion exchange resin-based composite material and its preparation method. Ce-MOF is first prepared by reacting a nitrogen-containing heterocyclic aromatic carboxylic acid compound and a cerium source. After carbonization, a carbon-nitrogen material-cerium oxide composite is obtained. Then, a strong acid styrene-based ion exchange resin is used for adsorption loading to prepare an ion exchange resin-based composite material. The directional enrichment effect of the porous carbon-nitrogen material is used to achieve the adsorption of organic pollutants. At the same time, cerium oxide is used as a photocatalyst. Its oxygen-rich vacancy characteristics can achieve the degradation of low-content organic matter, thereby achieving the effective removal of organic pollutants. For example, the invention patent with application number CN202211106636.5 discloses a particle-enhanced ion exchange resin, a preparation method and application thereof, including a carrier resin, an inorganic ion exchanger and a particle enhancer, wherein the inorganic ion exchanger and the particle enhancer are coated in the carrier resin; the carrier resin is calcium alginate; the inorganic ion exchanger includes one or both of ammonium phosphotungstate and ammonium phosphomolybdate; the particle enhancer includes at least one of silicon-containing inorganic micro-nanoparticles and titanium-containing inorganic micro-nanoparticles, and when the ion exchanger is pure ammonium phosphotungstate, it has good selective adsorption of cesium in a 0.1~5 mol / L nitric acid system, the adsorption rate can reach more than 97%, and the distribution coefficient is higher than 1000 cm 3 / g, can be used to separate cesium from high-level radioactive waste in strong nitric acid systems and to fill ion exchange columns to separate cesium from high-level radioactive waste. For example, patent application number CN202311216126.8 discloses an anion resin-based nano-cerium-manganese oxide composite material, its preparation method, and its application. The composite material comprises an anion exchange resin whose matrix is polystyrene-divinylbenzene or polyacrylic acid, whose functional groups are quaternary ammonium or tertiary amine groups, and whose pores are loaded with nano-hydrated cerium oxide particles and nano-hydrated manganese oxide particles. The composite material contains 7-16% cerium by mass and 6-15% manganese by mass. During the As(III) removal process, the Mn(IV) oxide nanoparticles first oxidize As(III) to the less toxic and more easily adsorbed As(V), which is then adsorbed by the Ce(IV) oxide nanoparticles. This achieves simultaneous oxidation and adsorption removal of As(III). The anion exchange groups on the resin can pre-enrich and enhance the diffusion of target pollutants through the Donnan membrane effect. For example, the invention patent with application number CN202310367802.5 discloses a preparation method and application of a resin-based magnetic composite adsorption material. Waste ion exchange resin is used as raw material, and after airflow expansion and pore expansion, it is magnetically modified, and sodium phosphite and sodium hypophosphite are added. After microwave heating reaction, the composite adsorption material is obtained. When the pH of the solution is 4, the removal rate of cadmium, chromium, copper, zinc, and nickel by the adsorption material reaches more than 90%, and the removal rate of manganese also reaches 87.01%, which has good performance in removing heavy metal ions. For example, the invention patent with application number CN202411282013.2 discloses an in-situ ecological restoration agent for river and lake sediments and its preparation process. PEG is fixed to the surface of carboxyl nitrile rubber modified SBS elastomer particles through an esterification reaction, and then crown ether, ethylenediaminetetraacetic acid, dimercaptosuccinic acid and the hydroxyl groups carried by PEG are subjected to an esterification reaction to obtain carboxyl nitrile rubber modified SBS elastomer composite ester particles. On the one hand, it can improve the adsorption capacity of heavy metals, and on the other hand, it can also reduce the introduction of harmful substances; by cooperating with montmorillonite particles, it can quickly remove heavy metal ions in aqueous solution, thereby improving the restoration effect on river and lake sediments; by adding anion and cation exchange resins and column chromatography silica gel, it can adsorb nitrogen and phosphorus compounds and other harmful ion groups in river and lake sediments, thereby improving the restoration effect; by adding coconut shell granular activated carbon, on the one hand, it can improve the restoration effect on organic pollutants and heavy metals, and on the other hand, it can also deodorize.

[0005] In order to further develop functional resin-based filter materials to meet the water treatment needs of complex wastewater environments, the present invention is the first to load CTF / CuS composite photocatalyst material on a cation exchange resin carrier and apply it to the treatment of antibiotic wastewater, especially for the degradation treatment of wastewater containing aminoglycoside antibiotics. Summary of the Invention

[0006] In view of this, the purpose of the present invention is to propose a resin-based filter material and its preparation method and application. On the one hand, a functional resin-based filter material that can be photocatalytically degraded is developed to meet the water treatment needs of complex wastewater environments. On the other hand, a new idea is provided for the treatment of antibiotic wastewater.

[0007] Based on the above objectives, the present invention provides a resin-based filter material, which is based on a cation exchange resin and loaded with a CTF / CuS composite photocatalyst; wherein CTF accounts for 8.71-12.04% of the total mass of the filter material, and nano-CuS accounts for 4.16-7.68% of the total mass of the filter material.

[0008] Furthermore, the cation exchange resin is a strongly acidic cation exchange resin.

[0009] Furthermore, the strongly acidic cation exchange resin is selected from one or more of D001, D072, Amberlite IRP69, Amberlite 200, and Lewatit Sp-210 cation exchange resins.

[0010] The present invention further provides a method for preparing a resin-based filter material, comprising the following steps:

[0011] S1: Add terephthalonitrile to trifluoromethanesulfonic acid, stir for 10-15 minutes, then add cation exchange resin, stir at 25-30°C for 18-24 hours, then heat to 70-85°C, stir and react for 3-6 hours, filter, wash, and dry to obtain CTF-loaded cation exchange resin;

[0012] S2: Add alkali metal sulfide salt to deionized water, stir to dissolve, add CTF-loaded cation exchange resin, stir for 10-15 minutes, then add soluble divalent copper salt, stir and react at 30-40°C for 12-18 hours, filter, wash, and dry to obtain a resin-based filter material.

[0013] Furthermore, the alkali metal sulfide salt is selected from one or more of sodium sulfide, potassium sulfide, and lithium sulfide.

[0014] Furthermore, the soluble divalent copper salt is selected from one or more of copper nitrate, copper sulfate, and copper acetate.

[0015] Furthermore, the usage ratio of the terephthalonitrile, trifluoromethanesulfonic acid, cation exchange resin, alkali metal sulfide salt, deionized water, and soluble divalent copper salt is (0.1-0.15) g:1 mL:1 g:(0.5-1) mmol:2 mL:(0.5-1) mmol.

[0016] The present invention further provides application of the resin-based filter material prepared by the preparation method in the treatment of antibiotic wastewater.

[0017] Furthermore, the antibiotic wastewater is wastewater containing aminoglycoside antibiotics.

[0018] Furthermore, the aminoglycoside antibiotic-containing wastewater is antibiotic wastewater containing one or more of kanamycin, gentamicin, tobramycin, ethimicin, and amikacin.

[0019] Beneficial effects of the present invention:

[0020] The present invention is the first to load a CTF / CuS composite photocatalyst material on a cation exchange resin carrier, presenting a core-shell structure, and is applied to the treatment of antibiotic wastewater, and is particularly suitable for the degradation treatment of difficult-to-degrade wastewater containing aminoglycoside antibiotics. The sulfonic acid groups rich in the surface of the strongly acidic cation exchange resin electrostatically adsorb aminoglycoside antibiotics, rapidly enriching the antibiotic pollutants on the resin matrix, and then utilizing the matrix-loaded CTF / CuS heterojunction photocatalyst to photocatalytically degrade the antibiotic molecules. The three synergistically enhance the efficiency, have high adsorption performance and high catalytic degradation performance, and realize the dynamic cycle treatment of "adsorption-photocatalytic degradation-re-adsorption-re-photocatalytic degradation..." of organic pollutants. Even in the absence of regeneration, the antibiotic wastewater can be continuously and effectively treated, and high adsorption-degradation performance can be maintained.

[0021] Compared to a single cation exchange resin, this resin-based filter material exhibits superior adsorption and degradation performance. This is due to the fact that, on the one hand, the photocatalyst on the resin-based filter material catalyzes the degradation of organic pollutants and, under illumination, remains in a dynamic, unsaturated adsorption state, making it difficult for the cation exchange resin to reach saturation equilibrium. On the other hand, the high specific surface area of the loaded CTF contributes to a certain degree of improvement in the filter material's adsorption capacity.

[0022] Compared with resin-based filter materials loaded with single CTF or single nano-CuS, this resin-based filter material uses cation exchange resin as a carrier, loads CTF, and further in situ chemically deposits nano-CuS. Unlike resin-based filter materials loaded with a single pure phase catalyst, the inventors constructed a heterojunction catalyst on the cation exchange resin to drive photogenerated electrons to jump from the valence band of nano-CuS to the conduction band of CTF, so that photogenerated holes remain in the valence band of nano-CuS, effectively improving the electron-hole separation efficiency and avoiding the agglomeration of nano-CuS particles. At the same time, the composite of CTF and nano-CuS expands the spectral response range, covering the entire visible light to near-infrared band, improving the utilization rate of sunlight, and thereby improving the light conversion efficiency and catalytic performance, and enhancing the catalytic degradation performance of antibiotics.

[0023] At the same time, under the premise of a certain amount of photocatalyst, compared with the CTF / CuS composite photocatalyst, the resin-based filter material breaks through the efficiency bottleneck of a single photocatalytic material through the triple synergistic effect of "adsorption → enrichment → degradation", and shows better catalytic degradation performance. The reason for this may be that, on the one hand, the cation exchange resin carrier itself can physically remove aminoglycoside antibiotics through electrostatic adsorption; on the other hand, the cation exchange resin is used to transform the catalyst component from "passive catalysis" to "active adsorption-catalysis", and the composite phase CTF / CuS is used as a photocatalyst, relying on the free diffusion of pollutants in the solution to contact the active sites. However, due to the low concentration of aminoglycoside antibiotics in wastewater, the photocatalytic reaction is limited by the mass transfer efficiency and the degradation rate is low. The present invention increases the "local concentration within the region" of antibiotic molecules through the pre-enrichment effect of the sulfonic acid groups in the resin matrix on aminoglycoside antibiotics, thereby significantly improving the contact efficiency between the loaded CTF / CuS heterojunction photocatalyst and the antibiotics, shortening the h + The distance of migration to the antibiotic contaminant can reduce the energy loss of the hole during the transmission process; at the same time, in the acidic microenvironment of the cation exchange resin, the aminoglycoside antibiotics Protonated , which reduces the electron cloud density of its glycosidic bond and amino side chain, making it easier to be or OH attack, thereby Directly oxidize the amino group to allow ·OH to attack and break the glycosidic bond, thereby improving the efficiency of selective and directional degradation of aminoglycoside antibiotics.

[0024] The resin-based filter material prepared by the present invention can efficiently remove aminoglycoside antibiotics in water bodies and has high circulation stability. When used for the second time, the kanamycin removal rate thereof can still be as high as over 97.5%. DETAILED DESCRIPTION

[0025] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to specific embodiments.

[0026] The present invention provides a resin-based filter material according to an embodiment of the present invention. The resin-based filter material is based on a cation exchange resin and loaded with a CTF / CuS composite photocatalyst. The CTF accounts for 8.71-12.04% of the total mass of the filter material, and the nano-CuS accounts for 4.16-7.68% of the total mass of the filter material.

[0027] In this embodiment, the cation exchange resin is a strongly acidic cation exchange resin;

[0028] In this embodiment, the strongly acidic cation exchange resin is preferably selected from one or more of D001, D072, Amberlite IRP69, Amberlite 200, and Lewatit Sp-210 cation exchange resins.

[0029] This embodiment is the first to load a CTF / CuS composite photocatalyst material on a cation exchange resin carrier, presenting a core-shell structure, and is applied to the treatment of antibiotic wastewater. It is particularly suitable for the degradation treatment of difficult-to-degrade wastewater containing aminoglycoside antibiotics. The sulfonic acid groups rich in the surface of the strongly acidic cation exchange resin electrostatically adsorb aminoglycoside antibiotics, rapidly enriching the antibiotic pollutants on the resin matrix. The CTF / CuS heterojunction photocatalyst loaded on the matrix is then used to photocatalytically degrade the antibiotic molecules. The three synergistically enhance the efficiency, have high adsorption performance and high catalytic degradation performance, and realize the dynamic cycle treatment of "adsorption-photocatalytic degradation-re-adsorption-re-photocatalytic degradation..." of organic pollutants. Even in the absence of regeneration, the antibiotic wastewater can be continuously and effectively treated, maintaining high adsorption-degradation performance.

[0030] Compared to a single cation exchange resin, this resin-based filter material exhibits superior adsorption and degradation performance. This is due to the fact that, on the one hand, the photocatalyst on the resin-based filter material catalyzes the degradation of organic pollutants and, under illumination, remains in a dynamic, unsaturated adsorption state, making it difficult for the cation exchange resin to reach saturation equilibrium. On the other hand, the high specific surface area of the loaded CTF contributes to a certain degree of improvement in the filter material's adsorption capacity.

[0031] Compared with resin-based filter materials loaded with single CTF or single nano-CuS, this resin-based filter material uses cation exchange resin as a carrier, loads CTF, and further in situ chemically deposits nano-CuS. Unlike resin-based filter materials loaded with a single pure phase catalyst, the inventors constructed a heterojunction catalyst on the cation exchange resin to drive photogenerated electrons to jump from the valence band of nano-CuS to the conduction band of CTF, so that photogenerated holes remain in the valence band of nano-CuS, effectively improving the electron-hole separation efficiency and avoiding the agglomeration of nano-CuS particles. At the same time, the composite of CTF and nano-CuS expands the spectral response range, covering the entire visible light to near-infrared band, improving the utilization rate of sunlight, and thereby improving the light conversion efficiency and catalytic performance, and enhancing the catalytic degradation performance of antibiotics.

[0032] At the same time, the inventors also found that under the premise of a certain amount of photocatalyst, compared with the CTF / CuS composite photocatalyst, the resin-based filter material breaks through the efficiency bottleneck of a single photocatalytic material through the triple synergistic effect of "adsorption → enrichment → degradation", and exhibits better catalytic degradation performance. The reason for this may be that, on the one hand, the cation exchange resin carrier itself can physically remove aminoglycoside antibiotics through electrostatic adsorption; on the other hand, the cation exchange resin is used to transform the catalyst component from "passive catalysis" to "active adsorption-catalysis", and the composite phase CTF / CuS is used as a photocatalyst, relying on the free diffusion of pollutants in the solution to contact the active sites. However, due to the low concentration of aminoglycoside antibiotics in wastewater, the photocatalytic reaction is limited by the mass transfer efficiency and the degradation rate is low. The present invention increases the "local concentration within the region" of antibiotic molecules through the pre-enrichment effect of the sulfonic acid groups in the resin matrix on aminoglycoside antibiotics, thereby significantly improving the contact efficiency between the loaded CTF / CuS heterojunction photocatalyst and the antibiotics, shortening h + The distance of migration to the antibiotic contaminant can reduce the energy loss of the hole during the transmission process; at the same time, in the acidic microenvironment of the cation exchange resin, the aminoglycoside antibiotics Protonated , which reduces the electron cloud density of its glycosidic bond and amino side chain, making it easier to be or OH attack, thereby Directly oxidize the amino group to allow ·OH to attack and break the glycosidic bond, thereby improving the efficiency of selective and directional degradation of aminoglycoside antibiotics.

[0033] The method for preparing the resin-based filter material of this embodiment comprises the following steps:

[0034] S1: Add terephthalonitrile to trifluoromethanesulfonic acid, stir for 10-15 minutes, then add cation exchange resin, stir at 25-30°C for 18-24 hours, then heat to 70-85°C, stir and react for 3-6 hours, filter, wash, and dry to obtain CTF-loaded cation exchange resin;

[0035] S2: Add alkali metal sulfide salt to deionized water, stir to dissolve, add CTF-loaded cation exchange resin, stir for 10-15 minutes, then add soluble divalent copper salt, stir and react at 30-40°C for 12-18 hours, filter, wash, and dry to obtain a resin-based filter material.

[0036] In this embodiment, the alkali metal sulfide salt is preferably one or more selected from sodium sulfide, potassium sulfide, and lithium sulfide.

[0037] In this embodiment, the soluble divalent copper salt is preferably selected from one or more of copper nitrate, copper sulfate, and copper acetate.

[0038] In this embodiment, the usage ratio of terephthalonitrile, trifluoromethanesulfonic acid, cation exchange resin, alkali metal sulfide salt, deionized water, and soluble divalent copper salt is (0.1-0.15) g:1 mL:1 g:(0.5-1) mmol:2 mL:(0.5-1) mmol.

[0039] In this embodiment, the resin-based filter material of this example is applied to the treatment of antibiotic wastewater.

[0040] In this embodiment, the antibiotic wastewater is preferably wastewater containing aminoglycoside antibiotics.

[0041] In this embodiment, the aminoglycoside antibiotic wastewater is preferably antibiotic wastewater containing one or more of kanamycin, gentamicin, tobramycin, ethimicin, and amikacin.

[0042] Example 1

[0043] A method for preparing a resin-based filter material comprises the following steps:

[0044] S1: Add 1 g of terephthalonitrile to 10 mL of trifluoromethanesulfonic acid, stir for 10 min, then add 10 g of D001 cation exchange resin, stir at 25 ° C for 18 h, then heat to 80 ° C, keep stirring and react for 3-6 h, filter, wash, and dry to obtain CTF-loaded cation exchange resin;

[0045] S2: Add 0.3902 g of sodium sulfide to 20 mL of deionized water, stir to dissolve, add the CTF-loaded cation exchange resin prepared in S1, stir for 10 min, then add 0.7981 g of copper sulfate, stir and react at 30°C for 12 h, filter, wash, and dry to obtain a resin-based filter material.

[0046] Example 2

[0047] A method for preparing a resin-based filter material comprises the following steps:

[0048] S1: Add 1.5 g of terephthalonitrile to 10 mL of trifluoromethanesulfonic acid, stir for 15 min, then add 10 g of D001 cation exchange resin, stir at 30 ° C for 24 h, then heat to 85 ° C, keep stirring for 6 h, filter, wash, and dry to obtain CTF-loaded cation exchange resin;

[0049] S2: Add 0.7804 g of sodium sulfide to 20 mL of deionized water, stir to dissolve, add the CTF-loaded cation exchange resin prepared in S1, stir for 15 min, then add 1.5961 g of copper sulfate, stir and react at 40°C for 18 h, filter, wash, and dry to obtain a resin-based filter material.

[0050] Comparative Example 1 used D001 cation exchange resin as the filter material.

[0051] Comparative Example 2 used CTF-loaded cation exchange resin as the filter material.

[0052] Comparative Example 3: Nano-CuS-loaded cation exchange resin was used as the filter material. The preparation method was as follows: 0.3902 g of sodium sulfide was added to 20 mL of deionized water, stirred to dissolve, D001 cation exchange resin was added, stirred for 10 min, and then 0.7981 g of copper sulfate was added. The mixture was stirred at 30° C. for 12 h, filtered, washed, and dried to obtain the nano-CuS-loaded cation exchange resin.

[0053] Comparative Example 4 uses a CTF / CuS composite photocatalyst as a treatment material, and its preparation method includes the following steps:

[0054] S1: Add 1 g of terephthalonitrile to 10 mL of trifluoromethanesulfonic acid, stir for 10 min, react at 25°C with stirring for 18 h, then heat to 80°C, keep stirring and react for 3-6 h, filter, wash, and dry to obtain CTF;

[0055] S2: Add 0.3902 g of sodium sulfide to 20 mL of deionized water, stir to dissolve, add CTF prepared in S1, stir for 10 min, then add 0.7981 g of copper sulfate, stir and react at 30°C for 12 h, filter, wash, and dry to obtain a CTF / CuS composite photocatalyst.

[0056] The treatment performance and cyclic stability of the products prepared in the examples and comparative examples for wastewater containing aminoglycoside antibiotics were measured:

[0057] 100 mg of the filter materials prepared in Examples 1-2 and Comparative Examples 1-3 and 12.9 mg of the composite photocatalyst prepared in Comparative Example 4 were weighed (consistent with the total photocatalyst content in the filter material in Example 1, where CTF and nano-CuS accounted for 8.71% and 4.16% of the total mass of the filter material, respectively); and then, in the dark, added to six groups of 300 mL of a 50 mg / L kanamycin aqueous solution. After stirring for 30 minutes, a 300 W xenon lamp was turned on and stirred for 60 minutes, and then the initial kanamycin removal rate was measured.

[0058] The test samples of Examples 1-3 and Comparative Examples 1-4 were collected and added to six new 300 mL 50 mg / L kanamycin aqueous solutions in the dark. The above experimental process was repeated and the cyclic stability was evaluated by measuring the kanamycin removal rate of the samples during the second use.

[0059] The test results are shown in Table 1:

[0060]

[0061] As shown in Table 1, the resin-based filter material prepared in the present invention can efficiently remove kanamycin from water bodies and has high cyclic stability. After secondary use, its kanamycin removal rate can still be as high as over 97.5%. However, the kanamycin removal rate of Comparative Example 1 using D001 cation exchange resin as the filter material is greatly reduced after secondary use. Analysis may be due to the fact that Comparative Example 1 reaches saturated adsorption during the second use without regeneration treatment, while the photocatalyst on the resin-based filter material prepared in Example 1 catalyzes the degradation of kanamycin under light conditions, keeping it in a dynamic unsaturated adsorption state. At the same time, the loaded CTF has a high specific surface area, which helps to increase the adsorption capacity of the filter material to a certain extent.

[0062] Comparing Example 1 with Comparative Examples 2-3, it can be seen that compared to the resin-based filter material loaded with a single pure phase catalyst, Example 1 improves the removal performance of the filter material for antibiotic wastewater by loading the CTF / CuS composite catalyst on the cation exchange resin carrier. The reason for this analysis is that the present invention constructs a heterojunction catalyst on the cation exchange resin, drives the photogenerated electrons to transition from the valence band of nano-CuS to the conduction band of CTF, and retains the photogenerated holes in the valence band of nano-CuS, effectively improving the electron-hole separation efficiency and avoiding the agglomeration of nano-CuS particles. At the same time, the composite of CTF and nano-CuS expands the spectral response range, covering the entire visible light to near-infrared band, improving the utilization rate of sunlight, thereby improving the light conversion efficiency and catalytic performance, and enhancing the catalytic degradation performance of antibiotics.

[0063] By comparing Example 1 and Comparative Example 4, it can be seen that Example 1 significantly improves the treatment performance of the filter material for kanamycin wastewater by loading the CTF / CuS composite photocatalyst on the D001 cation exchange resin carrier through the triple synergistic enhancement of "adsorption → enrichment → degradation".

[0064] It should be understood by those skilled in the art that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention (including the claims) is limited to these examples. Within the scope of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.

[0065] The present invention is intended to cover all such substitutions, modifications and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. Application of a resin-based filter material in the treatment of antibiotic wastewater, characterized in that: The resin-based filter material uses a cation exchange resin as a matrix and is loaded with a CTF / CuS composite photocatalyst; wherein CTF accounts for 8.71-12.04% of the total mass of the filter material, and nano-CuS accounts for 4.16-7.68% of the total mass of the filter material; the antibiotic wastewater is wastewater containing aminoglycoside antibiotics; the aminoglycoside antibiotic wastewater is antibiotic wastewater containing one or more of kanamycin, gentamicin, tobramycin, azithromycin, and amikacin; the initial kanamycin removal rate of the resin-based filter material is above 99.1%, and the kanamycin removal rate during the second use is above 97.5%.

2. The use of a resin-based filter material in the treatment of antibiotic wastewater according to claim 1, characterized in that: The cation exchange resin is a strongly acidic cation exchange resin.

3. The use of a resin-based filter material in the treatment of antibiotic wastewater according to claim 2, characterized in that: The strongly acidic cation exchange resin is selected from one or more of D001, D072, Amberlite IRP69, Amberlite 200, and Lewatit Sp-210 cation exchange resins.

4. The use of a resin-based filter material in the treatment of antibiotic wastewater according to claim 1, characterized in that: The preparation method of the resin-based filter material comprises the following steps: S1: Add terephthalonitrile to trifluoromethanesulfonic acid, stir for 10-15 minutes, then add cation exchange resin, stir at 25-30°C for 18-24 hours, then heat to 70-85°C, stir and react for 3-6 hours, filter, wash, and dry to obtain CTF-loaded cation exchange resin; S2: Add alkali metal sulfide salt to deionized water, stir to dissolve, add CTF-loaded cation exchange resin, stir for 10-15 minutes, then add soluble divalent copper salt, stir and react at 30-40°C for 12-18 hours, filter, wash, and dry to obtain a resin-based filter material.

5. The use of a resin-based filter material in the treatment of antibiotic wastewater according to claim 4, characterized in that: The alkali metal sulfide salt is selected from one or more of sodium sulfide, potassium sulfide and lithium sulfide.

6. The use of a resin-based filter material in the treatment of antibiotic wastewater according to claim 4, characterized in that: The soluble divalent copper salt is selected from one or more of copper nitrate, copper sulfate and copper acetate.

7. The use of a resin-based filter material in the treatment of antibiotic wastewater according to claim 4, characterized in that: The usage ratio of the terephthalonitrile, trifluoromethanesulfonic acid, cation exchange resin, alkali metal sulfide salt, deionized water, and soluble divalent copper salt is (0.1-0.15) g:1 mL:1 g:(0.5-1) mmol:2 mL:(0.5-1) mmol.

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