CN112138635A - Preparation method and application of modified polymer adsorption material - Google Patents
Preparation method and application of modified polymer adsorption material Download PDFInfo
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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
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
With the progress of science, the field of analytical chemistry has developed rapidly. Antibiotics are widely used in human medicine and livestock breeding because of their excellent therapeutic effects. However, it is troublesome that most antibiotics cannot be absorbed by human or animal body, and they are discharged from the body in the form of their prototypes or metabolites, and enter the sewage system. Most domestic sewage treatment plants can not carry out directional processing to the antibiotic, lead to most antibiotic to remain, get into the surface water, cause the water pollution. Therefore, the research on the removal method of the antibiotics has important significance for treating water pollution.
The pefloxacin belongs to quinolone antibiotics, the antibiotics are mainly applied to the breeding industry and medical systems, and because the antibiotics are not easy to absorb, the residual pefloxacin usually enters a sewage treatment plant along with water bodies such as breeding industry wastewater, medical wastewater, domestic sewage and the like. People are not aware of the seriousness of the situation that low-concentration antibiotics in the environment can induce the drug resistance of bacteria to change, and finally seriously threaten the health of human beings and the safety of ecological environment, and a lot of students do not study the field emphatically, so that the effect of the sewage treatment means adopted by the common sewage plant on the pefloxacin is limited, and the pefloxacin in the sewage is difficult to remove. The pefloxacin entering the surface water system can cause a large amount of surface water and rivers to be polluted, and the soil irrigated by the polluted water body can also be polluted.
Compared with other methods for treating environmental sewage, the advanced oxidation method has the greatest characteristics of high pollutant removal efficiency and difficulty in generating secondary pollution. The advanced oxidation method improves the biodegradability of organic polymer pollutants by a strong oxidant, and can completely decompose refractory polymer organic matters generally, so that the pefloxacin treated by the advanced oxidation technology can be theoretically oxidized into small molecular substances which can be decomposed by microorganisms. Although some scholars have proved the point, the advanced oxidation method is often very harsh in reaction conditions, extremely dependent on equipment and high in cost, and needs to be applied to a common sewage treatment plant and further needs to be researched by scholars at home and abroad.
The mechanism of photocatalytic degradation is to degrade organic polymer pollutants by a series of free radicals generated in a reaction system by using an intermediate such as a photocatalyst or radiation. The efficiency of the photocatalysis method is very high, and the photocatalysis method has the characteristic of strong selectivity, so that the photocatalysis method has wide research value. Many contemporary scholars are studying to degrade quinolone antibiotics contained in wastewater by photocatalysis, but the photocatalysis method has huge use cost and is not suitable for large-scale sewage plants, so that the scholars need to continuously make efforts to popularize the photocatalysis method. Therefore, the method for treating the antibiotics is low in equipment material cost, wide in application range and strong in adaptability, and is used for removing the antibiotics.
Disclosure of Invention
The invention aims to provide a simple and low-cost preparation method of a modified polymer adsorption material; the prepared modified polymer adsorption material is used for adsorbing antibiotics in wastewater, and has excellent adsorption performance, stable chemical property and reusability.
The invention is realized by the following technical scheme:
a preparation method of a modified polymer adsorption material comprises 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. The polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material modified by concentrated hydrochloric acid is prepared by taking methacrylic acid (MAA) as a polymerization monomer, ethylene glycol dimethacrylate (EDMA) as a cross-linking agent, toluene and lauryl alcohol as pore-foaming agents, Azodiisobutyronitrile (AIBN) as an initiator and concentrated hydrochloric acid as a modifier, is used for adsorbing antibiotics in wastewater, and has excellent adsorption performance, good regeneration performance and reusability.
Further, preparation of the polymer adsorbing material: the cross-linking agent in the step (1) is ethylene glycol dimethacrylate (EDMA); the initiator is Azobisisobutyronitrile (AIBN).
Further, preparation of the polymer adsorbing material: 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.
Further, preparation of the polymer adsorbing material: the first pore-forming agent in the step (2) is toluene; the second pore-foaming agent is dodecanol.
Further, preparation of the polymer adsorbing material: 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.
Further, preparation of the polymer adsorbing material: 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.
Further, preparing the modified polymer adsorption material: 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.
Further, preparing the modified polymer adsorption material: 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.
The application of the modified polymer adsorption material is characterized in that the modified polymer adsorption material prepared by the preparation method is used for adsorbing antibiotics in wastewater. When the prepared modified polymer adsorption material is used for adsorbing antibiotics in wastewater, the adsorption performance is excellent (the adsorption performance is excellent because the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material prepared by the method has a uniform, continuous and compact surface structure, a pore structure with uniform size on the surface, obvious pore channels in the polymer and can be used as an adsorption material to adsorb an antibiotic aqueous solution, and the polymer adsorption material modified by the concentrated hydrochloric acid has a rougher surface, a large specific surface area and a better adsorption effect), and the chemical property is stable and can be repeatedly used.
Further, the concentration of antibiotics in the wastewater is 1-20 mug/mL, and the mass-volume ratio of the modified polymer adsorbing material to the wastewater is 1-10 mg/mL.
Compared with the prior art, the invention has the beneficial effects that:
(1) the modified polymer adsorption material has the advantages of simple preparation method, no need of expensive production equipment, low cost and convenience for industrial production;
(2) the surface of the modified polymer adsorption material prepared by the method has a continuous and compact pore structure, the specific surface area is large, and the adsorption effect on antibiotics is improved;
(3) when the concentrated hydrochloric acid modified polymer adsorption material prepared by the method is used for adsorbing antibiotics in wastewater, the adsorption performance is excellent, the chemical property is stable, the concentrated hydrochloric acid modified polymer adsorption material can be repeatedly used, and the regeneration performance is good.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a standard curve of concentration versus absorbance for a standard solution of pefloxacin;
FIG. 2 is a graph showing the relationship between the number of recycling times of the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared in example 1 of the present invention and the amount of pefloxacin adsorbed;
fig. 3 is a scanning electron microscope image of the polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared in the first embodiment of the present invention and the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared in the second embodiment of the present invention;
fig. 4 is an infrared spectrum of the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and 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. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, 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 comprises the following steps:
firstly, preparing a polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material:
(1) accurately weighing 0.096g of methacrylic acid (MAA), 0.840g of ethylene glycol dimethacrylate (EDMA) and 0.010g of Azobisisobutyronitrile (AIBN) respectively, placing the materials in a 5mL centrifuge tube, and carrying out ultrasonic treatment for 30 minutes to obtain a mixed solution;
(2) adding 0.220g of toluene and 1.720g of dodecanol into the centrifuge tube containing the mixed solution, then carrying out ultrasonic treatment for 30 minutes, placing the centrifuge tube into a drying oven after ultrasonic treatment, and drying for 16 hours (initiating polymerization) at 60 ℃ to obtain polymer solid;
(3) grinding the polymer into powder, washing with methanol for 3 times, performing ultrasonic treatment for 30 minutes after washing, centrifuging for 5 minutes again, removing the centrifuged supernatant, and collecting precipitate; then the precipitate is placed in a drying box and dried for 10 hours at the temperature of 50 ℃ to obtain the polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material (MAA/EDMA);
secondly, preparing the modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material:
(1) adding 50mL of methanol and 0.8mL of concentrated hydrochloric acid with the mass fraction of 36% into the polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material (MAA/EDMA), magnetically stirring for 48 hours, and removing the methanol by using a suction filter after stirring is finished to obtain a pre-product;
(2) washing the obtained pre-product with methanol for 5 times, then carrying out ultrasonic treatment for 30 minutes, then centrifuging for 5 minutes again, and placing the centrifuged precipitate in an oven at 60 ℃ for drying for 8 hours to obtain the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material.
Application example 1
The concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared in the example 1 is used for adsorbing antibiotics in wastewater.
The method for adsorbing antibiotics in wastewater comprises the following steps:
(1) preparing wastewater containing antibiotics: a standard solution is prepared by taking pefloxacin as an example.
0.01g of pefloxacin was weighed into a clean and dry beaker, and then 10mL of 3mmol/L NaOH solution was addedDissolving the pefloxacin, transferring the dissolved pefloxacin into a 100mL volumetric flask for constant volume, and preparing a 100 mu g/mL pefloxacin solution. Then, the pefloxacin solution is diluted step by step to obtain standard pefloxacin solutions with the concentrations of 1 mu g/mL, 2 mu g/mL, 5 mu g/mL, 10 mu g/mL, 15 mu g/mL and 20 mu g/mL. Then measuring the wavelength lambda of the pefloxacin standard solution with the corresponding concentration by an ultraviolet spectrophotometermaxAnd (3) drawing a standard curve by taking the concentration of the pefloxacin standard solution as an abscissa and the absorbance as an ordinate, and obtaining a standard curve equation after linear fitting, wherein the absorbance is 283 nm: y ═ 0.045X +0.0077, R20.9971, its linear relationship is good as shown in fig. 1;
(2) pouring 4.0mL of the pefloxacin standard solution with the concentration of 2 mu g/mL into a centrifuge tube, adding 0.01g of the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared in the example 1 into the centrifuge tube, then placing the centrifuge tube into a water bath constant temperature oscillator, oscillating the centrifuge tube at 40 ℃ for 20 minutes (enabling the pefloxacin to be adsorbed on the prepared modified polymer adsorbing material), placing the centrifuge tube into a centrifuge for centrifugal treatment for 5 minutes after oscillation is finished, taking the centrifuged supernatant, and then measuring the pefloxacin standard solution adsorbed by the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared in the example 1 at the wavelength lambda by using an ultraviolet spectrophotometermaxAbsorbance at 283 nm;
comparing the measured absorbance with the standard curve obtained in the step (1), so as to obtain the concentration of the pefloxacin standard solution after the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared in the example 1 is adsorbed, and then according to the formula:
calculating the adsorption rate (R%) of pefloxacin, wherein: c0(. mu.g/mL) and Ce(mu g/mL) are respectively the initial concentration and the equilibrium concentration after adsorption of the pefloxacin standard solution, and then the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared in example 1 is calculated to obtain the pefloxacinThe adsorption rate of the fleroxacin is 98.7%.
Example 2
A preparation method of a concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material comprises the following steps:
firstly, preparing a polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material:
(1) accurately weighing 0.100g of methacrylic acid (MAA), 1.000g of ethylene glycol dimethacrylate (EDMA) and 0.015g of Azobisisobutyronitrile (AIBN) respectively, placing the materials in a 5mL centrifuge tube, and carrying out ultrasonic treatment for 20 minutes to obtain a mixed solution;
(2) adding 0.200g of toluene and 2.000g of dodecanol into the centrifuge tube containing the mixed solution, then carrying out ultrasonic treatment for 10 minutes, placing the centrifuge tube into a drying oven after ultrasonic treatment, and drying for 14 hours (initiating polymerization) at 50 ℃ to obtain polymer solid;
(3) grinding the polymer into powder, washing with methanol for 5 times, performing ultrasonic treatment for 20 minutes after washing, centrifuging for 10 minutes again, removing the centrifuged supernatant, and collecting precipitate; putting the precipitate in a drying box, and drying at 60 ℃ for 8 hours to obtain a polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material (MAA/EDMA);
secondly, preparing the modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material:
(1) adding 50mL of methanol and 0.9mL of concentrated hydrochloric acid with the mass fraction of 30% into the polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material (MAA/EDMA), magnetically stirring for 36 hours, and removing the methanol by using a suction filter after stirring is finished to obtain a pre-product;
(2) washing the obtained pre-product with methanol for 3 times, then carrying out ultrasonic treatment for 20 minutes, then centrifuging for 8 minutes, and placing the centrifuged precipitate in an oven at 55 ℃ for drying for 10 hours to obtain the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material.
Application example 2
The concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared in the example 2 is used for adsorbing antibiotics in wastewater.
The method for adsorbing antibiotics in wastewater comprises the following steps:
(1) pouring 4.0mL of the 10. mu.g/mL pefloxacin standard solution into a centrifuge tube, adding 0.02g concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared in the example 2 into the centrifuge tube, then putting the centrifuge tube into a water bath constant temperature oscillator, oscillating the centrifuge tube at 40 ℃ for 20 minutes (enabling pefloxacin to be adsorbed on the prepared modified polymer adsorbing material), after oscillation is finished, putting the centrifuge tube into a centrifuge for centrifugal treatment for 5 minutes, taking the centrifuged supernatant, and then measuring the wavelength lambda of the pefloxacin standard solution adsorbed by the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared in the example 2 by using an ultraviolet spectrophotometermaxAbsorbance at 283 nm;
comparing the measured absorbance with the standard curve obtained in the step (1) of the application example 1 (namely, fig. 1), the concentration of the pefloxacin standard solution after the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared in the example 2 is adsorbed can be obtained, and then according to the formula:
calculating the adsorption rate (R%) of pefloxacin, wherein: c0(. mu.g/mL) and CeThe initial concentration and the equilibrium concentration after adsorption of the standard solution of pefloxacin are respectively (mu g/mL), and then the adsorption rate of pefloxacin by the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared in example 2 is 98.1 percent by calculation.
Example 3
A preparation method of a concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material comprises the following steps:
firstly, preparing a polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material:
(1) accurately weighing 0.100g of methacrylic acid (MAA), 0.800g of ethylene glycol dimethacrylate (EDMA) and 0.020g of Azobisisobutyronitrile (AIBN) respectively, placing the materials in a 5mL centrifuge tube, and then carrying out ultrasonic treatment for 10 minutes to obtain a mixed solution;
(2) adding 0.300g of toluene and 1.500g of dodecanol into the centrifuge tube containing the mixed solution, then carrying out ultrasonic treatment for 10 minutes, placing the centrifuge tube into a drying oven after ultrasonic treatment, and drying for 12 hours (initiating polymerization) at 55 ℃ to obtain polymer solid;
(3) grinding the polymer into powder, washing with methanol for 4 times, performing ultrasonic treatment for 10 minutes after washing, centrifuging for 8 minutes again, removing the centrifuged supernatant, and collecting precipitate; then the precipitate is placed in a drying box and dried for 8 hours at the temperature of 55 ℃ to obtain the polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material (MAA/EDMA);
secondly, preparing the modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material:
(1) adding 50mL of methanol and 0.77mL of concentrated hydrochloric acid with the mass fraction of 38% into the polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material (MAA/EDMA), magnetically stirring for 40 hours, and removing the methanol by using a suction filter after stirring is finished to obtain a pre-product;
(2) washing the obtained pre-product with methanol for 4 times, then carrying out ultrasonic treatment for 10 minutes, then centrifuging for 10 minutes, and placing the centrifuged precipitate in a drying oven at 65 ℃ for drying for 8 hours to obtain the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material.
Application example 3
The concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared in the example 3 is used for adsorbing antibiotics in wastewater.
The method for adsorbing antibiotics in wastewater comprises the following steps:
(1) 4.0mL of the pefloxacin standard solution 20. mu.g/mL is poured into a centrifuge tube, 0.04g of the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared in example 3 is added into the centrifuge tube, and then the centrifuge tube is placed into a water bath to be shaken at constant temperatureShaking in a container at 40 deg.C for 20 min (to adsorb pefloxacin on the prepared modified polymer adsorbent), centrifuging in a centrifuge for 5 min, collecting the supernatant, and measuring by ultraviolet spectrophotometer at λ of wavelength of pefloxacin standard solution adsorbed on the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbent prepared in example 3maxAbsorbance at 283 nm;
(2) comparing the measured absorbance with the standard curve obtained in the step (1) of the application example 1 (namely, fig. 1), the concentration of the pefloxacin standard solution after the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared in the example 3 is adsorbed can be obtained, and then according to the formula:
calculating the adsorption rate (R%) of pefloxacin, wherein: c0(. mu.g/mL) and CeThe initial concentration and the equilibrium concentration after adsorption of the standard solution of pefloxacin are respectively (mu g/mL), and then the adsorption rate of pefloxacin by the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared in example 3 is 97.6 percent by calculation.
Example 4
In order to examine the recycling rate of the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared by the invention, ethanol is used as a desorbent, 5 adsorption-desorption cyclic regeneration experimental studies are carried out on the modified polymer adsorbing material prepared in example 1, and the cyclic use performance of the prepared modified polymer adsorbing material is tested.
The adsorption-desorption cyclic regeneration process is as follows:
(1) 4.0mL of the 2. mu.g/mL pefloxacin standard solution prepared in step (1) of application example 1 was added to a centrifuge tube, and then 0.01g concentrated hydrochloric acid-modified polymethacrylene prepared in example 1 was added to the centrifuge tubeAdsorbing acid/ethylene glycol dimethacrylate, placing the centrifuge tube into a water bath constant temperature oscillator, oscillating at 40 deg.C for 20 min, placing the centrifuge tube into a centrifuge for centrifuging for 5 min after oscillation is completed, collecting the centrifuged supernatant, and measuring with ultraviolet spectrophotometer at wavelength lambdamaxObtaining the concentration of the pefloxacin standard solution after the first adsorption by using the adsorption material according to a standard curve shown in figure 1, wherein the absorbance is 283nm, and then removing the supernatant; adding 2.0mL of ethanol (ethanol is used as a desorbent to desorb the adsorbing material so that the adsorbing material can be recycled) and 4.0mL of pefloxacin standard solution (2 mu g/mL) into the centrifuge tube, placing the centrifuge tube into a water bath constant temperature oscillator at 40 ℃ to oscillate for 20 minutes, placing the centrifuge tube into a centrifuge after oscillation is finished, centrifuging the centrifuge tube, taking the centrifuged supernatant, and measuring the wavelength lambda of the centrifuged supernatant again by using an ultraviolet spectrophotometermaxObtaining the concentration of the pefloxacin standard solution repeatedly adsorbed by the adsorbing material for the second time by comparing the absorbance of the corresponding solution at 283nm with the standard curve shown in figure 1, then removing the supernatant, and repeating the steps; sequentially measuring the absorbance of the pefloxacin standard solution after the adsorption of the adsorbing material for the third time, the fourth time and the fifth time by using an ultraviolet spectrophotometer, and sequentially comparing the standard curves shown in the figure 1 to obtain the concentration of the pefloxacin standard solution after the adsorption of the adsorbing material for the third time, the fourth time and the fifth time;
(2) then, the adsorption quantity (Qe) of pefloxacin after the concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorption material is used each time is calculated according to a formula, wherein the calculation formula is as follows:
The adsorption material which is recycled for 5 times is obtained through calculation, the adsorption amount of the adsorption material to the pefloxacin is 0.7896mg/g, 0.7833mg/g, 0.7865mg/g, 0.7835mg/g and 0.7848mg/g in sequence, and the calculation results are summarized, as shown in figure 2, the results show that the ethanol has a good regeneration effect on the prepared modified polymer adsorption material, and after the adsorption-desorption is recycled for 5 times, the relative average deviation of the adsorption amount is calculated to be less than 10%. Therefore, the modified polymer adsorption material prepared by the invention is a recyclable adsorption material and is worthy of popularization and application.
Example 5
The polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material prepared in the first step of the example 1 and the polymethacrylic acid/ethylene glycol dimethacrylate adsorbing material modified by the concentrated hydrochloric acid prepared in the second step of the example 1 are taken and then characterized by a Scanning Electron Microscope (SEM), and the result is shown in fig. 3 (in the figure, a is an SEM spectrum of the polymer adsorbing material before modification, and b is an SEM spectrum of the polymer adsorbing material after modification by the concentrated hydrochloric acid), so that the surface structure of the polymer adsorbing material before modification is uniform, continuous and compact, the surface has a pore structure with uniform size, the interior of the polymer has obvious pore channels, and the surface of the polymer adsorbing material after modification by the concentrated hydrochloric acid is rougher, and the adsorbing effect of the polymer adsorbing material is improved.
Example 6
The concentrated hydrochloric acid modified polymethacrylic acid/ethylene glycol dimethacrylate adsorbent material prepared in the above example 1 was taken and subjected to infrared spectroscopic analysis: the characterization analysis was performed by Fourier transform infrared (FT-IR) spectrometer, and the result is shown in FIG. 4, which shows that the spectrum is 1160cm-1A C-O telescopic absorption peak is formed and is derived from alcohol; at 1660cm-1The peak is C ═ O stretching vibration peak, and is derived from the surface carboxylic acid of polymethacrylic acid/ethylene glycol dimethacrylate (MAA/EDMA); at 2960cm-1Has C-H antisymmetric telescopic vibration peak and should contain-CH3(ii) a At 3650cm-1has-OH stretching vibration peak and is derived from alcohol. In conclusion, the present invention has been shown to successfully modify polymethacrylic acid @, using concentrated hydrochloric acidEthylene glycol dimethacrylate (MAA/EDMA).
The above-mentioned preferred embodiments of the present invention are provided for illustration only and not for the purpose of limiting the invention. Obvious variations or modifications of the present invention are within the 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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