Polymer microsphere, ammonia nitrogen removing agent and preparation method and application of polymer microsphere and ammonia nitrogen removing agent

Abstract

The invention provides polymer microspheres, an ammonia nitrogen remover and a preparation method and application of the polymer microspheres and the ammonia nitrogen remover. Polymer microspheres are prepared by using a suspension polymerization method, and an acrylate or methacrylate monomer containing EO and aryl is introduced to participate in a free radical polymerization reaction in the microsphere preparation process, so that the electron cloud density on a benzene ring is increased, introduction of more-SO3H in the sulfonation process is facilitated, and the sulfonation efficiency is improved. Therefore, the hydrophilicity of the polymer microspheres is improved, wrinkles on the surfaces of the microspheres are increased, and the specific surface area of the polymer microspheres and the adsorption capacity of the polymer microspheres to ammonia nitrogen compounds are further improved.

Description

Technical Field

[0001] The present invention relates to the technical field of environmental pollution control, and in particular to a polymer microsphere and a preparation method thereof, an ammonia nitrogen remover and a preparation method and use thereof. Background Art

[0002] Ammonia-containing wastewater is the main component of domestic sewage, coking wastewater and printing and dyeing wastewater, and has the characteristics of large water volume and complex pollutant types. The reason why the ammonia nitrogen content in ammonia-containing wastewater is high is that the wastewater contains inorganic nitrogen and organic nitrogen, among which inorganic nitrogen is NH 3 and NH 4 + , organic nitrogen mainly includes urea, pyridine and quinoline. If ammonia nitrogen wastewater enters natural water bodies without treatment, it will cause the ammonia nitrogen content in the water body to exceed the standard, thus seriously endangering human production and life. The hazards of excessive ammonia nitrogen concentration in water bodies include eutrophication of water bodies, high-concentration ammonia nitrogen substances themselves have biological toxicity, which directly harms aquatic organisms, and ammonia nitrogen undergoes nitrification reaction under the action of microorganisms to produce highly toxic nitrites, which are a direct threat to human health. Therefore, it is urgent to develop new technologies for the effective treatment of high-concentration ammonia nitrogen wastewater.

[0003] For the treatment of ammonia nitrogen wastewater, the current more mature technologies are mainly the following: (1) Ammonia nitrogen stripping technology: With the help of a stripping tower or aeration tank, the free ammonia in the wastewater is converted into gaseous ammonia, and then carried away by air or other gases. However, this technology has strict requirements on process equipment, consumes a lot of energy for aeration and heating, and cannot completely remove ammonia nitrogen. It will also cause secondary pollution, such as ammonia emissions into the atmosphere.

[0004] (2) Breakpoint chlorination method: using strong chlorine-containing oxidants to oxidize ammonia nitrogen in wastewater into nitrogen gas or nitrate ions. The ammonia nitrogen removal rate is relatively high, but it will cause secondary pollution of the water body due to excessive residual chlorine and hypochlorite, resulting in the death of a large number of fish and other organisms in the water body.

[0005] (3) Chemical precipitation method: The most common MAP method removes ammonia nitrogen by adding magnesium salts and phosphates to form magnesium ammonium phosphate precipitation. It is suitable for eutrophic wastewater, and the generated magnesium ammonium phosphate can also be used as a slow-release fertilizer. However, this method has not yet been widely used and is only in the laboratory stage. It will also cause the total phosphorus content to be too high.

[0006] In view of the fact that the above-mentioned existing ammonia nitrogen wastewater treatment methods all have certain limitations, it is particularly necessary to develop a technology that can effectively remove ammonia nitrogen from wastewater without generating secondary pollution that is harmful to the environment. Summary of the invention

[0007] In view of the above-mentioned shortcomings of the prior art, the object of the present invention is to provide a polymer microsphere that can be used as an ammonia nitrogen remover to adsorb ammonia nitrogen impurities in water, thereby reducing NH 3 -N concentration, with higher adsorption capacity and regeneration rate, is used to solve the problems in the existing technology.

[0008] To achieve the above object, the present invention is obtained through the following technical solutions.

[0009] In a first aspect, a polymer microsphere comprises: a monofunctional monomer and a difunctional monomer obtained by suspension polymerization and sulfonation, wherein the monofunctional monomer is selected from: a styrene monomer and an acrylate containing EO and an aromatic group, a styrene monomer and a methacrylate containing EO and an aromatic group, wherein the aromatic group is directly connected to the EO, and the aromatic group is an aromatic ring or a heteroaromatic ring composed of 3-30 carbon atoms, and preferably, the aromatic group is a benzene ring.

[0010] Wherein, the styrene monomer is selected from one or more of styrene, methyl styrene and ethyl styrene; Wherein, the difunctional monomer is selected from divinylbenzene, including o-divinylbenzene, m-divinylbenzene or p-divinylbenzene, or a mixture of more thereof.

[0011] Among them, the structural formulas of styrene monomers and acrylates containing EO and aromatic groups, and styrene monomers and methacrylates containing EO and aromatic groups are: , , or Any one of , where n is a positive integer greater than or equal to 1.

[0012] Preferably, the monofunctional monomer further comprises a hydroxyl group-containing or epoxy group-containing (meth)acrylate monomer.

[0013] Preferably, the monofunctional monomer further comprises: one or more of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, dodecyl (meth)acrylate and octadecyl (meth)acrylate.

[0014] Preferably, the acrylate or methacrylate containing EO and aromatic groups is selected from: ethylene glycol phenyl ether acrylate (PHEA) or polyethylene glycol o-phenyl phenyl ether acrylate (OPPEA).

[0015] In a second aspect, the method for preparing the above-mentioned polymer microspheres comprises: suspension polymerization and sulfonation; The suspension polymerization includes using a solvent to dissolve a stabilizer, dropping an initiator and a polymerizable monomer into a solvent containing the stabilizer to carry out a polymerization reaction, and controlling the temperature of the polymerization reaction to be 75-85°C.

[0016] Wherein, the stabilizer is selected from polyvinyl pyrrolidone, the solvent is selected from: any one or more of ethanol, ethyl acetate, isopropanol or n-butanol; the initiator is selected from any one or more of azobisisoheptanenitrile (ABVN), azobisisovaleronitrile (AMBN), azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO) or dilauroyl peroxide (LPO); the polymerizable monomer molecule includes at least one unsaturated double bond, and is divided into monofunctional monomers and difunctional monomers according to the number of unsaturated double bonds.

[0017] The suspended polymerization product is obtained through centrifugation, suction filtration and drying.

[0018] Preferably, the drying method includes: baking drying, vacuum drying or spray drying.

[0019] Preferably, the vacuum drying is performed at room temperature to 50°C.

[0020] The sulfonation comprises adding the suspended polymerization product into concentrated sulfuric acid to carry out a sulfonation reaction.

[0021] Preferably, the sulfonation further comprises adding P to the mixture of concentrated sulfuric acid and the suspended polymer product. 2 O 5。

[0022] Preferably, the sulfonation reaction is carried out at 30-60°C.

[0023] Preferably, after the suspension polymerization product is added into concentrated sulfuric acid, it is dispersed uniformly using ultrasound.

[0024] The sulfonated product is obtained through centrifugation, suction filtration and drying.

[0025] Preferably, the drying method includes: baking drying, vacuum drying or spray drying.

[0026] Preferably, the vacuum drying is performed at room temperature to 50°C.

[0027] In a third aspect, an ammonia nitrogen remover comprises: the polymer microspheres described above.

[0028] In a fourth aspect, an ammonia nitrogen remover comprises: the polymer microspheres and aluminum sol described above.

[0029] In a fifth aspect, the preparation method of the above-mentioned ammonia nitrogen remover comprises: dispersing polymer microspheres in aluminum sol, and obtaining the ammonia nitrogen remover after drying and evaporating the water in the aluminum sol.

[0030] The drying method includes: baking drying, vacuum drying or spray drying.

[0031] Preferably, the polymer microspheres are dispersed in the aluminum sol using ultrasound, and the ultrasound time is 15-60 min.

[0032] Preferably, the baking and drying is carried out at a temperature of 100-150°C.

[0033] A sixth aspect is a use of the polymer microspheres described above for removing ammonia nitrogen compounds from water.

[0034] The present invention has the following beneficial effects: In the process of preparing polymer microspheres, acrylate or methacrylate monomers containing EO and aromatic groups are introduced to participate in the free radical polymerization reaction, in which the O atom is connected to the aromatic group, and the conjugation effect is greater than the induction effect. The overall result is that the O atom directly connected to the benzene ring is donating to the aromatic group, which increases the electron cloud density on the aromatic group, especially the electron cloud density of the ortho (C2, C6) and para (C4) positions of the O atom. It is easier to undergo electrophilic substitution reaction during subsequent sulfonation, and -SO is grafted at the ortho and para positions of the oxygen atom. 3 H, resulting in an enhanced ability to exchange ammonia nitrogen compounds, and a significant increase in the total amount of adsorption. At the same time, the introduction of EO-containing segments into the polymerizable monomers helps to improve the hydrophilicity of the microspheres and increase the wrinkles on the surface of the microspheres, thereby increasing the specific surface area of ​​the microspheres and the adsorption capacity of ammonia nitrogen compounds. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 The infrared spectra of the sulfonated P(OPPEA-HEMA-St-DVP) microspheres and P(OPPEA-HEMA-St-DVP) microspheres prepared in Example 7, wherein (1) is the P(OPPEA-HEMA-St-DVP) microspheres; (2) is the sulfonated P(OPPEA-HEMA-St-DVP) microspheres.

[0036] Figure 2 The SEM images of the polymer microspheres prepared in Examples 1 and 3 and Comparative Example 1 are shown. DETAILED DESCRIPTION

[0037] The following is a description of the implementation of the present invention by means of specific embodiments. Those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification.

[0038] Before further describing the specific embodiments of the present invention, it should be understood that the scope of protection of the present invention is not limited to the specific embodiments described below; it should also be understood that the terms used in the examples of the present invention are intended to describe specific embodiments, rather than to limit the scope of protection of the present invention. The test methods in the following examples without specifying specific conditions are generally carried out under conventional conditions or under conditions recommended by the manufacturers.

[0039] When the embodiments give numerical ranges, it should be understood that, unless otherwise specified in the present invention, both endpoints of each numerical range and any numerical value between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as those generally understood by those skilled in the art. In addition to the specific methods, equipment, and materials used in the embodiments, according to the grasp of the prior art by those skilled in the art and the record of the present invention, any methods, equipment, and materials of the prior art similar or equivalent to the methods, equipment, and materials described in the embodiments of the present invention can also be used to realize the present invention.

[0040] Embodiment 1: P(PHEA-GMA-St-DVP) microspheres were prepared by dispersion polymerization with ethylene glycol phenyl ether acrylate(PHEA), glycidyl methacrylate(GMA), styrene(St) and divinylbenzene(DVP) as polymerizable monomers, polyvinylpyrrolidone(PVP-K30) as stabilizer, azobisisobutyronitrile(AIBN) as initiator and ethanol as solvent.

[0041] Free radical polymerization reaction: add 250 mL of 0.6 wt% PVP ethanol solution into a flask, heat to 78 °C, and mechanically stir for 15 minutes. Then, add 10 mL of DVP monomer, 5 mL of PHEA monomer, 5 mL of GMA monomer, and 40 mL of St monomer containing initiator AIBN dropwise into the above solution, wherein the amount of AIBN is 1 wt% of the total weight of the monomers. Control the temperature within the range of 77-83 °C for polymerization. After 12 hours of reaction, obtain a crude product by centrifugation, wash the crude product with an ethanol / water mixed solution, and filter it. Then, vacuum dry the solid particles obtained by filtration at room temperature to obtain P (PHEA-GMA-St-DVP) microspheres.

[0042] Sulfonation reaction: 15 g of dried P(PHEA-GMA-St-DVP) microspheres and 250 mL of concentrated sulfuric acid were added to a flask and then ultrasonically dispersed to form a uniform suspension. Then, 0.5 g of P 2 O 5The sulfonation reaction was carried out in a water bath at 40±1°C, and mechanical stirring was maintained for 10 hours. After the reaction was completed, the suspension was slowly added to 200 mL of deionized water, and then the crude product was separated by centrifugation. The crude product was washed with deionized water and filtered, and the solid particles obtained by filtration were soaked in 5wt% sulfuric acid for 8 hours to form microspheres with H + After soaking, the microspheres were washed with clean water to pH = 7, and the product was vacuum dried at 40 ° C to obtain sulfonated P (PHEA-GMA-St-DVP) microspheres.

[0043] Example 2 Under the assistance of ultrasound, 5 g of the sulfonated P (PHEA-GMA-St-DVP) microspheres prepared in Example 1 were dispersed in 50 mL of nano-aluminum sol BRD-300B (Suzhou Baird New Materials) with a solid content of 20%. The ultrasonic dispersion time was 30 minutes. The water in the aluminum sol was evaporated after high-temperature baking at 125°C for 3 hours to obtain aluminum-hybridized sulfonated P (PHEA-GMA-St-DVP) microspheres.

[0044] Example 3 The preparation method is the same as that of Example 1, except that the monomers participating in the free radical polymerization reaction use 10 mL of DVP monomer, 10 mL of PHEA monomer and 40 mL of St monomer containing initiator AIBN.

[0045] Example 4 Under the assistance of ultrasound, 5 g of the sulfonated P (PHEA-St-DVP) microspheres prepared in Example 3 were dispersed in 50 mL of nano-aluminum sol BRD-300B (Suzhou Baird New Materials) with a solid content of 20%. The ultrasonic dispersion time was 30 minutes. The water in the aluminum sol was evaporated after high-temperature baking at 125°C for 3 hours to obtain aluminum-hybridized sulfonated P (PHEA-St-DVP) microspheres.

[0046] Example 5 P(OPPEA-St-DVP) microspheres were prepared by dispersion polymerization with polyethylene glycol o-phenylphenyl ether acrylate (OPPEA), styrene (St) and divinylbenzene (DVP) as polymerizable monomers, polyvinyl pyrrolidone (PVP-K30) as stabilizer, azobisisobutyronitrile (AIBN) as initiator and ethanol as solvent.

[0047] Free radical polymerization reaction: Add 250 mL of 0.6 wt% PVP ethanol solution into a flask, heat to 78 ° C, and mechanically stir for 15 minutes. Then, add 10 mL of DVP, 5 mL of OPPEA, and 45 mL of St monomer containing initiator AIBN dropwise into the above solution, wherein the amount of AIBN is 1 wt% of the total weight of the monomers. The polymerization reaction is carried out at a temperature controlled in the range of 77-83 ° C. After 12 hours of reaction, the crude product is obtained by centrifugation, and the crude product is washed with an ethanol / water mixed solution and filtered. The solid particles obtained by filtration are then vacuum dried at room temperature to obtain P (OPPEA-St-DVP) microspheres.

[0048] Sulfonation reaction: 15 g of dried P(OPPEA-St-DVP) microspheres and 250 mL of concentrated sulfuric acid were added to a flask and then ultrasonically dispersed to form a uniform suspension. Then, 0.5 g of P 2 O 5 The sulfonation reaction was carried out in a water bath at 40±1°C, and mechanical stirring was maintained for 10 hours. After the reaction was completed, the suspension was slowly added to 200 mL of deionized water, and then the crude product was separated by centrifugation. The crude product was washed with deionized water and filtered, and the solid particles obtained by filtration were soaked in 5wt% sulfuric acid for 8 hours to form microspheres with H + After soaking, the microspheres were washed with clean water to pH = 7, and the product was vacuum dried at 40 ° C to obtain sulfonated P (OPPEA-St-DVP) microspheres.

[0049] Example 6 Under the assistance of ultrasound, 5 g of the sulfonated P (OPPEA-St-DVP) microspheres prepared in Example 5 were dispersed in 50 mL of nano-aluminum sol BRD-300B (Suzhou Baird New Materials) with a solid content of 20%. The ultrasonic dispersion time was 30 minutes. The water in the aluminum sol was evaporated after high-temperature baking at 125°C for 3 hours to obtain aluminum-hybridized sulfonated P (OPPEA-St-DVP) microspheres.

[0050] Example 7 The preparation method is the same as that of Example 5, except that the monomers participating in the free radical polymerization reaction use 10 mL of DVP monomer, 5 mL of OPPEA monomer, 5 mL of hydroxyethyl methacrylate (HEMA) monomer and 40 mL of St monomer containing initiator AIBN, thereby obtaining sulfonated P (OPPEA-HEMA-St-DVP) microspheres.

[0051] Example 8 Under the assistance of ultrasound, 5 g of the sulfonated P (OPPEA-HEMA-St-DVP) microspheres prepared in Example 7 were dispersed in 50 mL of nano-aluminum sol BRD-300B (Suzhou Baird New Materials) with a solid content of 20%. The ultrasonic dispersion time was 30 minutes. The water in the aluminum sol was evaporated after high-temperature baking at 125°C for 3 hours to obtain aluminum-hybridized sulfonated P (OPPEA-HEMA-St-DVP) microspheres.

[0052] Comparative Example 1 P(St-DVP) microspheres were prepared by dispersion polymerization with styrene(St) and divinylbenzene(DVP) as polymerizable monomers, polyvinylpyrrolidone(PVP-K30) as stabilizer, azobisisobutyronitrile(AIBN) as initiator and ethanol as solvent.

[0053] Free radical polymerization reaction: add 250 mL of 0.6 wt% PVP ethanol solution into a flask, heat to 78 °C, and mechanically stir for 15 minutes. Then, add 10 mL of DVP and 50 mL of St monomer containing initiator AIBN dropwise into the above solution, wherein the amount of AIBN is 1 wt% of the total weight of the monomer. Control the temperature within the range of 77-83 °C for polymerization. After 12 hours of reaction, obtain a crude product by centrifugation, wash the crude product with an ethanol / water mixed solution, and filter it. Then, vacuum dry the solid particles obtained by filtration at room temperature to obtain P (St-DVP) microspheres.

[0054] Sulfonation reaction: 15 g of dried P(St-DVP) microspheres and 250 mL of concentrated sulfuric acid were added to a flask and then ultrasonically dispersed to form a uniform suspension. Then 0.5 g of P was added to the above suspension. 2 O 5 The sulfonation reaction was carried out in a water bath at 40±1°C, and the reaction was kept under mechanical stirring for 10 hours. After the reaction was completed, the suspension was slowly added to 200 mL of deionized water, and then the crude product was separated by centrifugation, and the crude product was washed with deionized water and filtered, and the solid particles obtained by filtration were vacuum dried at room temperature to obtain sulfonated P (St-DVP) microspheres.

[0055] Comparative Example 2 Under the assistance of ultrasound, 5 g of sulfonated P (St-DVP) microspheres prepared in Comparative Example 1 were dispersed in 50 mL of nano-aluminum sol BRD-300B (Suzhou Baird New Materials) with a solid content of 20%. The ultrasonic dispersion time was 30 minutes. The water in the aluminum sol was evaporated after high-temperature baking at 125°C for 3 hours to obtain aluminum-hybridized sulfonated P (St-DVP) microspheres.

[0056] Structural characterization and surface observation of the microspheres: specifically, using infrared spectroscopy (FTIR) to compare the P (OPPEA-HEMA-St-DVP) microspheres prepared in Example 7 with the sulfonated P (OPPEA-HEMA-St-DVP) microspheres, using scanning electron microscopy (SEM) to observe the surface morphology of the microspheres prepared in Examples 1, 3 and Comparative Example 1, and using BET specific surface area capacity measurement method and Malvern laser particle size analyzer to test the specific surface area and average diameter of the polymer microspheres prepared in Examples 1, 3, 5, 7 and Comparative Example 1.

[0057] Ammonia nitrogen removal agent penetration adsorption Through the initial NH 3 -N concentration and adsorbed NH 3 The penetration adsorption capacity of the microspheres is calculated by multiplying the difference in N concentration by the volume of sewage, which is used to evaluate the adsorption capacity of the microsphere material for ammonia nitrogen. The calculation formula is as follows: ; Where Q is the penetration adsorption amount, is the initial NH 3 -N concentration, is the adsorbed NH 3 -N concentration, V is the volume of sewage.

[0058] Ammonia nitrogen remover regeneration rate: The regeneration rate is used to indicate the change in the adsorption capacity of the ammonia nitrogen remover after desorption, and its calculation formula is as follows: ; in, is the regeneration rate of the ammonia nitrogen remover, is the NH after initial adsorption 3 -N concentration, is the NH after secondary adsorption after desorption and regeneration 3 -N concentration.

[0059] Determination of the penetration adsorption amount of the ammonia nitrogen remover: 5.0 g of the microspheres prepared in Examples 1-8 and Comparative Examples 1 and 2 were weighed in a 250 mL conical flask, and 100 mL of ammonia nitrogen-containing printing and dyeing wastewater discharged by Taizhou Wannuo Textile Co., Ltd. was added respectively. 3 -N concentration is 120mg / L, the conical flask is placed in a water bath constant temperature oscillator, and stirred at 100r / min for 12h at room temperature to allow the adsorption to reach equilibrium. After standing for 12h, the supernatant is taken to determine the ammonia nitrogen concentration. The method for detecting the ammonia nitrogen concentration is spectrophotometry, and the ammonia nitrogen removal rate is calculated from it.

[0060] Determination of the regeneration rate of ammonia nitrogen remover: Accurately weigh 5g of saturated adsorbed microspheres in a beaker, and add saturated NaCl solution, 5wt% NaOH solution, 5wt% H 2 SO 4 15 mL of each solution was used to regenerate the saturated adsorption microspheres, and finally 25 mL of deionized water was added for rinsing. After soaking in clean water for 2 hours, the water was removed by filtration. After regeneration, a secondary adsorption was carried out under the same experimental conditions, and the ammonia nitrogen concentration of the adsorbed water was measured to calculate the penetration adsorption amount after regeneration and the regeneration rate of the ammonia nitrogen adsorbent.

[0061] The test results of the specific surface area, average diameter, ammonia nitrogen removal agent adsorption amount and regeneration rate of the polymer microspheres prepared in Examples 1-8 and Comparative Examples 1 and 2 are listed in Table 1.

[0062] Table 1

[0063] Figure 1 The infrared spectra of P(OPPEA-HEMA-St-DVP) microspheres (1) and sulfonated P(OPPEA-HEMA-St-DVP) microspheres (2) are shown at 1600 cm -1 The peak at 1723 cm-1 is attributed to the vibration band of the benzene ring. -1 The peak at 1490 cm-1 is attributed to the stretching vibration of C=O. -1 The peak at 907 cm-1 is attributed to the stretching vibration of -CO-. -1 The peak at 1190 cm is attributed to the epoxy group. For the sulfonated P(OPPEA-HEMA-St-DVP) microspheres (2), the peak at 1190 cm is increased based on (1). -1 、1068 cm -1 The peak at , indicating that -SO was successfully introduced on the surface of the microspheres 3 H group. Figure 2 The surface morphologies of different microspheres are shown. In Examples 1 and 3, PHEA is added as a polymerizable monomer for suspension polymerization of microspheres, and the surfaces of the prepared microspheres have more wrinkles. In Comparative Example 1, only styrene and divinylbenzene are used as polymerizable monomers, and the surfaces of the prepared microspheres are flatter and smoother without obvious wrinkles.

[0064] According to the adsorption amount and regeneration rate of the microspheres as ammonia nitrogen removers in Table 1, the adsorption amount of Examples 1-8 is significantly higher. The adsorption amount after hybridization of the polymer microspheres with aluminum sol can be further improved, but the regeneration rate will be reduced. The adsorption amount of Comparative Examples 1 and 2 is significantly lower than that of Examples 1-8. The reason for this is that the sulfonated P (St-DVP) microspheres prepared in Comparative Example 1 are found to have too smooth surface after SEM observation. The BET test shows that their specific surface area is significantly lower than that of the microspheres prepared in Examples 1-8. The contact area with ammonia nitrogen adsorbents in sewage is smaller, resulting in the adsorption and removal effect of ammonia nitrogen adsorbents being inferior to that of the microspheres in Examples 1-8. In addition, the sulfonated P (St-DVP) microspheres prepared in Comparative Example 1 do not use monomers containing EO segments, have poor hydrophilicity, lack the conjugation effect of oxygen atoms on the benzene ring, increase the electron cloud density on the benzene ring, and make the subsequent sulfonation reaction more difficult to carry out.

[0065] Examples 2, 4, 6, 8 and Comparative Example 2 add aluminum sol on the basis of Examples 1, 3, 5, 7 and Comparative Example 1, and introduce Al on the surface of the polymer microspheres. 3+ , which is conducive to cation exchange with ammonia nitrogen adsorbents, but after the exchange, Al 3+ It is difficult to regenerate using conventional methods, resulting in a low regeneration rate of the ammonia nitrogen remover.

[0066] Finally, it should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments, or to perform equivalent replacements on parts thereof. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention. Although the above describes the specific implementation methods of the present invention, it is not intended to limit the protection scope of the present invention. Those skilled in the art should understand that, based on the technical solution of the present invention, various modifications or deformations that can be made by those skilled in the art without creative labor are still within the protection scope of the present invention.

Claims

1. A polymer microsphere, characterized in that: It is obtained by suspension polymerization and sulfonation of a monofunctional monomer and a difunctional monomer; wherein the monofunctional monomer is selected from: a styrene monomer and an acrylate containing EO and an aromatic group, a styrene monomer and a methacrylate containing EO and an aromatic group, wherein the aromatic group is directly connected to the EO, and the aromatic group is an aromatic ring or a heteroaromatic ring composed of 3 to 30 carbon atoms; Wherein, the difunctional monomer is selected from divinylbenzene, and divinylbenzene includes one or more mixtures of o-divinylbenzene, m-divinylbenzene or p-divinylbenzene; Wherein, the styrene monomer is selected from: one or more of styrene, methyl styrene and ethyl styrene; Among them, the structural formulas of styrene monomers and acrylates containing EO and aromatic groups, and styrene monomers and methacrylates containing EO and aromatic groups are: , , or Any one of , where n is a positive integer greater than or equal to 1.

2. The polymer microsphere according to claim 1, characterized in that The aryl group is a benzene ring.

3. The polymer microsphere according to claim 1, characterized in that The monofunctional monomer includes a hydroxyl-containing or epoxy-containing (meth)acrylate; And / or, the monofunctional monomer includes: one or more of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, dodecyl (meth)acrylate and octadecyl (meth)acrylate.

4. The method for preparing polymer microspheres according to any one of claims 1 to 3, characterized in that: The preparation method includes: suspension polymerization and sulfonation; Suspension polymerization includes using a solvent to dissolve a stabilizer, dropping an initiator and a polymerizable monomer into a solvent containing a stabilizer to carry out a polymerization reaction, and controlling the polymerization reaction temperature to be 75-85°C; Sulfonation involves adding the suspension polymerization product to concentrated sulfuric acid to carry out a sulfonation reaction.

5. The preparation method according to claim 4, characterized in that: The stabilizer is selected from polyvinyl pyrrolidone; And / or, the solvent is selected from any one or more of ethanol, ethyl acetate, isopropanol or n-butanol; And / or, the initiator is selected from any one or more of azobisisoheptanenitrile, azobisisovaleronitrile, azobisisobutyronitrile, benzoyl peroxide and dilauroyl peroxide; And / or, the polymerizable monomer includes at least one unsaturated double bond in the molecule.

6. The preparation method according to claim 4, characterized in that: The suspension polymerization product is obtained by centrifugation, filtration and drying; And / or, sulfonation comprises adding P2O to a mixture of concentrated sulfuric acid and the suspended polymer product. 5； and / or, the sulfonation reaction is carried out at 30-60° C.; and / or, after adding the suspended polymer product into concentrated sulfuric acid, using ultrasound to disperse it uniformly; And / or, the sulfonated product is obtained by centrifugation, suction filtration and drying.

7. An ammonia nitrogen remover, characterized in that: The ammonia nitrogen remover comprises: the polymer microspheres described in any one of claims 1-3.

8. An ammonia nitrogen remover, characterized in that: The ammonia nitrogen remover comprises: the polymer microspheres described in any one of claims 1 to 3 and aluminum sol.

9. The method for preparing the ammonia nitrogen remover according to claim 8, characterized in that: The polymer microspheres are dispersed in aluminum sol, and then dried to obtain an ammonia nitrogen remover; the drying method includes: baking drying, vacuum drying or spray drying.

10. A use, characterized in that: The polymer microspheres according to any one of claims 1 to 3 are used to remove ammonia nitrogen compounds in water.

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