阅读说明：本技术 一种改性聚合物微球吸附剂的制备方法与应用 (Preparation method and application of modified polymer microsphere adsorbent ) 是由 刘丹 黄丽萍 蒙莉莉 于 2020-07-09 设计创作，主要内容包括：本发明公开一种改性聚合物微球吸附剂的制备方法与应用。制备：一、聚合物微球吸附剂：(1)GMA、交联剂、第一致孔剂和第二致孔剂混合并超声；(2)加引发剂,振荡,干燥,得聚合物；(3)将聚合物研磨,加入甲醇,离心,除去上清液,重复上述过程,烘干,得聚合物微球吸附剂；二、改性聚合物微球吸附剂：(1)将聚合物微球吸附剂和乙二胺加入试管中并封口,振荡；(2)然后搅拌,得到吸附剂悬浮液；(3)将吸附剂悬浮液离心,除去上清液,得到改性聚合物微球吸附剂。应用：将改性聚合物微球吸附剂用于去除印染废水中的苯酚红。本发明采用原位聚合法制备改性聚合物微球吸附剂,方法简单；所得吸附剂对苯酚红的吸附效果好,可重复使用。(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.)

1. 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 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) and centrifuging the adsorbent suspension, and removing the supernatant to obtain the modified polymer microsphere adsorbent.

2. The method for preparing the modified polymer microsphere adsorbent according to claim 1, wherein the first step is to prepare 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); the cross-linking agent is ethylene glycol dimethacrylate; the first pore former is cyclohexanol; the second pore-foaming agent is dodecanol.

3. The method for preparing the modified polymer microsphere adsorbent according to claim 1, wherein the first step is to prepare the polymer microsphere adsorbent: in the step (2), the initiator is azobisisobutyronitrile.

4. The method for preparing the modified polymer microsphere adsorbent according to claim 1, wherein the first step is to prepare 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 50-70 ℃, and the drying time is 8-16 hours.

5. The method for preparing the modified polymer microsphere adsorbent according to claim 1, wherein the first step is to prepare 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.

6. The method for preparing the modified polymer microsphere adsorbent according to claim 1, wherein the preparation of the modified polymer microsphere adsorbent comprises the following steps: 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.

7. The method for preparing the modified polymer microsphere adsorbent according to claim 1, wherein the preparation of the modified polymer microsphere adsorbent comprises the following steps: step (2) stirring and magnetically stirring for 8-12 hours at the temperature of 60-70 ℃.

8. The method for preparing the modified polymer microsphere adsorbent according to claim 1, wherein the preparation of the modified polymer microsphere adsorbent comprises the following steps: the centrifugation time in the step (3) is 5-10 minutes.

9. The application of the modified polymer microsphere adsorbent prepared by the preparation method of any one of claims 1 to 8 in removing phenol red in printing and dyeing wastewater.

10. The use of the modified polymeric microsphere adsorbent of claim 9, 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.

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.