CN111892681B - Preparation method and application of modified polymer microsphere adsorbent - Google Patents

Preparation method and application of modified polymer microsphere adsorbent Download PDF

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CN111892681B
CN111892681B CN202010656910.0A CN202010656910A CN111892681B CN 111892681 B CN111892681 B CN 111892681B CN 202010656910 A CN202010656910 A CN 202010656910A CN 111892681 B CN111892681 B CN 111892681B
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CN111892681A (en
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刘丹
黄丽萍
蒙莉莉
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Jiangsu University of Technology
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Abstract

The invention discloses a preparation method and application of a modified polymer microsphere adsorbent. Preparation: firstly, polymeric microsphere adsorbent: (1) mixing GMA, a cross-linking agent, a first pore-forming agent and a second pore-forming agent and performing ultrasonic treatment; (2) adding an initiator, oscillating and drying to obtain a polymer; (3) grinding the polymer, adding methanol, centrifuging, removing supernatant, repeating the above process, and oven drying to obtain polymer microsphere adsorbent; II, modified polymer microsphere adsorbent: (1) adding a polymer microsphere adsorbent and ethylenediamine into a test tube, sealing the test tube, and oscillating; (2) then stirring to obtain an adsorbent suspension; (3) and centrifuging the adsorbent suspension, and removing the supernatant to obtain the modified polymer microsphere adsorbent. The application comprises the following steps: the modified polymer microsphere adsorbent is used for removing phenol red in printing and dyeing wastewater. The modified polymer microsphere adsorbent is prepared by adopting an in-situ polymerization method, and the method is simple; the obtained adsorbent has good adsorption effect on phenol red and can be repeatedly used.

Description

Preparation method and application of modified polymer microsphere adsorbent
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a preparation method and application of a modified polymer microsphere adsorbent.
Background
The most difficult-to-treat current printing and dyeing wastewater in the industrial wastewater depends on the characteristics of the printing and dyeing wastewater, the water quality of the printing and dyeing wastewater varies greatly in different production processes, the organic pollutants are high in content and complex in type, and the discharge amount of the printing and dyeing wastewater is also huge. Therefore, the treatment of the printing and dyeing wastewater is the key of the serious difficulty of wastewater treatment means and sustainable development of the industry in China.
The high molecular polymer is used as a novel adsorbent, and has wide application prospect due to simple preparation, stable structure and personalized customization. However, the adsorption property of the polymer matrix material is not ideal in general, and in order to improve the adsorption property, a method of modifying the polymer matrix material may be used to solve this problem. The invention adopts a method of chemically modifying the surface of the high polymer by anhydrous ethylenediamine to improve the adsorption performance of the high polymer adsorbent.
Phenol red has a very wide application in life, can be used for detecting the pH value of water, assisting in diagnosing the renal function, measuring the total amount of carbon dioxide in blood and the like, and causes environmental pollution due to the fact that a large amount of phenol red enters a water body because of large usage amount. Therefore, the removal of phenol red from water bodies is of great research significance.
Disclosure of Invention
The invention aims to provide a simple preparation method of a modified polymer microsphere adsorbent, the surface of the modified polymer microsphere adsorbent prepared by the method has rich pore structures, and the adsorption effect is good; when the prepared modified polymer microsphere adsorbent is used for removing phenol red in printing and dyeing wastewater, the adsorbent has excellent adsorption performance, stable chemical property, good regenerability and reusability.
The invention is realized by the following technical scheme:
a preparation method of a modified polymer microsphere adsorbent is characterized by comprising the following steps:
firstly, preparing a polymer microsphere adsorbent:
(1) mixing glycidyl methacrylate, a cross-linking agent, a first pore-forming agent and a second pore-forming agent in a container and performing ultrasonic treatment;
(2) adding an initiator into the container, oscillating, drying and initiating polymerization to obtain a polymer;
(3) grinding the polymer, adding methanol, centrifuging, removing supernatant, adding methanol again, centrifuging, removing supernatant, repeating the above process, and drying to obtain polymer microsphere adsorbent;
secondly, preparing the modified polymer microsphere adsorbent:
(1) adding the polymer microsphere adsorbent and anhydrous ethylenediamine into a container, sealing the container, and oscillating;
(2) heating and stirring after oscillation to obtain an adsorbent suspension;
(3) and centrifuging the adsorbent suspension, and removing the supernatant to obtain the modified polymer microsphere adsorbent. The invention takes Glycidyl Methacrylate (GMA) as a monomer, ethylene glycol dimethacrylate (EDMA) as a cross-linking agent, dodecanol and cyclohexanol as pore-foaming agents, Azodiisobutyronitrile (AIBN) as an initiator, and adopts an in-situ polymerization method to prepare the ethylenediamine modified glycidyl methacrylate/ethylene glycol dimethacrylate (GMA/EDMA) microsphere adsorbent, which has good adsorption performance.
Further, firstly, preparing the polymer microsphere adsorbent: in the step (1), the mass ratio of the glycidyl methacrylate to the cross-linking agent to the first pore-forming agent to the second pore-forming agent is (0.3-0.5): (0.2-0.3): (1.0-1.5): (0.1-0.2), wherein the crosslinking agent is ethylene glycol dimethacrylate; the first pore former is cyclohexanol; the second pore-foaming agent is dodecanol.
Further, firstly, preparing the polymer microsphere adsorbent: in the step (2), the initiator is azobisisobutyronitrile.
Further, firstly, preparing the polymer microsphere adsorbent: in the step (2), the mass ratio of the initiator to the dodecanol is 1: (10-20); the oscillation is ultrasonic oscillation, and the oscillation time is 10-30 minutes; the drying temperature is 50-60 ℃, and the drying time is 8-16 hours.
Further, firstly, preparing the polymer microsphere adsorbent: the methanol submerges the polymer in step (3); the centrifugation time is 5-10 minutes; the repetition times are 3-5 times; the drying temperature is 50-60 ℃, and the drying time is 8-12 hours.
Further, preparing the modified polymer microsphere adsorbent: the mass-volume ratio of the polymer microsphere adsorbent to the anhydrous ethylenediamine in the step (1) is 0.5-1.0 g/mL; the oscillation is ultrasonic oscillation, the oscillation temperature is 30-40 ℃, and the oscillation time is 1-3 hours.
Further, preparing the modified polymer microsphere adsorbent: step (2) stirring and magnetically stirring for 8-12 hours at the temperature of 60-70 ℃.
Further, preparing the modified polymer microsphere adsorbent: the centrifugation time in the step (3) is 5-10 minutes.
The application of the modified polymer adsorbent is characterized in that the modified polymer microsphere adsorbent prepared by the preparation method is used for removing phenol red in printing and dyeing wastewater. When the prepared modified polymer microsphere adsorbent (modified glycidyl methacrylate/ethylene glycol dimethacrylate microsphere adsorbent) is used for removing phenol red in printing and dyeing wastewater, the adsorption performance is excellent (the adsorption performance is excellent because a plurality of micropores with larger pore diameters exist on the surface of the modified glycidyl methacrylate/ethylene glycol dimethacrylate microsphere adsorbent prepared by the invention, the existence of the micropores greatly increases the contact chance of phenol red dye molecules and the surface of the adsorbent, is beneficial to improving the adsorption performance of the adsorbent on the dye molecules), and the chemical property is stable and can be reused; the modified polymer microsphere adsorbent prepared by the invention can be put into production in large quantity, is applied to a printing and dyeing wastewater treatment process to adsorb phenol red dye, and provides a new idea for treating dye industrial wastewater.
Furthermore, the concentration of phenol red in the printing and dyeing wastewater is 1-20 mug/mL, and the mass-volume ratio of the modified polymer microsphere adsorbent to the printing and dyeing wastewater is 5-10 mg/mL.
Compared with the prior art, the invention has the beneficial effects that:
(1) the modified polymer microsphere adsorbent is prepared by adopting an in-situ polymerization method, and the preparation method is simple and convenient for industrial production;
(2) the surface of the modified polymer microsphere adsorbent (modified poly glycidyl methacrylate/ethylene glycol dimethacrylate microsphere adsorbent (GMA/EDMA)) prepared by the method has rich micropores and good adsorption effect;
(3) when the modified poly glycidyl methacrylate/ethylene glycol dimethacrylate microsphere adsorbent (GMA/EDMA) prepared by the method is used for removing phenol red in printing and dyeing wastewater, the adsorbent has excellent adsorption performance, stable chemical property, reusability and good regeneration performance.
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 phenol red standard solution;
FIG. 2 is a graph showing the relationship between the number of times of recycling and the amount of phenol red adsorbed by the modified poly (glycidyl methacrylate)/ethylene glycol dimethacrylate microsphere adsorbent prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of a poly glycidyl methacrylate/ethylene glycol dimethacrylate microsphere adsorbent prepared in example 1 (one) and a modified poly glycidyl methacrylate/ethylene glycol dimethacrylate microsphere adsorbent prepared in example 1 (two) of the present invention;
FIG. 4 is an infrared spectrum of the modified poly (glycidyl methacrylate)/ethylene glycol dimethacrylate microsphere adsorbent 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 modified polymer microsphere adsorbent comprises the following steps:
firstly, preparing a polymer microsphere adsorbent:
(1) weighing 0.36g of Glycidyl Methacrylate (GMA), 0.24g of ethylene glycol dimethacrylate (EDMA), 1.2g of cyclohexanol and 0.2g of dodecanol, mixing in a 5.0mL centrifuge tube, and uniformly performing ultrasonic treatment;
(2) adding 0.01g of Azobisisobutyronitrile (AIBN) into the centrifuge tube, then putting the centrifuge tube filled with various reaction reagents into an ultrasonic cleaner, ultrasonically oscillating for 30 minutes at room temperature, covering the centrifuge tube after ultrasonic oscillation with a cover, putting the centrifuge tube into an oven, and drying (initiating polymerization) for 16 hours at 60 ℃ to obtain a polymer;
(3) grinding the obtained full polymer, adding methanol to immerse the polymer, centrifuging for 5 minutes, removing the centrifuged supernatant, adding methanol again to immerse the polymer, centrifuging for 5 minutes again, removing the centrifuged supernatant, repeating the process for 4 times, finally placing the mixture in an electric heating constant-temperature air-blast drying oven, and drying the mixture for 12 hours at 50 ℃ to obtain the poly (glycidyl methacrylate)/ethylene glycol dimethacrylate (GMA-EDMA) microsphere adsorbent;
secondly, preparing the modified polymer microsphere adsorbent:
(1) respectively adding 1.0g of poly glycidyl methacrylate/ethylene glycol dimethacrylate (GMA-EDMA) microsphere adsorbent and 1.5mL of anhydrous ethylenediamine into a test tube, sealing the opening of the test tube by using a preservative film, and then putting the test tube filled with a reaction reagent into an ultrasonic oscillator at 30 ℃ for oscillation for 2 hours;
(2) after the oscillation is finished, putting the sealed test tube into a heat collection type magnetic heating stirrer with the temperature set to 70 ℃ for heating and stirring for 12 hours to obtain an adsorbent suspension;
(3) adding the adsorbent suspension into a centrifuge tube, centrifuging for 10 minutes, removing the centrifuged supernatant, and collecting the precipitate to obtain the anhydrous ethylenediamine modified poly (glycidyl methacrylate)/ethylene glycol dimethacrylate (GMA-EDMA) microsphere adsorbent.
Application example 1
The modified poly glycidyl methacrylate/ethylene glycol dimethacrylate (GMA-EDMA) microsphere adsorbent prepared in example 1 is applied to removing phenol red in printing and dyeing wastewater.
Removing phenol red in the printing and dyeing wastewater, comprising the following steps:
(1) simulation of printing and dyeing wastewater containing phenol red: weighing 0.01g of phenol red powder, placing the phenol red powder in a clean and dry beaker, adding a small amount of absolute ethyl alcohol to fully dissolve the phenol red powder, transferring the dissolved solution to a 100mL volumetric flask, and adding distilled water to mark the position of a scale mark, thus preparing the phenol red mother liquor with the concentration of 100 mu g/mL. This mother liquor was diluted stepwise to give phenol red standard solutions at concentrations of 1. mu.g/mL, 2. mu.g/mL, 5. mu.g/mL, 10. mu.g/mL and 20. mu.g/mL. Then measuring the phenol red standard solution with the corresponding concentration at the wavelength lambda by an ultraviolet spectrophotometermaxAnd (3) drawing a standard curve by taking the concentration of the phenol red standard solution as an abscissa and the absorbance as an ordinate, and obtaining a standard curve equation after linear fitting, wherein the standard curve equation is as follows: Y0.0407X +0.0771, R20.9929, which shows good linearity, as shown in fig. 1;
(2) pouring 4.0mL of the phenol red standard solution of 20 microgram/mL into a centrifuge tube, adding 0.03g of the modified polyglycidyl methacrylate/ethylene glycol dimethacrylate (GMA/EDMA) microsphere adsorbent prepared in example 1 into the centrifuge tube, placing the centrifuge tube into a water bath constant temperature oscillator, oscillating for 30 minutes at 45 ℃, placing the centrifuge tube into a centrifuge for centrifugal treatment for 15 minutes after oscillation is finished, taking the centrifuged supernatant, and measuring the phenol red standard solution adsorbed by the modified polyglycidyl methacrylate/ethylene glycol dimethacrylate microsphere adsorbent prepared in example 1 at the wavelength lambda by using an ultraviolet spectrophotometermaxAbsorbance at 431 nm;
(3) the absorbance thus measured was compared with the standard curve obtained in the above step (1), and the modified polymethacrylene obtained in example 1 was obtainedThe concentration of the phenol red standard solution after adsorption of the acid glycidyl ester/ethylene glycol dimethacrylate microsphere adsorbent is determined according to the formula:
Figure BDA0002577093360000081
calculating the adsorption rate (R%) of phenol red, wherein C0: (. mu.g/mL) and CeThe initial concentration and the concentration after adsorption of the standard solution of phenol red (μ g/mL) respectively show that the adsorption rate of the modified polyglycidyl methacrylate/ethylene glycol dimethacrylate microsphere adsorbent prepared in example 1 to phenol red is 68.8% by calculation.
Example 2
A preparation method of a modified polymer microsphere adsorbent comprises the following steps:
firstly, preparing a polymer microsphere adsorbent:
(1) weighing 0.30g of Glycidyl Methacrylate (GMA), 0.30g of ethylene glycol dimethacrylate (EDMA), 1.0g of cyclohexanol and 0.1g of dodecanol, mixing in a 5.0mL centrifuge tube, and uniformly performing ultrasonic treatment;
(2) adding 0.01g of Azobisisobutyronitrile (AIBN) into the centrifuge tube, then putting the centrifuge tube filled with various reaction reagents into an ultrasonic cleaner, ultrasonically oscillating for 10 minutes at room temperature, covering the centrifuge tube after ultrasonic oscillation with a cover, putting the centrifuge tube into an oven, and drying (initiating polymerization) for 8 hours at 50 ℃ to obtain a polymer;
(3) grinding the obtained full polymer, adding methanol to immerse the polymer, centrifuging for 10 minutes, removing the centrifuged supernatant, adding methanol again to immerse the polymer, centrifuging for 10 minutes again, removing the centrifuged supernatant, repeating the process for 3 times, and finally placing the mixture in an electric heating constant-temperature air-blast drying oven to dry for 8 hours at 60 ℃ to obtain the poly (glycidyl methacrylate)/ethylene glycol dimethacrylate (GMA-EDMA) microsphere adsorbent;
secondly, preparing the modified polymer microsphere adsorbent:
(1) respectively adding 1.0g of poly glycidyl methacrylate/ethylene glycol dimethacrylate (GMA-EDMA) microsphere adsorbent and 2.0mL of anhydrous ethylenediamine into a test tube, sealing the opening of the test tube by using a preservative film, and then putting the test tube filled with a reaction reagent into an ultrasonic oscillator at 40 ℃ for oscillation for 1 hour;
(2) after the oscillation is finished, putting the sealed test tube into a heat collection type magnetic heating stirrer with the temperature set to 65 ℃ for heating and stirring for 8 hours to obtain an adsorbent suspension;
(3) adding the adsorbent suspension into a centrifuge tube, centrifuging for 5 minutes, removing the centrifuged supernatant, and collecting the precipitate to obtain the anhydrous ethylenediamine modified poly (glycidyl methacrylate)/ethylene glycol dimethacrylate (GMA-EDMA) microsphere adsorbent.
Application example 2
The modified poly glycidyl methacrylate/ethylene glycol dimethacrylate (GMA-EDMA) microsphere adsorbent prepared in example 2 is applied to removing phenol red in printing and dyeing wastewater.
Removing phenol red in the printing and dyeing wastewater, comprising the following steps:
(1) taking 4.0mL of the phenol red standard solution with the concentration of 1 μ g/mL prepared in the step (1) of the application example 1, pouring the phenol red standard solution into a centrifuge tube, adding 0.02g of the modified polyglycidyl methacrylate/ethylene glycol dimethacrylate (GMA/EDMA) microsphere adsorbent 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 45 ℃ for 30 minutes, putting the centrifuge tube into a centrifuge for centrifuging for 15 minutes after oscillation is finished, taking the centrifuged supernatant, and measuring the wavelength λ of the phenol red standard solution adsorbed by the modified polyglycidyl methacrylate/ethylene glycol dimethacrylate microsphere adsorbent prepared in the example 2 by using an ultraviolet spectrophotometermaxAbsorbance at 431 nm;
(2) the measured absorbance corresponds to the standard curve obtained in the step (1) of the application example 1, so as to obtain the concentration of the phenol red standard solution adsorbed by the modified polyglycidyl methacrylate/ethylene glycol dimethacrylate microsphere adsorbent prepared in the example 2, and then according to the formula:
Figure BDA0002577093360000101
calculating the adsorption rate (R%) of phenol red, wherein C0: (. mu.g/mL) and CeThe initial concentration and the concentration after adsorption of the standard solution of phenol red (μ g/mL) respectively, and the adsorption rate of the modified polyglycidyl methacrylate/ethylene glycol dimethacrylate microsphere adsorbent prepared in example 2 to phenol red was calculated to be 68.3%.
Example 3
A preparation method of a modified polymer microsphere adsorbent comprises the following steps:
firstly, preparing a polymer microsphere adsorbent:
(1) weighing 0.50g of Glycidyl Methacrylate (GMA), 0.20g of ethylene glycol dimethacrylate (EDMA), 1.5g of cyclohexanol and 0.15g of dodecanol, mixing in a 5.0mL centrifuge tube, and uniformly performing ultrasonic treatment;
(2) adding 0.01g of Azobisisobutyronitrile (AIBN) into the centrifuge tube, then putting the centrifuge tube filled with various reaction reagents into an ultrasonic cleaner, ultrasonically oscillating for 20 minutes at room temperature, covering the centrifuge tube after ultrasonic oscillation with a cover, putting the centrifuge tube into an oven, and drying (initiating polymerization) for 12 hours at 55 ℃ to obtain a polymer;
(3) grinding the obtained full polymer, adding methanol to immerse the polymer, centrifuging for 5 minutes, removing the centrifuged supernatant, adding methanol again to immerse the polymer, centrifuging for 5 minutes again, removing the centrifuged supernatant, repeating the above process for 5 times, and finally placing the mixture in an electric heating constant temperature blast drying oven to dry for 10 hours at 55 ℃ to obtain the poly glycidyl methacrylate/ethylene glycol dimethacrylate (GMA-EDMA) microsphere adsorbent;
secondly, preparing the modified polymer microsphere adsorbent:
(1) respectively adding 1.0g of poly glycidyl methacrylate/ethylene glycol dimethacrylate (GMA-EDMA) microsphere adsorbent and 1.0mL of anhydrous ethylenediamine into a test tube, sealing the opening of the test tube by using a preservative film, and then placing the test tube filled with a reaction reagent into an ultrasonic oscillator at 35 ℃ for oscillation for 3 hours;
(2) after the oscillation is finished, putting the sealed test tube into a heat collection type magnetic heating stirrer with the temperature set to be 60 ℃ for heating and stirring for 10 hours to obtain an adsorbent suspension;
(3) adding the adsorbent suspension into a centrifuge tube, centrifuging for 10 minutes, removing the centrifuged supernatant, and collecting the precipitate to obtain the anhydrous ethylenediamine modified poly (glycidyl methacrylate)/ethylene glycol dimethacrylate (GMA-EDMA) microsphere adsorbent.
Application example 3
The modified poly glycidyl methacrylate/ethylene glycol dimethacrylate (GMA-EDMA) microsphere adsorbent prepared in example 3 is applied to removing phenol red in printing and dyeing wastewater.
Removing phenol red in the printing and dyeing wastewater, comprising the following steps:
(3) taking 4.0mL of the phenol red standard solution of 10. mu.g/mL prepared in the step (1) of the application example 1, pouring the solution into a centrifuge tube, adding 0.03g of the modified polyglycidyl methacrylate/ethylene glycol dimethacrylate (GMA/EDMA) microsphere adsorbent prepared in the example 3 into the centrifuge tube, then putting the centrifuge tube into a water bath constant temperature oscillator, oscillating the centrifuge tube at 45 ℃ for 30 minutes, putting the centrifuge tube into a centrifuge for centrifuging for 15 minutes after oscillation is finished, taking the centrifuged supernatant, and measuring the wavelength lambda of the phenol red standard solution adsorbed by the modified polyglycidyl methacrylate/ethylene glycol dimethacrylate microsphere adsorbent prepared in the example 3 by using an ultraviolet spectrophotometermaxAbsorbance at 431 nm;
(4) the measured absorbance corresponds to the standard curve obtained in the step (1) of the application example 1, so as to obtain the concentration of the phenol red standard solution adsorbed by the modified polyglycidyl methacrylate/ethylene glycol dimethacrylate microsphere adsorbent prepared in the example 3, and then according to the formula:
Figure BDA0002577093360000121
calculating the adsorption rate (R%) of phenol red, wherein: c0(. mu.g/mL) and Ce(μ g/mL) are the initial concentrations of phenol Red Standard solutions, respectivelyThe degree and the concentration after adsorption are calculated to obtain that the adsorption rate of the modified poly glycidyl methacrylate/ethylene glycol dimethacrylate microsphere adsorbent prepared in example 3 on phenol red is 68.5%.
Example 4
In order to examine the repeated utilization rate of the modified poly glycidyl methacrylate/ethylene glycol dimethacrylate microsphere adsorbent prepared by the invention, 1mol/L HCl is used as desorption liquid, and 5 times of adsorption-desorption cyclic regeneration test researches are carried out on the modified poly glycidyl methacrylate/ethylene glycol dimethacrylate microsphere adsorbent prepared in example 1.
The adsorption-desorption cyclic regeneration process is as follows:
(1) taking 4.0mL of the phenol red standard solution with the concentration of 20 mu g/mL prepared in the step (1) of the application example 1, adding the phenol red standard solution into a centrifuge tube, adding 0.03g of the modified poly (glycidyl methacrylate)/ethylene glycol dimethacrylate microsphere adsorbent prepared in the example 1 into the centrifuge tube, putting the centrifuge tube into a water bath constant temperature oscillator, oscillating the centrifuge tube at 45 ℃ for 30 minutes, putting the centrifuge tube into a centrifuge after oscillation is finished, centrifuging the centrifuge tube for 15 minutes, taking the centrifuged supernatant, and measuring the wavelength lambda of the supernatant by using an ultraviolet spectrophotometermaxComparing the absorbance at 431nm with the standard curve drawn in the step (1) of the application example 1 to obtain the concentration of the phenol red standard solution adsorbed by the modified polymer microsphere adsorbent for the first time, and then removing the supernatant; adding 2.0mL of 1mol/L HCl (HCl is used as desorption solution to desorb the adsorbent so that the adsorbent can be recycled) and 4.0mL of 20 mu g/mL phenol red standard solution into a centrifuge tube, placing the centrifuge tube into a water bath constant temperature oscillator for oscillation, placing the centrifuge tube into a centrifuge for centrifugation after oscillation is finished, taking the centrifuged supernatant, and measuring the wavelength lambda of the supernatant by using an ultraviolet spectrophotometermaxComparing the absorbance with that at 431nm, and obtaining the concentration of the phenol red standard solution after repeated adsorption by using the adsorbent for the second time according to the standard curve drawn in the step (1) of the application example 1, and then removing the supernatant; then 2.0m of the solution was added again to the centrifuge tubeL of 1mol/L HCl and 4.0mL of 20 mu g/mL phenol red standard solution, continuously placing the centrifuge tube in a water bath constant temperature oscillator for oscillation, placing the centrifuge tube in a centrifuge for centrifugation after oscillation is finished, taking the centrifuged supernatant, and continuously measuring the wavelength lambda of the supernatant by using an ultraviolet spectrophotometermaxComparing the absorbance with that at 431nm, and obtaining the concentration of the phenol red standard solution after the adsorption by using the adsorbent for the third time by referring to the standard curve drawn in the step (1) of the application example 1; then, repeating the steps, sequentially measuring the absorbances of the phenol red standard solution subjected to adsorption by using the adsorbent for the fourth time and the fifth time by using an ultraviolet spectrophotometer, and sequentially contrasting and contrasting the standard curves drawn in the step (1) of the application example 1 to obtain the concentrations of the phenol red standard solution subjected to adsorption by using the adsorbent for the fourth time and the fifth time;
(2) then, the adsorption capacity (Qe) of the modified poly glycidyl methacrylate/ethylene glycol dimethacrylate microsphere adsorbent to phenol red after each use is calculated according to a formula, wherein the calculation formula is as follows:
Figure BDA0002577093360000131
in the formula: c0(. mu.g/mL) and Ce(. mu.g/mL) are the initial concentration and the post-adsorption concentration of the phenol red standard solution, respectively, V represents the volume (mL) of the phenol red standard solution, and m represents the mass (g) of the adsorbent.
Summarizing the calculation results, as shown in fig. 2, the experimental results show that HCl has a better regeneration effect on the prepared modified polymer microsphere adsorbent, and after 5 times of adsorption-desorption cycle use, the relative average deviation of the adsorption amount is calculated to be 6.89% and less than 10%, so that the modified poly (glycidyl methacrylate)/ethylene glycol dimethacrylate microsphere adsorbent prepared by the invention is easy to regenerate in HCl solution and can be reused, which fully indicates that it is a high-efficiency adsorbent in wastewater treatment.
Example 5
Taking the poly (glycidyl methacrylate)/ethylene glycol dimethacrylate microsphere adsorbent prepared in the first step of the example 1 and the modified poly (glycidyl methacrylate)/ethylene glycol dimethacrylate microsphere adsorbent prepared in the second step of the example 1, observing the poly (glycidyl methacrylate)/ethylene glycol dimethacrylate microsphere adsorbent by a Scanning Electron Microscope (SEM), wherein a and b are SEM spectrums of the polymer microsphere adsorbent before modification and c and d are SEM spectrums of the modified polymer microsphere adsorbent, comparing the modified poly (glycidyl methacrylate)/ethylene glycol dimethacrylate microsphere adsorbent with the microsphere adsorbent before modification, the balling performance of the modified poly (glycidyl methacrylate)/ethylene glycol dimethacrylate microsphere adsorbent is better than that of the microsphere adsorbent before modification, and the particle size is observed to be about 100 μm, which shows that the modified poly (glycidyl methacrylate)/ethylene glycol dimethacrylate microsphere adsorbent prepared by the invention has a plurality of pore diameters on the surface which are larger than those of the microsphere adsorbent prepared by the invention A large aperture. Due to the existence of the large-diameter holes, the opportunity of the phenol red dye molecules to contact the surface of the modified polymer microsphere adsorbent is greatly increased, which is beneficial to improving the adsorption performance of the modified polymer microsphere adsorbent on the dye molecules.
Example 6
Infrared spectroscopic analysis is a common material characterization technique, and is helpful for analyzing the structure of the material and the condition of functional groups on the surface of the material, determining the structure of the product, and performing infrared spectroscopic analysis on the poly (glycidyl methacrylate)/ethylene glycol dimethacrylate) microsphere adsorbent prepared in the above example 1 (one) and the modified poly (glycidyl methacrylate)/ethylene glycol dimethacrylate microsphere adsorbent prepared in the above example 1 (two): the characterization analysis is carried out by using a Fourier transform infrared spectrometer (FT-IR), the result is shown in FIG. 4, and it can be seen from the figure that the polymeric microsphere adsorbent before modification is 1050cm at the wavelength lambda-1Has C-O-C stretching vibration peak at wavelength of 1720cm-1Has a C ═ O stretching vibration peak at 2929cm-1Has a-CH2C-H stretching vibration peak of (a); the modified polymer microsphere adsorbent also has several stretching vibration peaks, but the wavelength is 3400cm-1Nearby, because the polymer microsphere adsorbent is modified by ethylenediamine, secondary alcohol is generated after the ring opening of an epoxy group, and a weaker O-H stretching vibration peak appears in a spectrogramAnd the spectral band is wider; at a wavelength of 3000cm-1And nearby, the C-H stretching vibration strength is increased, and further, the polymer microspheres are successfully grafted and modified by the ethylenediamine.
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 (8)

1. The application of the modified polymer microsphere adsorbent is characterized in that the preparation method of the modified polymer microsphere adsorbent comprises the following steps:
firstly, preparing a polymer microsphere adsorbent:
(1) mixing glycidyl methacrylate, a cross-linking agent, a first pore-forming agent and a second pore-forming agent in a container and performing ultrasonic treatment;
(2) adding an initiator into the container, oscillating and drying to obtain a polymer;
(3) grinding the polymer, adding methanol, centrifuging, removing supernatant, adding methanol again, centrifuging, removing supernatant, repeating the above process, and drying to obtain polymer microsphere adsorbent;
secondly, preparing the modified polymer microsphere adsorbent:
(1) adding the polymer microsphere adsorbent and anhydrous ethylenediamine into a container, sealing the container, and oscillating;
(2) heating and stirring after oscillation to obtain an adsorbent suspension;
(3) centrifuging the adsorbent suspension, and removing supernatant to obtain a modified polymer microsphere adsorbent;
the mass ratio of the glycidyl methacrylate to the cross-linking agent to the first porogen to the second porogen is (0.3-0.5): (0.2-0.3): (1.0-1.5): (0.1-0.2); the cross-linking agent is ethylene glycol dimethacrylate; the first pore former is cyclohexanol; the second pore-foaming agent is dodecanol;
application of the modified polymer microsphere adsorbent: the prepared modified polymer microsphere adsorbent is used for removing phenol red in printing and dyeing wastewater.
2. The use of a modified polymeric microsphere adsorbent according to claim 1, wherein the first step of the preparation of the polymeric microsphere adsorbent is: in the step (2), the initiator is azobisisobutyronitrile.
3. The use of a modified polymeric microsphere adsorbent according to claim 1, wherein the first step of the preparation of the polymeric microsphere adsorbent is: in the step (2), the mass ratio of the initiator to the dodecanol is 1: (10-20); the oscillation is ultrasonic oscillation, and the oscillation time is 10-30 minutes; the drying temperature is 50-70 ℃, and the drying time is 8-16 hours.
4. The use of a modified polymeric microsphere adsorbent according to claim 1, wherein the first step of the preparation of the polymeric microsphere adsorbent is: the methanol submerges the polymer in step (3); the centrifugation time is 5-10 minutes; the repetition times are 3-5 times; the drying temperature is 50-60 ℃, and the drying time is 8-12 hours.
5. The use of the modified polymeric microsphere adsorbent of claim 1, wherein the preparation of the modified polymeric microsphere adsorbent comprises: the mass-volume ratio of the polymer microsphere adsorbent to the anhydrous ethylenediamine in the step (1) is 0.5-1.0 g/mL; the oscillation is ultrasonic oscillation, the oscillation temperature is 30-40 ℃, and the oscillation time is 1-3 hours.
6. The use of the modified polymeric microsphere adsorbent of claim 1, wherein the preparation of the modified polymeric microsphere adsorbent comprises: step (2) stirring and magnetically stirring for 8-12 hours at the temperature of 60-70 ℃.
7. The use of the modified polymeric microsphere adsorbent of claim 1, wherein the preparation of the modified polymeric microsphere adsorbent comprises: the centrifugation time in the step (3) is 5-10 minutes.
8. The use of the modified polymeric microsphere adsorbent of claim 1, wherein the concentration of phenol red in the printing and dyeing wastewater is 1-20 μ g/mL, and the mass-to-volume ratio of the modified polymeric microsphere adsorbent to the printing and dyeing wastewater is 5-10 mg/mL.
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