CN112138635A - Preparation method and application of modified polymer adsorption material - Google Patents

Abstract

The invention discloses a preparation method and application of a modified polymer adsorption material. The preparation method comprises the following steps: firstly, preparing a polymer adsorption material: (1) ultrasonically mixing MAA, a cross-linking agent and an initiator to obtain a mixture; (2) adding a first pore-forming agent and a second pore-forming agent into the mixture, and then performing ultrasonic treatment and drying to obtain a polymer; (3) grinding, washing, ultrasonically treating, centrifuging and drying the polymer to obtain a polymer adsorption material; secondly, preparing the modified polymer adsorption material: (1) adding an organic solvent and a modifier into the polymer adsorbing material, stirring, and then removing the organic solvent to obtain a pre-product; (2) and washing, ultrasonically treating, centrifuging and drying the pre-product to obtain the modified polymer adsorbing material. The application comprises the following steps: the modified polymer adsorption material is used for adsorbing antibiotics in wastewater. The modified polymer adsorption material disclosed by the invention is simple in preparation method, can be used for adsorbing antibiotics in wastewater, is excellent in adsorption effect, can be repeatedly used and is good in reproducibility.

Description

A kind of preparation method and application of modified polymer adsorption material

technical field

The invention relates to the technical field of wastewater treatment, in particular to a preparation method and application of a modified polymer adsorption material.

Background technique

With the advancement of science, the field of analytical chemistry has developed rapidly. Antibiotics are widely used in human medicine and animal husbandry because of their good therapeutic effects. But the trouble is that most of the antibiotics cannot be absorbed by the human body or animals, and will be excreted with the body wastewater in the state of their prototypes or metabolites, thereby entering the sewage system. Most domestic sewage treatment plants do not carry out directional treatment of antibiotics, resulting in most of the antibiotics remaining and entering surface water, causing water pollution. Therefore, it is of great significance to study the removal methods of antibiotics for the treatment of water pollution.

Pefloxacin is a quinolone antibiotic, which is mainly used in aquaculture and medical systems. Since antibiotics are not easily absorbed, residual pefloxacin usually enters into water bodies such as aquaculture wastewater, medical wastewater and domestic sewage. Sewage treatment plant. Since people have not yet realized the seriousness of the situation that even low concentrations of antibiotics in the environment may induce changes in bacterial resistance, which will eventually seriously threaten human health and the safety of the ecological environment, there are not many scholars to focus on this field. , resulting in the limited effect of sewage treatment methods used by general sewage plants on pefloxacin, so it is difficult to remove pefloxacin in sewage. After being treated by the sewage treatment plant, it will enter the surface water system. After entering the surface water system, pefloxacin can cause a large amount of surface water and rivers to be polluted, and the soil irrigated by the polluted water body will also be polluted.

Compared with other environmental sewage treatment methods, the advanced oxidation method not only has high removal efficiency of pollutants, but also is not easy to produce secondary pollution, which is also its biggest feature. The advanced oxidation method uses strong oxidants to improve the biochemical properties of organic polymer pollutants. Generally, the refractory polymer organic substances can be completely decomposed. Therefore, in theory, pefloxacin treated by advanced oxidation technology will be oxidized into Small molecules that can be broken down by microorganisms. Of course, some scholars have proved this, but advanced oxidation methods often have very harsh reaction conditions, are extremely dependent on equipment, and have high costs. To apply advanced oxidation methods to ordinary sewage treatment plants, domestic and foreign scholars need to continue to work hard.

The mechanism of photocatalytic degradation is to use a series of free radicals generated by intermediates such as photocatalyst or radiation in the reaction system to degrade organic polymer pollutants. The efficiency of the photocatalytic method is very high, and the photocatalytic method has the characteristics of strong selectivity, so it has a wide range of research value. Many contemporary scholars are studying the photocatalytic degradation of quinolone antibiotics contained in wastewater, but the use of photocatalytic method is very costly, and it is not suitable for large-scale sewage plants. Therefore, to promote the photocatalytic method, scholars still need to continue to work hard. Therefore, the present application provides a treatment method with low equipment material cost, wide application range and strong adaptability to remove antibiotics.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a simple and low-cost preparation method of modified polymer adsorbent material; the prepared modified polymer adsorbent material is used to adsorb antibiotics in wastewater, which has excellent adsorption performance and stable chemical properties. reusable.

The present invention is achieved through the following technical solutions:

A preparation method of a modified polymer adsorbent material, comprising the following steps:

First, the preparation of polymer adsorption materials:

(1) ultrasonically mixing methacrylic acid, crosslinking agent and initiator to obtain mixture;

(2) adding the first pore-forming agent and the second pore-forming agent to the mixture, then sonicating and drying to obtain a polymer;

(3) grinding the polymer, then washing, sonicating, centrifuging, and drying to obtain a polymer adsorption material;

Second, the preparation of modified polymer adsorption material:

(1) adding an organic solvent and a modifier to the polymer adsorbent material and stirring, then removing the organic solvent to obtain a pre-product;

(2) Washing, sonicating, centrifuging and drying the pre-product to obtain a modified polymer adsorbent material. In the present invention, methacrylic acid (MAA) is used as a polymerized monomer, ethylene glycol dimethacrylate (EDMA) is used as a crosslinking agent, toluene and dodecanol are used as porogens, and azobisisobutyronitrile ( AIBN) as the initiator, and concentrated hydrochloric acid as the modifier, a polymethacrylic acid/ethylene glycol dimethacrylate adsorption material modified by concentrated hydrochloric acid was prepared, and used to adsorb the antibiotics in the wastewater, and its adsorption performance was excellent, It has good regeneration performance and can be reused.

Further, 1. Preparation of polymer adsorption material: in step (1), the crosslinking agent is ethylene glycol dimethacrylate (EDMA); the initiator is azobisisobutyronitrile (AIBN).

Further, 1. Preparation of polymer adsorption material: the mass ratio between the methacrylic acid, the crosslinking agent and the initiator in step (1) is 1:(8-10):(0.1-0.2 ), the ultrasonic time is 10-30 minutes.

Further, 1. Preparation of polymer adsorption material: in step (2), the first porogen is toluene; the second porogen is dodecanol.

Further, 1. Preparation of polymer adsorption material: in step (2), the mass ratio between the first pore-forming agent, the second pore-forming agent and the methacrylic acid is (2-3): (15 -20): 1; the ultrasonic treatment time is 10-30 minutes; the drying temperature is 50-60°C, and the drying time is 12-16 hours.

Further, 1. the preparation of polymer adsorption material: step (3) using methanol to wash 3-5 times, the ultrasonic treatment time is 10-30 minutes, the centrifugation time is 5-10 minutes, the drying temperature It is 50-60 ℃, and the drying time is 8-10 hours.

Further, 2. Preparation of modified polymer adsorption material: in step (1), the organic solvent is methanol; the modifier is concentrated hydrochloric acid with a mass fraction of 30-38%; the organic solvent and the modified The volume ratio of the agent is (55-65): 1; the mass volume ratio of the methacrylic acid to the modifier is 0.1-0.15g/mL; the stirring is magnetic stirring, and the stirring time is 36-48 hours .

Further, 2. Preparation of modified polymer adsorption material: in step (2), methanol is used to wash the pre-product 3-5 times; the ultrasonic treatment time is 10-30 minutes; the centrifugation time is 5-10 minutes ; Described drying temperature is 55-65 ℃, drying 8-10 hours.

An application of a modified polymer adsorption material, characterized in that the modified polymer adsorption material prepared by the above preparation method is used to adsorb antibiotics in wastewater. When the prepared modified polymer adsorbent material is used to adsorb the antibiotics in the waste water, its adsorption performance is excellent (the excellent adsorption performance is because the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethyl methacrylate prepared by the method of the present invention) The surface structure of the acrylic acid ester adsorption material is uniform, continuous and dense, the surface has a pore structure of uniform size, and there are obvious pores inside the polymer, which can be used as an adsorption material to adsorb antibiotic aqueous solution. The surface is rougher, the specific surface area is large, and it has better adsorption effect), and the chemical properties are stable and can be reused.

Further, the concentration of antibiotics in the wastewater is 1-20 μg/mL, and the mass-volume ratio of the modified polymer adsorption material to the wastewater is 1-10 mg/mL.

Compared with the prior art, the beneficial effects of the present invention:

(1) the preparation method of the modified polymer adsorption material of the present invention is simple, does not need to use expensive production equipment, the cost is low, and it is convenient for industrialized production;

(2) the surface of the modified polymer adsorption material prepared by the method of the present invention has a continuous and dense pore structure, and the specific surface area is large, which improves the adsorption effect on antibiotics;

(3) When the concentrated hydrochloric acid-modified polymer adsorbent material prepared by the method of the present invention is used for adsorbing antibiotics in wastewater, its adsorption performance is excellent, its chemical properties are stable, it can be used repeatedly, and its regeneration performance is good.

Description of drawings

In order to illustrate the technical solutions of the embodiments of the present invention more clearly, the following briefly introduces the accompanying drawings used in the description of the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those skilled in the art, other drawings can also be obtained from these drawings without any creative effort.

Fig. 1 is the standard curve of the concentration and absorbance of pefloxacin standard solution;

Fig. 2 is the graph of the relationship between the number of cycles of use of the concentrated hydrochloric acid-modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material prepared in Example 1 of the present invention and the amount of adsorption to pefloxacin;

Fig. 3 is the polymethacrylic acid/ethylene glycol dimethacrylate adsorption material prepared in Example 1 (1) of the present invention and the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol prepared in Example 1 (2) Scanning electron microscope image of alcohol dimethacrylate adsorption material;

4 is an infrared spectrum diagram of the concentrated hydrochloric acid-modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material prepared in Example 1 of the present invention.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Example 1

A preparation method of a concentrated hydrochloric acid-modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material, comprising the following steps:

1. Preparation of polymethacrylic acid/ethylene glycol dimethacrylate adsorption material:

(1) Accurately weigh 0.096g of methacrylic acid (MAA), 0.840g of ethylene glycol dimethacrylate (EDMA) and 0.010g of azobisisobutyronitrile (AIBN), respectively, and place them in a 5mL centrifuge tube , and then ultrasonically treated for 30 minutes to obtain a mixed solution;

(2) Add 0.220g of toluene and 1.720g of dodecanol to the above centrifuge tube containing the mixed solution, then ultrasonically treat for 30 minutes, place the centrifuge tube in a drying box after ultrasonication, and dry it at 60°C for 16 minutes. hours (initiating polymerization) to obtain polymer solids;

(3) Grind the polymer into powder, then repeatedly wash with methanol 3 times, ultrasonically treat for 30 minutes after washing, then centrifuge for 5 minutes, remove the supernatant after centrifugation to collect the precipitate; then place the precipitate in a drying box Inside, drying at 50°C for 10 hours to obtain polymethacrylic acid/ethylene glycol dimethacrylate adsorption material (MAA/EDMA);

2. Preparation of modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material:

(1) Add 50 mL of methanol and 0.8 mL of concentrated hydrochloric acid with a mass fraction of 36% to the above-mentioned polymethacrylic acid/ethylene glycol dimethacrylate adsorbent (MAA/EDMA) and stir magnetically for 48 hours, and the stirring is completed Afterwards, the methanol is removed by suction filtration with a suction filter to obtain the pre-product;

(2) washing the obtained pre-product with methanol 5 times, then sonicating for 30 minutes, then centrifuging for 5 minutes, placing the centrifuged precipitate in an oven at 60 ° C and drying for 8 hours to obtain a concentrated hydrochloric acid modified polymethyl methacrylate Acrylic acid/ethylene glycol dimethacrylate adsorption material.

Application example 1

The concentrated hydrochloric acid-modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material prepared in Example 1 was used to adsorb antibiotics in wastewater.

The adsorption of antibiotics in wastewater includes the following steps:

(1) Preparation of wastewater containing antibiotics: take pefloxacin as an example to prepare a standard solution.

Weigh 0.01g of pefloxacin and place it in a clean and dry beaker, then add 10mL of 3mmol/L NaOH solution to dissolve it, then transfer it to a 100mL volumetric flask to make up to 100μg/mL of pefloxacin solution. The pefloxacin solution was then diluted stepwise to obtain standard solutions of pefloxacin with concentrations of 1 μg/mL, 2 μg/mL, 5 μg/mL, 10 μg/mL, 15 μg/mL and 20 μg/mL. Then measure the absorbance of the pefloxacin standard solution of the corresponding concentration at wavelength λ _max =283nm by ultraviolet spectrophotometer, then take the concentration of the pefloxacin standard solution as the abscissa and the absorbance as the ordinate, draw a standard curve , the standard curve equation obtained after linear fitting is: Y=0.045X+0.0077, R ² =0.9971, as shown in Figure 1, its linear relationship is good;

(2) Pour 4.0 mL of the above-mentioned 2 μg/mL pefloxacin standard solution into a centrifuge tube and add 0.01 g of the concentrated hydrochloric acid-modified polymethacrylic acid/ethylene glycol dimethyl ester prepared in Example 1 to it Acrylate adsorption material, then put the centrifuge tube into a water bath constant temperature oscillator and shake at 40 ° C for 20 minutes (to make pefloxacin adsorbed on the prepared modified polymer adsorption material), and then centrifuge after the shaking is completed. The tube was placed in a centrifuge for centrifugation for 5 minutes, and the centrifuged supernatant was taken, and then the concentrated hydrochloric acid-modified polymethacrylic acid/ethylene glycol dimethyl ester obtained in Example 1 was measured using an ultraviolet spectrophotometer. Absorbance of pefloxacin standard solution adsorbed by acrylate adsorption material at wavelength λ _max =283nm;

计算出培氟沙星的吸附率(R％)，式中：C₀(μg/mL)和C_e(μg/mL)分别为培氟沙星标准溶液的初始浓度和吸附后的平衡浓度，然后计算得出实施例1制备的浓盐酸改性的聚甲基丙烯酸/乙二醇二甲基丙烯酸酯吸附材料对培氟沙星的吸附率为98.7％。By comparing the measured absorbance to the standard curve obtained in the above step (1), the polymethacrylic acid/ethylene glycol dimethacrylate adsorption material modified by the concentrated hydrochloric acid obtained in Example 1 can be obtained. After the concentration of pefloxacin standard solution, then according to the formula:

Calculate the adsorption rate (R%) of pefloxacin, where: C ₀ (μg/mL) and C _e (μg/mL) are the initial concentration of pefloxacin standard solution and the equilibrium concentration after adsorption, respectively, Then, it was calculated that the adsorption rate of pefloxacin by the concentrated hydrochloric acid-modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material prepared in Example 1 was 98.7%.

Example 2

A preparation method of a concentrated hydrochloric acid-modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material, comprising the following steps:

1. Preparation of polymethacrylic acid/ethylene glycol dimethacrylate adsorption material:

(1) Accurately weigh 0.100g of methacrylic acid (MAA), 1.000g of ethylene glycol dimethacrylate (EDMA) and 0.015g of azobisisobutyronitrile (AIBN), respectively, and place them in a 5mL centrifuge tube , and then ultrasonically treated for 20 minutes to obtain a mixed solution;

(2) Add 0.200g of toluene and 2.000g of dodecanol to the above centrifuge tube containing the mixed solution, then ultrasonically treat for 10 minutes, place the centrifuge tube in a drying box after ultrasonication, and dry it at 50°C for 14 minutes. hours (initiating polymerization) to obtain polymer solids;

(3) Grind the polymer into powder, then repeatedly wash with methanol for 5 times, ultrasonically treat for 20 minutes after washing, and then centrifuge for 10 minutes, remove the supernatant after centrifugation to collect the precipitate; put the precipitate in a drying box , and dried at 60°C for 8 hours to obtain polymethacrylic acid/ethylene glycol dimethacrylate adsorption material (MAA/EDMA);

2. Preparation of modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material:

(1) Add 50 mL of methanol and 0.9 mL of concentrated hydrochloric acid with a mass fraction of 30% to the above-mentioned polymethacrylic acid/ethylene glycol dimethacrylate adsorption material (MAA/EDMA) and stir magnetically for 36 hours, and the stirring is completed Afterwards, the methanol is removed by suction filtration with a suction filter to obtain the pre-product;

(2) the obtained pre-product was washed 3 times with methanol, then ultrasonically treated for 20 minutes, then centrifuged for 8 minutes, and the centrifuged precipitate was placed in an oven at 55 ° C and dried for 10 hours to obtain concentrated hydrochloric acid-modified polymethyl methacrylate Acrylic acid/ethylene glycol dimethacrylate adsorption material.

Application example 2

The concentrated hydrochloric acid-modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material prepared in Example 2 was used to adsorb antibiotics in wastewater.

The adsorption of antibiotics in wastewater includes the following steps:

(1) Pour 4.0 mL of the above-mentioned 10 μg/mL pefloxacin standard solution into a centrifuge tube and add 0.02 g of the concentrated hydrochloric acid-modified polymethacrylic acid/ethylene glycol dimethyl ester prepared in Example 2 to it Acrylate adsorption material, then put the centrifuge tube into a water bath constant temperature oscillator and shake at 40 ° C for 20 minutes (to make pefloxacin adsorbed on the prepared modified polymer adsorption material), and then centrifuge after the shaking is completed. The tube was placed in a centrifuge for 5 minutes for centrifugation, and the centrifuged supernatant was taken, and then an ultraviolet spectrophotometer was used to measure the polymethacrylic acid/ethylene glycol dimethyl ester modified with concentrated hydrochloric acid obtained in Example 2. Absorbance of pefloxacin standard solution adsorbed by acrylate adsorption material at wavelength λ _max =283nm;

计算出培氟沙星的吸附率(R％)，式中：C₀(μg/mL)和C_e(μg/mL)分别为培氟沙星标准溶液的初始浓度和吸附后的平衡浓度，然后通过计算得出实施例2制备的浓盐酸改性的聚甲基丙烯酸/乙二醇二甲基丙烯酸酯吸附材料对培氟沙星的吸附率为98.1％。By comparing the measured absorbance with the standard curve obtained in step (1) of the above application example 1 (i.e., Fig. 1), the polymethacrylic acid/ethylene glycol modified with concentrated hydrochloric acid obtained in Example 2 can be obtained. The concentration of pefloxacin standard solution after adsorption by dimethacrylate adsorption material, and then according to the formula:

Calculate the adsorption rate (R%) of pefloxacin, where: C ₀ (μg/mL) and C _e (μg/mL) are the initial concentration of pefloxacin standard solution and the equilibrium concentration after adsorption, respectively, Then, the adsorption rate of pefloxacin by the concentrated hydrochloric acid-modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material prepared in Example 2 was calculated to be 98.1%.

Example 3

A preparation method of a concentrated hydrochloric acid-modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material, comprising the following steps:

1. Preparation of polymethacrylic acid/ethylene glycol dimethacrylate adsorption material:

(1) Accurately weigh 0.100g of methacrylic acid (MAA), 0.800g of ethylene glycol dimethacrylate (EDMA) and 0.020g of azobisisobutyronitrile (AIBN), respectively, and place them in a 5mL centrifuge tube , and then ultrasonically treated for 10 minutes to obtain a mixed solution;

(2) Add 0.300g of toluene and 1.500g of dodecanol to the above centrifuge tube containing the mixed solution, then ultrasonically treat for 10 minutes, place the centrifuge tube in a drying box after ultrasonication, and dry it for 12 minutes at 55°C. hours (initiating polymerization) to obtain polymer solids;

(3) Grind the polymer into powder, then repeat washing with methanol for 4 times, ultrasonic treatment for 10 minutes after washing, then centrifuge for 8 minutes, remove the supernatant after centrifugation to collect the precipitate; then place the precipitate in a drying box Inside, drying at 55°C for 8 hours to obtain polymethacrylic acid/ethylene glycol dimethacrylate adsorption material (MAA/EDMA);

2. Preparation of modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material:

(1) Add 50 mL of methanol and 0.77 mL of concentrated hydrochloric acid with a mass fraction of 38% to the above-mentioned polymethacrylic acid/ethylene glycol dimethacrylate adsorbent (MAA/EDMA) and stir magnetically for 40 hours, and the stirring is completed Afterwards, the methanol is removed by suction filtration with a suction filter to obtain the pre-product;

(2) the obtained pre-product was washed 4 times with methanol, then ultrasonically treated for 10 minutes, then centrifuged for 10 minutes, and the centrifuged precipitate was placed in an oven at 65 ° C and dried for 8 hours to obtain concentrated hydrochloric acid-modified polymethyl methacrylate Acrylic acid/ethylene glycol dimethacrylate adsorption material.

Application example 3

The concentrated hydrochloric acid-modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material prepared in Example 3 was used to adsorb antibiotics in wastewater.

The adsorption of antibiotics in wastewater includes the following steps:

(1) Pour 4.0 mL of the above-mentioned 20 μg/mL pefloxacin standard solution into a centrifuge tube and add 0.04 g of the concentrated hydrochloric acid-modified polymethacrylic acid/ethylene glycol dimethyl ester prepared in Example 3 to it Acrylate adsorption material, then put the centrifuge tube into a water bath constant temperature oscillator and shake at 40 ° C for 20 minutes (to make pefloxacin adsorbed on the prepared modified polymer adsorption material), and then centrifuge after the shaking is completed. The tube was placed in a centrifuge for centrifugation for 5 minutes, and the centrifuged supernatant was taken, and then an ultraviolet spectrophotometer was used to measure the polymethacrylic acid/ethylene glycol dimethyl ester modified with concentrated hydrochloric acid prepared in Example 3. Absorbance of pefloxacin standard solution adsorbed by acrylate adsorption material at wavelength λ _max =283nm;

计算出培氟沙星的吸附率(R％)，式中：C₀(μg/mL)和C_e(μg/mL)分别为培氟沙星标准溶液的初始浓度和吸附后的平衡浓度，然后通过计算得出实施例3制备的浓盐酸改性的聚甲基丙烯酸/乙二醇二甲基丙烯酸酯吸附材料对培氟沙星的吸附率为97.6％。(2) the measured absorbance is compared with the standard curve obtained in the step (1) of the above application example 1 (i.e. Fig. 1), and the concentrated hydrochloric acid modified polymethacrylic acid/ The concentration of pefloxacin standard solution after adsorption by ethylene glycol dimethacrylate adsorption material, and then according to the formula:

Calculate the adsorption rate (R%) of pefloxacin, where: C ₀ (μg/mL) and C _e (μg/mL) are the initial concentration of pefloxacin standard solution and the equilibrium concentration after adsorption, respectively, Then, the adsorption rate of pefloxacin by the concentrated hydrochloric acid-modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material prepared in Example 3 was calculated to be 97.6%.

Example 4

The recyclable and renewable performance of the polymer adsorbent is an important feature that can be widely used in industry. In order to investigate the reuse of the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbent prepared by the present invention The modified polymer adsorbent prepared in Example 1 was subjected to five adsorption-desorption cyclic regeneration experiments using ethanol as the desorbent, and the cyclic performance of the prepared modified polymer adsorbent was tested.

The above-mentioned adsorption-desorption cycle regeneration process is as follows:

(1) Take 4.0 mL of the 2 μg/mL pefloxacin standard solution prepared in step (1) of the above application example 1, add it to a centrifuge tube, and then add 0.01 g of the standard solution prepared in Example 1 to the centrifuge tube Concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material, then put the centrifuge tube into a water bath thermostatic oscillator and shake at 40 °C for 20 minutes, and then put the centrifuge tube into the Centrifuge for 5 minutes in a centrifuge, take the supernatant after centrifugation, and then use an ultraviolet spectrophotometer to measure the absorbance at a wavelength of λ _max = 283 nm, and compare the standard curve shown in Figure 1 to obtain the first use of this product. The concentration of pefloxacin standard solution after adsorption of the adsorption material, and then remove the supernatant; then add 2.0 mL of ethanol to the centrifuge tube (ethanol is used as a desorbent to desorb the adsorption material, so that the adsorption material can be recycled) and 4.0 mL of ethanol. mL of standard solution of pefloxacin (2 μg/mL), and then placed the centrifuge tube in a water bath thermostatic oscillator at 40°C for 20 minutes. Then use an ultraviolet spectrophotometer to measure the absorbance of the corresponding solution at a wavelength of λ _max = 283 nm again, and compare the standard curve shown in Figure 1 to obtain the standard solution of pefloxacin after repeating the second adsorption using the adsorbent material. concentration, then remove the supernatant, and repeat this; use the UV spectrophotometer to measure the absorbance of the standard solution of pefloxacin after repeating the third, fourth, and fifth times using the adsorbent material in turn, and compare the graphs in turn. The standard curve shown in 1 can obtain the concentration of the standard solution of pefloxacin after repeating the third, fourth and fifth time using the adsorption material;

(2) Then according to the formula, calculate the adsorption capacity (Qe) of pefloxacin after using the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material each time, and the calculation formula is as follows:

式中：C₀(μg/mL)和C_e(μg/mL)分别为培氟沙星标准溶液的初始浓度和吸附后的平衡浓度，V表示培氟沙星标准溶液的体积(mL)，m表示所用吸附材料的质量(g)。

In the formula: C ₀ (μg/mL) and _Ce (μg/mL) are the initial concentration of pefloxacin standard solution and the equilibrium concentration after adsorption, respectively, V is the volume (mL) of pefloxacin standard solution, m represents the mass (g) of the adsorbent material used.

Through calculation, it is concluded that the adsorption material is recycled 5 times, and the adsorption capacity of the adsorption material to pefloxacin is 0.7896mg/g, 0.7833mg/g, 0.7865mg/g, 0.7835mg/g and 0.7848mg/g. The calculation results are shown in Figure 2. The results show that ethanol has a good regeneration effect on the prepared modified polymer adsorption material. After 5 adsorption-desorption cycles, the relative average deviation of the calculated adsorption capacity is less than 10. %. It can be seen that the modified polymer adsorbent material prepared by the present invention is a recyclable adsorbent material and is worthy of popularization and use.

Example 5

Get the polymethacrylic acid/ethylene glycol dimethacrylate adsorption material prepared by above-mentioned embodiment 1 (one) and the polymethacrylic acid/ethylene glycol dimethacrylate modified with concentrated hydrochloric acid prepared by embodiment 1 (two). The methacrylate adsorption material was then characterized by scanning electron microscopy (SEM). The results are shown in Figure 3 (a in the figure is the SEM spectrum of the polymer adsorption material before modification, and b in the figure is the modification of concentrated hydrochloric acid. It can be seen from Figure a that the surface structure of the polymer adsorbent before modification is uniform, continuous and dense, the surface has a pore structure of uniform size, and there are obvious pore structures inside the polymer. It can be seen from Figure b that the surface of the polymer adsorbent modified with concentrated hydrochloric acid is rougher, which improves the adsorption effect of the polymer adsorbent.

Example 6

Take the concentrated hydrochloric acid-modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbent prepared as described in Example 1, and carry out infrared spectroscopy analysis: Fourier transform infrared spectroscopy (FT-IR) was used to carry out Characterization analysis, the results are shown in Figure 4. It can be seen from the figure that there is a C-O stretching absorption peak at 1160 cm ^-1 , which is derived from alcohol; at 1660 cm ^-1 , there is a C=O stretching vibration peak, which is derived from polymer Methacrylic acid/ethylene glycol dimethacrylate (MAA/EDMA) surface carboxylic acid; C-H antisymmetric stretching vibration peak at 2960cm ^-1 , should contain -CH ₃ ; -OH at 3650cm ^-1 The stretching vibration peaks are derived from alcohols. To sum up, it shows that the present invention successfully uses concentrated hydrochloric acid to modify polymethacrylic acid/ethylene glycol dimethacrylate (MAA/EDMA).

The above-mentioned preferred embodiments of the present invention are only used to explain the present invention, and are not intended to limit the present invention. Any obvious changes or changes derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims (10)

1. A preparation method of a modified polymer adsorption material is characterized by comprising the following steps:

firstly, preparing a polymer adsorption material:

(1) ultrasonically mixing methacrylic acid, a cross-linking agent and an initiator to obtain a mixture;

(2) adding a first pore-forming agent and a second pore-forming agent into the mixture, and then carrying out ultrasonic treatment and drying to obtain a polymer;

(3) grinding the polymer, washing, performing ultrasonic treatment, centrifuging and drying to obtain a polymer adsorption material;

secondly, preparing the modified polymer adsorption material:

(1) adding an organic solvent and a modifier into the polymer adsorbing material, stirring, and then removing the organic solvent to obtain a pre-product;

(2) and washing, ultrasonically treating, centrifuging and drying the pre-product to obtain the modified polymer adsorbing material.

2. The method for preparing the modified polymer adsorbing material according to claim 1, wherein the preparation of the polymer adsorbing material comprises the following steps: in the step (1), the cross-linking agent is ethylene glycol dimethacrylate; the initiator is azobisisobutyronitrile.

3. The method for preparing the modified polymer adsorbing material according to claim 1, wherein the preparation of the polymer adsorbing material comprises the following steps: in the step (1), the mass ratio of the methacrylic acid to the crosslinking agent to the initiator is 1: (8-10): (0.1-0.2), and the ultrasonic time is 10-30 minutes.

4. The method for preparing the modified polymer adsorbing material according to claim 1, wherein the preparation of the polymer adsorbing material comprises the following steps: the first pore-forming agent in the step (2) is toluene; the second pore-foaming agent is dodecanol.

5. The method for preparing the modified polymer adsorbing material according to claim 1, wherein the preparation of the polymer adsorbing material comprises the following steps: in the step (2), the mass ratio of the first pore-forming agent to the second pore-forming agent to the methacrylic acid is (2-3): (15-20): 1; the ultrasonic treatment time is 10-30 minutes; the drying temperature is 50-60 ℃, and the drying time is 12-16 hours.

6. The method for preparing the modified polymer adsorbing material according to claim 1, wherein the preparation of the polymer adsorbing material comprises the following steps: and (3) washing for 3-5 times by adopting methanol, wherein the ultrasonic treatment time is 10-30 minutes, the centrifugation time is 5-10 minutes, the drying temperature is 50-60 ℃, and the drying time is 8-10 hours.

7. The method for preparing the modified polymer adsorbent material according to claim 1, wherein the preparation of the modified polymer adsorbent material comprises the following steps: the organic solvent in the step (1) is methanol; the modifier is concentrated hydrochloric acid with the mass fraction of 30-38%; the volume ratio of the organic solvent to the modifier is (55-65): 1; the mass-volume ratio of the methacrylic acid to the modifier is 0.1-0.15 g/mL; the stirring is magnetic stirring, and the stirring time is 36-48 hours.

8. The method for preparing the modified polymer adsorbent material according to claim 1, wherein the preparation of the modified polymer adsorbent material comprises the following steps: in the step (2), the pre-product is washed for 3-5 times by adopting methanol; the ultrasonic treatment time is 10-30 minutes; the centrifugation time is 5-10 minutes; the drying temperature is 55-65 ℃, and the drying time is 8-10 hours.

9. Use of a modified polymeric adsorbent material prepared by the method of any one of claims 1 to 8 for adsorbing antibiotics in wastewater.

10. The use of a modified polymeric adsorbent material according to claim 9, wherein the concentration of said antibiotic in said wastewater is 1-20 μ g/mL, and the mass to volume ratio of said modified polymeric adsorbent material to said wastewater is 1-10 mg/mL.

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