Modified ion exchange resin with high adsorption capacity and application of modified ion exchange resin in wastewater

Abstract

The invention provides a modified ion exchange resin with high adsorption capacity, which is characterized in that the resin is modified through a copolymerization reaction, and the copolymerization reaction comprises copolymerization of a nonionic surfactant and a polyacrylic acid monomer so as to form the modified resin with enhanced dispersibility; the modified ion exchange resin is in the form of spherical small particles. The modified ion exchange resin has the advantages of higher dispersity, strong flowability and more convenience in the filling process, and the problem of difficulty in filling is reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and more specifically, relates to a modified ion exchange resin with high adsorption capacity and its application in waste water. Background Art

[0002] Cationic exchange resin is a polymer compound with a three-dimensional network structure, which is widely used in many fields, including electricity, petroleum, chemical industry, electronics, food fermentation, drinking water, medicine, biomedicine, non-ferrous metals, new energy, military and steel. These resins can undergo ion exchange reactions and show "ion exchange capacity", which is the number of milligram equivalents of ions that can be exchanged per gram of dry resin or per milliliter of wet resin. The total exchange capacity, working exchange capacity and regeneration exchange capacity of cation exchange resin are its important performance indicators.

[0003] In general, cation exchange resins play an important role in multiple industries due to their unique selectivity, exchange capacity and durability, and their application scope and market size are expected to expand further through continuous technological innovation and product upgrading.

[0004] However, traditional acrylic cationic resins have some limitations in practical applications, such as easy aggregation of particles and poor fluidity, which not only affects the filling efficiency of the resin, but also limits its performance in dynamic systems. Summary of the invention

[0005] The purpose of the present invention is to provide a modified ion exchange resin with high adsorption capacity and its application in wastewater. The modified ion exchange resin has high dispersibility and strong fluidity, is more convenient in the filling process, and reduces the problem of filling difficulty.

[0006] The technical solution provided by the present application is a modified ion exchange resin with high adsorption capacity, comprising: the resin is modified by a copolymerization reaction, the copolymerization reaction comprises copolymerizing a nonionic surfactant with a polyacrylic acid monomer to form a modified resin with enhanced dispersibility; the modified ion exchange resin is in the form of small spherical particles.

[0007] Wherein, the nonionic surfactant is selected from one or more of polyethylene glycol nonionic surfactants, alkylphenol polyoxyethylene ethers, fatty acid polyoxyethylene esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides or polyethers.

[0008] Wherein, the preparation method of the modified resin comprises the following steps:

[0009] a. Mix a nonionic surfactant, a polyacrylic acid monomer and a crosslinking agent, add an initiator, and carry out a copolymerization reaction at a certain temperature and pressure;

[0010] b. separating, washing and drying the copolymerization product to obtain an initial polymer;

[0011] c. Mix the initial polymer with sulfuric acid, heat to 130-150°C at a heating rate of 2-3°C / min, and keep the temperature for reaction for 12-18h;

[0012] d. cooling, washing, filtering, and drying to obtain the modified ion exchange resin.

[0013] Wherein, the polyacrylic acid monomer includes one or more of allyl itaconate, acrylic acid, methacrylic acid, acrylonitrile, itaconic acid and hydroxyethyl acrylate.

[0014] Wherein, the washing process in step d comprises mixing and stirring the modified ion exchange resin and the nonionic surfactant for 1-2 hours and then rinsing.

[0015] Wherein, the cross-linking agent is one of divinylbenzene, glycerol, melamine or ethylene glycol diglycidyl ether.

[0016] Wherein, the modified ion exchange resin is a spherical small particle with a particle size between 0.3-1.25 mm.

[0017] Wherein, the water content of the modified ion exchange resin is 45%-60%.

[0018] Another solution provided by the present application is a method for treating sewage using the modified ion exchange resin with high adsorption capacity as described in any one of the above items, the method comprising using the modified ion exchange resin to remove pollutants in the sewage.

[0019] Wherein, the sewage treatment includes: industrial wastewater treatment or metal recovery.

[0020] The beneficial effect of the present invention is that the acrylic cationic resin is modified by introducing a nonionic surfactant, and the introduction of the nonionic surfactant can form a protective film on the surface of the resin particles, reduce the direct contact and friction between the particles, and effectively prevent the particles from agglomerating. After the polymerization reaction is completed, the excess surfactant is removed through a thorough cleaning process to ensure the cleanliness of the resin surface while retaining a sufficient modification effect. The modified resin is more convenient in the filling process and can be directly poured, reducing the problems of filling difficulty and low efficiency caused by particle aggregation. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a picture of the properties of traditional acrylic cationic resin.

[0022] Figure 2This is a picture of the properties of a modified ion exchange resin with high adsorption capacity prepared in one embodiment. DETAILED DESCRIPTION

[0023] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the present invention is further described in detail below in combination with specific descriptions and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0024] Traditional acrylic cationic resins have some limitations in practical applications, such as easy aggregation of particles and poor fluidity. Figure 1 As shown, this not only affects the filling efficiency of the resin, but also limits its performance in a dynamic system. In order to overcome these limitations, the present application provides a method for modifying acrylic cationic resin by introducing a nonionic surfactant. During the synthesis of the resin, the addition of a nonionic surfactant can significantly improve the dispersibility of the resin, so that the resin particles maintain a distinct form after drying, thereby enhancing its fluidity. This modified resin is more convenient during the filling process and can be directly poured, reducing the problem of difficulty in filling and inefficiency caused by particle aggregation.

[0025] The technical solution provided by the present application is a modified ion exchange resin with high adsorption capacity, comprising: the resin is modified by copolymerization, wherein the copolymerization reaction comprises copolymerizing a nonionic surfactant with a polyacrylic acid monomer to form a modified resin with enhanced dispersibility; the modified ion exchange resin is in the form of spherical small particles, such as Figure 2 shown.

[0026] Wherein, the nonionic surfactant is selected from one or more of polyethylene glycol nonionic surfactants, alkylphenol polyoxyethylene ethers, fatty acid polyoxyethylene esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides or polyethers.

[0027] Wherein, the preparation method of the modified resin comprises the following steps:

[0028] a. mixing a nonionic surfactant, a polyacrylic acid monomer and a crosslinking agent, adding an initiator, and performing a copolymerization reaction at a certain temperature and pressure; b. separating, washing and drying the copolymerization product to obtain an initial polymer; c. mixing the initial polymer with sulfuric acid, heating the temperature to 130-150°C at a heating rate of 2-3°C / min, and keeping the temperature for reaction for 12-18h; d. cooling, washing, filtering, and drying to obtain the modified ion exchange resin.

[0029] In one embodiment, the drying method in step d is low-temperature air drying.

[0030] Wherein, the polyacrylic acid monomer includes one or more of allyl itaconate, acrylic acid, methacrylic acid, acrylonitrile, itaconic acid and hydroxyethyl acrylate.

[0031] In one embodiment, the usage ratio of the polyacrylic acid monomer is, by weight: 100 parts of allyl itaconate, 80-90 parts of acrylic acid, 60-80 parts of methacrylic acid, 20-40 parts of acrylonitrile, 10-30 parts of itaconic acid, and 10-20 parts of hydroxyethyl acrylate.

[0032] The washing process in step d comprises mixing and stirring the modified ion exchange resin with a nonionic surfactant for 1-2 hours and then rinsing. The nonionic surfactant is one or more of polyethylene glycol nonionic surfactant, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide or polyether.

[0033] Wherein, the initiator is selected from one or more of persulfate, dibenzoyl peroxide, azobisisobutyronitrile or photoinitiator. Preferably, the initiator is sodium persulfate.

[0034] Wherein, the cross-linking agent is one of divinylbenzene, glycerol, melamine or ethylene glycol diglycidyl ether. Preferably, the cross-linking agent is divinylbenzene.

[0035] The modified ion exchange resin is a spherical small particle with a particle size between 0.3-1.25 mm, preferably 0.4-0.6 mm.

[0036] Wherein, the water content of the modified ion exchange resin is 45%-60%.

[0037] The introduction of nonionic surfactants can form a protective film on the surface of resin particles, reducing direct contact and friction between particles, thereby effectively preventing particles from agglomerating. After the polymerization reaction is completed, the excess surfactant is removed through a thorough cleaning process to ensure the cleanliness of the resin surface while retaining sufficient modification effects. In addition, in the step of removing free water, the use of appropriate drying technology can further ensure the clarity and fluidity of the resin particles.

[0038] In addition, the modified resin also showed potential advantages in water treatment efficiency and adsorption performance. The introduction of non-ionic surfactants did not have a negative impact on the chemical structure and exchange capacity of the resin. Instead, it may have improved the kinetic performance of the resin in a dynamic water treatment system by improving the interaction between particles. This modified polyacrylic acid cationic resin not only performs well in the filling process, is easy to pour directly and evenly distribute, but also shows better dynamic performance and treatment efficiency in actual sewage treatment applications. By improving the dispersibility of the resin, the contact area between it and the pollutants in the sewage is increased, thereby improving the adsorption efficiency and treatment capacity.

[0039] In summary, the modified polyacrylic acid cationic resin of the present invention, by ingeniously introducing a nonionic surfactant during the preparation process, not only solves the aggregation problem of traditional resins, but also improves its application performance in the fields of sewage treatment, etc., and has important practical value and broad market prospects.

[0040] Another solution provided by the present application is a method for treating sewage using the modified ion exchange resin with high adsorption capacity as described in any one of the above items, the method comprising using the modified ion exchange resin to remove pollutants in the sewage.

[0041] Wherein, the sewage treatment includes: industrial wastewater treatment or metal recovery.

[0042] The modified ion exchange resin can also be used in drinking water systems and the separation and extraction of biopharmaceuticals.

[0043] Embodiment 1,

[0044] Resin preparation: Polyethylene glycol type nonionic surfactant is used as a modifier, mixed with allyl itaconate and acrylic acid monomers, divinylbenzene is added as a cross-linking agent, persulfate is used as an initiator, and copolymerization is carried out at 80°C.

[0045] The usage ratio of the polyacrylic acid monomer is, by weight: 100 parts of allyl itaconate, 80 parts of acrylic acid, 60 parts of methacrylic acid, 20 parts of acrylonitrile, 10 parts of itaconic acid, and 10 parts of hydroxyethyl acrylate.

[0046] Post-treatment: The product after the reaction is separated, washed and dried to obtain the initial polymer. The initial polymer is then mixed with sulfuric acid, heated to 140°C at a heating rate of 2.5°C / min, and kept warm for 15 hours. The washing process includes mixing the modified ion exchange resin with the non-ionic surfactant for 1-2 hours and then rinsing.

[0047] Resin morphology: The modified ion exchange resin finally obtained is spherical small particles with a particle size between 0.5-1.0 mm and a water content of 45%. Specific embodiment 2:

[0049] Resin preparation: Alkylphenol polyoxyethylene ether is used as a nonionic surfactant, mixed with methacrylic acid and acrylonitrile monomers, glycerol is added as a cross-linking agent, dibenzoyl peroxide is used as an initiator, and copolymerization is carried out at 75°C.

[0050] The usage ratio of the polyacrylic acid monomer is, by weight: 100 parts of allyl itaconate, 90 parts of acrylic acid, 80 parts of methacrylic acid, 40 parts of acrylonitrile, 30 parts of itaconic acid, and 20 parts of hydroxyethyl acrylate.

[0051] Post-treatment: The reaction product is separated, washed and dried to obtain an initial polymer, which is then mixed with sulfuric acid, heated to 135°C at a heating rate of 3°C / min, and kept warm for 12 hours. The washing process includes mixing and stirring the modified ion exchange resin with a nonionic surfactant for 1-2 hours and then rinsing.

[0052] Resin morphology: The obtained modified ion exchange resin is spherical small particles with a particle size between 0.3-0.6 mm and a water content of 50%. Specific embodiment 3:

[0054] Resin preparation: fatty acid polyoxyethylene ester is used as a non-ionic surfactant, mixed with itaconic acid and hydroxyethyl acrylate monomers, melamine is added as a cross-linking agent, azobisisobutyronitrile is used as an initiator, and copolymerization is carried out at 85°C.

[0055] The usage ratio of the polyacrylic acid monomer is, by weight: 100 parts of allyl itaconate, 82 parts of acrylic acid, 65 parts of methacrylic acid, 25 parts of acrylonitrile, 15 parts of itaconic acid, and 12 parts of hydroxyethyl acrylate.

[0056] Post-treatment: The product after the reaction is separated, washed and dried to obtain the initial polymer. The initial polymer is then mixed with sulfuric acid, heated to 145°C at a heating rate of 2.8°C / min, and kept warm for 16 hours. The washing process includes mixing the modified ion exchange resin with the non-ionic surfactant for 1-2 hours and then rinsing.

[0057] Resin morphology: The modified ion exchange resin finally obtained is spherical small particles with a particle size between 0.7-1.25 mm and a water content of 50%. Specific embodiment 4:

[0059] Resin preparation: Polyoxyethylene alkylamine is used as a nonionic surfactant, mixed with acrylic monomer, ethylene glycol diglycidyl ether is added as a cross-linking agent, and a photoinitiator is used to carry out copolymerization under ultraviolet light.

[0060] The usage ratio of the polyacrylic acid monomer is, by weight: 100 parts of allyl itaconate, 88 parts of acrylic acid, 70 parts of methacrylic acid, 35 parts of acrylonitrile, 22 parts of itaconic acid, and 18 parts of hydroxyethyl acrylate.

[0061] Post-treatment: The reaction product is separated, washed and dried to obtain the initial polymer, and then the initial polymer is mixed with sulfuric acid, heated to 130°C at a heating rate of 2.2°C / min, and kept warm for 14 hours. The washing process includes mixing and stirring the modified ion exchange resin with the non-ionic surfactant for 1-2 hours and then rinsing.

[0062] Resin morphology: The obtained modified ion exchange resin is spherical small particles with a particle size of 0.4-0.6 mm and a water content of 55%.

[0063] The present application also conducted a number of tests on the resin prepared in the above examples, and the specific test results are shown in Table 1.

[0064] Table 1

[0065]

[0066]

[0067] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A modified ion exchange resin with high adsorption capacity, characterized in that, include: The resin is modified by a copolymerization reaction, wherein the copolymerization reaction includes copolymerizing a nonionic surfactant with a polyacrylic acid monomer to form a modified resin with enhanced dispersibility; The modified ion exchange resin is in the form of small spherical particles.

2. The modified ion exchange resin with high adsorption capacity according to claim 1, characterized in that The nonionic surfactant is selected from one or more of polyethylene glycol nonionic surfactants, alkylphenol polyoxyethylene ethers, fatty acid polyoxyethylene esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides or polyethers.

3. The modified ion exchange resin with high adsorption capacity according to claim 1 or 2, characterized in that The preparation method of the modified resin comprises the following steps: a. Mix a nonionic surfactant, a polyacrylic acid monomer and a crosslinking agent, add an initiator, and carry out a copolymerization reaction at a certain temperature and pressure; b. separating, washing and drying the copolymerization product to obtain an initial polymer; c. Mix the initial polymer with sulfuric acid, heat to 130-150°C at a heating rate of 2-3°C / min, and keep the reaction for 12-18 hours; d. cooling, washing, filtering, and drying to obtain the modified ion exchange resin.

4. The modified ion exchange resin with high adsorption capacity according to claim 3, characterized in that The polyacrylic acid monomer includes one or more of allyl itaconate, acrylic acid, methacrylic acid, acrylonitrile, itaconic acid and hydroxyethyl acrylate.

5. The modified ion exchange resin with high adsorption capacity according to claim 3, characterized in that The washing process in step d includes mixing the modified ion exchange resin and the nonionic surfactant and stirring for 1-2 hours, followed by rinsing.

6. The modified ion exchange resin with high adsorption capacity according to claim 3, characterized in that The cross-linking agent is one of divinylbenzene, glycerol, melamine or ethylene glycol diglycidyl ether.

7. The modified ion exchange resin with high adsorption capacity according to claim 1, characterized in that The modified ion exchange resin is a spherical small particle with a particle size between 0.3 and 1.25 mm.

8. The modified ion exchange resin with high adsorption capacity according to claim 1, characterized in that The water content of the modified ion exchange resin is 45%-60%.

9. A method for treating sewage using the modified ion exchange resin with high adsorption capacity according to any one of claims 1 to 8, characterized in that: The method comprises using the modified ion exchange resin to remove pollutants from wastewater.

10. The sewage treatment method according to claim 9, characterized in that: The sewage treatment includes industrial wastewater treatment or metal recovery.

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