CN111013554A - Composite macroporous adsorption resin for removing perfluorinated compounds in water - Google Patents
Composite macroporous adsorption resin for removing perfluorinated compounds in water Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a composite adsorption resin for removing perfluorinated compounds in water. By introducing functional group modified macroporous adsorption resin, perfluorinated compounds in water are adsorbed based on hydrophobic-charge synergistic effect, so that adsorption capacity and efficiency are improved. The invention epoxidizes the residual double bonds in the skeleton molecule, then carries out ring opening on the skeleton molecule, grafts amino functional groups, and utilizes the charge effect to improve the adsorption effect of the resin on adsorbates. The composite adsorption resin with proper microporous structure, narrow particle size distribution, uniform pore diameter, high specific surface area and specific functional groups is finally obtained, and the screening capacity and adsorption rate of perfluorinated compounds in water are effectively improved.
Description
Technical Field
The invention relates to a composite macroporous adsorption resin for removing perfluorinated compounds in water, in particular to a composite macroporous adsorption resin for removing perfluorinated compounds in water as well as a preparation method and application thereof, belonging to the field of functional polymer materials and environmental protection.
Background
Perfluorooctanesulfonate (Perluorooctane Sulfonate) is used as a final degradation product of a perfluorinated compound, and the structure of the perfluorooctanesulfonate contains a plurality of groups such as carbon fluorine long chains, sulfonic acid and carboxylic acid, so that the perfluorooctanesulfonate has the characteristics of hydrophobicity and oleophobicity. Because of the strong polarity of the C-F bond, PFOS is one of the most recalcitrant organic pollutants. Because of the environmental and human harm of PFOS, the production of related products has been started to be stopped on a global basis.
Traditional materials such as cotton, cellulose, nylon and reverse osmosis membranes can be used for removing perfluorinated compounds, for example, patents CN102489260B, CN102500338B, CN105776404A and CN103408103A describe the application methods of the above materials respectively, which have certain popularization possibilities, but the removal efficiency is low or the industrial application is less due to the cost problem. In addition, some novel treatment methods such as light radiation, photocatalysis, molecular imprinting, induced electrochemistry and the like are mentioned in patents CN104193056B, CN108264127A and CN105001371B to degrade trace perfluorinated compounds in water, but due to harsh conditions, difficult operation, high energy consumption and the like, the practical application cannot be popularized in a large scale.
According to the molecular characteristics of PFOS, the anion exchange resin and the activated carbon material with proper pore diameter can effectively remove trace pollutants in water. The application of ion exchange resins, particularly quaternary amine type anion resins containing more than C8, in water treatment is limited as detailed in patent publication No. CN101605728B, and treatment efficiency is limited in application due to high cost and low exchange capacity of ion exchange resins; activated carbon (granules or powder) is used as the most commonly used filtering and adsorbing material in patents CN106732379A, CN108144572A for removing perfluorooctanoic acid.
Therefore, the prior art for removing perfluorinated compounds in water still lacks of an adsorbent which has low cost, simple operation and high treatment efficiency.
Disclosure of Invention
The invention focuses on the preparation of macroporous adsorption resin with large adsorption capacity, easy elution and long service cycle, starts with the design of a high molecular structure, selects common divinylbenzene as a comonomer and a cross-linking agent, prepares the macroporous adsorption resin with a proper pore structure by adjusting the proportion of a pore-forming agent, epoxidizes residual dangling double bonds in the resin by organic peroxyacid, and then utilizes an aminated nucleophilic reagent to open rings of epoxy groups and graft amino functional groups to prepare the composite resin taking hydrophobic effect as the main consideration and charge effect. The resin product has reasonable microstructure, such as specific surface area, aperture and particle size distribution, and is grafted with groups having strong charge function on perfluoroacids and perfluorosulfonate, so that the resin can effectively remove perfluorooctanoic acid (or salt) pollutants in water.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is divided into three steps: preparing a polystyrene macroporous adsorption resin base sphere, epoxidizing residual suspended double bonds on the base sphere to obtain a resin intermediate, and functionalizing epoxy groups on the resin intermediate.
The specific scheme comprises the following steps:
the method comprises the following steps: preparation of polystyrene macroporous adsorption resin base ball
Styrene, divinylbenzene or polyvinyl benzene are taken as monomers, a pore-foaming agent is added, and the macroporous adsorption resin base ball is prepared by suspension polymerization, and is dried for standby after the pore-foaming agent is removed;
step two: epoxidation of dangling double bonds
Fully swelling the resin-based spheres obtained in the step (1), epoxidizing the dangling double bonds which do not participate in the suspension polymerization reaction in molecular chains by using organic peroxyacid, and washing away the solvent and excessive reactants to obtain a resin intermediate;
step three: functionalization of epoxide groups
And (3) after the resin intermediate in the step (2) is fully swelled, replacing the solvent with water, carrying out ring-opening functionalization reaction on an epoxy group by using an amination nucleophilic reagent in a mixed solvent of water and dioxane, and washing away the solvent to obtain the macroporous adsorption resin grafted with the amino functional group.
More specifically, weighing the resin-based spheres (dried) prepared in the step (1) in a reactor, adding a solvent to ensure that the resin is fully swelled, adding organic peroxy acid into the reactor to react at a low temperature of 0-5 ℃, heating to room temperature after the reaction is finished, soaking and cleaning with ethanol, washing with deionized water, and filtering to obtain a product, thereby obtaining a resin intermediate. Then taking the resin intermediate obtained in the step (2), soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water or pure water, and adding a mixed solvent; mechanically stirring for 0.5-1 hour, adding an amination reagent, heating to 60-75 ℃, and reacting at constant temperature for 24-30 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
In the step (1), the polyvinyl benzene monomer can be one or a mixture of more of styrene, divinylbenzene and divinyl xylene; the pore-forming agent can be one or a mixture of more of toluene, gasoline, methylcyclohexane and n-butanol; the mass ratio of the pore-foaming agent to the polyvinyl benzene monomer is 1-1.4: 1.
In the step (2), the solvent can be one or a mixture of more of acetone, dichloroethane, toluene and xylene, and the mass ratio of the solvent to the resin-based spheres (dried) is 4-6.5: 1; the organic peroxy acid is one or a mixture of more of m-chloroperoxybenzoic acid, peroxyacetic acid, peroxybenzoic acid and trifluoro peroxyacetic acid, and the mass ratio of the organic peroxy acid to the resin-based spheres (dried) is 0.45-0.65: 1.
In the step (3), the mixed solvent is dioxane and water, the mass ratio of the dioxane to the water is 0.5-1:1, and the mass ratio of the mixed solvent to the resin intermediate is 2-3: 1; the amination reagent is one or more of dimethylamine, dimethylethanolamine, trimethylamine, tri-n-butylamine, diethylenetriamine, triethylene tetramine and tetraethylene pentamine, and the mass ratio of the amination reagent to the resin intermediate (dry weight) is 0.25-0.5: 1.
The invention provides a preparation method of composite adsorption resin. The resin main body is macroporous adsorption resin, and has a charge function through a grafting functional group, so that the adsorption efficiency is greatly improved, the resin regeneration can be realized through a conventional treatment method, the service life is long, the industrial application cost can be effectively saved, and the method is suitable for removing the perfluorinated substances in sewage and drinking water with large scale and high treatment capacity. The invention can effectively remove the perfluorooctanoic acid (or salt) contained in the water, and the content of perfluorochemicals in the treated water is lower than 70 ng/L. The method has the advantages of simple material synthesis process, no secondary pollution, easy amplification and large-scale product application, and effectively overcomes the defects of other various methods for removing the perfluorooctanoic acid.
Detailed Description
Example one
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 45 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, and slowly adding the oil phase; adjusting the stirring speed to ensure that the size of oil droplets is distributed in 45-20 meshes; heating to 75 ℃, preserving heat for 3 hours, heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one (1) into a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and finishing the reaction for 24 hours under mechanical stirring; and (4) filtering out the liquid in the reactor, adding pure water for washing, cooling to room temperature, soaking and washing with ethanol, washing with deionized water, and filtering out the product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 40 g of dioxane and 60 g of water are added; mechanically stirring for 0.5 hour, adding 20 g of dimethylamine, raising and keeping the temperature of 65 ℃ for constant reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
Example two
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
step one, suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, and slowly adding the oil phase; adjusting the stirring speed to ensure that the size of oil droplets is distributed in 45-20 meshes; heating to 75 ℃, preserving heat for 3 hours, heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and keeping the reaction for 24 hours under mechanical stirring to finish the reaction; the liquid in the reactor was filtered off with suction and washed with pure water. Cooling to room temperature, soaking in ethanol, washing with deionized water, and filtering to obtain the final product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 48 g of dioxane and 72 g of water are added; mechanically stirring for 0.5 hour, adding 40 g of dimethylethanolamine, raising and keeping the temperature of 65 ℃ for constant reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
EXAMPLE III
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, and slowly adding the oil phase; adjusting the stirring speed to ensure that the size of oil droplets is distributed in 45-20 meshes; heating to 75 ℃, preserving heat for 3 hours, heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and finishing the reaction for 24 hours under mechanical stirring; the liquid in the reactor was filtered off with suction and washed with pure water. Cooling to room temperature, soaking in ethanol, washing with deionized water, and filtering to obtain the final product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 56 g of dioxane and 84 g of water are contained; mechanically stirring for 0.5 hour, adding 26 g of trimethylamine, raising the temperature, and keeping the constant temperature of 65 ℃ for reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
Example four
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, and preserving the heat for 3 hours. Heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, and then washing residual ethanol in the resin with a large amount of deionized water; drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and finishing the reaction for 24 hours under mechanical stirring; the liquid in the reactor was filtered off with suction and washed with pure water. Cooling to room temperature, soaking in ethanol, washing with deionized water, and filtering to obtain the final product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 48 g of dioxane and 72 g of water are added; mechanically stirring for 0.5 hour, adding 15 g of diethylenetriamine, raising the temperature, and keeping the constant temperature of 65 ℃ for reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
EXAMPLE five
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, and slowly adding the oil phase; adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, preserving heat for 3 hours, heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and finishing the reaction for 24 hours under mechanical stirring; and (4) filtering out the liquid in the reactor, adding pure water for washing, cooling to room temperature, soaking and washing with ethanol, washing with deionized water, and filtering out the product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 40 g of dioxane and 60 g of water are added; mechanically stirring for 0.5 hour, adding 16 g of triethylene tetramine, raising the temperature, and keeping the temperature of 65 ℃ for constant-temperature reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
EXAMPLE six
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, preserving heat for 3 hours, heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and stopping the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and finishing the reaction for 24 hours under mechanical stirring; and (4) filtering out the liquid in the reactor, adding pure water for washing, cooling to room temperature, soaking and washing with ethanol, washing with deionized water, and filtering out the product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 40 g of dioxane and 60 g of water are added; mechanically stirring for 0.5 hour, adding 16.5 g of tetraethylenepentamine, raising and keeping the temperature of 65 ℃ for constant reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
EXAMPLE seven
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, and preserving the heat for 3 hours. Heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and finishing the reaction for 24 hours under mechanical stirring; and (4) filtering out the liquid in the reactor, adding pure water for washing, cooling to room temperature, soaking and washing with ethanol, washing with deionized water, and filtering out the product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 40 g of dioxane and 60 g of water are added; mechanically stirring for 0.5 hour, adding 17 g of tri-n-butylamine, raising the temperature, keeping the temperature at 65 ℃ and reacting for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
Example eight
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, and preserving the heat for 3 hours. Heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 62 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and finishing the reaction for 24 hours under mechanical stirring; and (4) filtering out the liquid in the reactor, adding pure water for washing, cooling to room temperature, soaking and washing with ethanol, washing with deionized water, and filtering out the product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 48 g of dioxane and 72 g of water are added; mechanically stirring for 0.5 hour, adding 40 g of dimethylethanolamine, raising and keeping the temperature of 65 ℃ for constant reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
Comparative example 1
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, and preserving the heat for 3 hours. Heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
comparative example No. two
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 45 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, preserving heat for 3 hours, heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and stopping the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: macroporous resin post-crosslinking reaction:
accurately weighing the dry resin-based spheres prepared in the step one in a reactor, adding 800 g of dichloroethane, stirring and swelling for 10 hours at room temperature to ensure that the spheres are fully swelled, cooling to 0-5 ℃ by adopting an ice salt bath, adding 20 g of ferric chloride in batches, keeping the reaction for 30 minutes by adopting the ice salt bath, reacting for 45 minutes at room temperature, heating to 80 ℃, reacting for 10 hours, and finishing the reaction. And soaking and cleaning the resin by using acetone, washing the resin by using deionized water, washing the resin by using ethanol and the deionized water respectively, and filtering to obtain a product.
Comparative example No. three
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
accurately weighing 500 g of deionized water, 4 g of polyvinyl alcohol and 5 g of sodium chloride in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 140 g of toluene, 70 g of gasoline and 1 g of benzoyl peroxide, and fully and uniformly mixing;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, and preserving the heat for 3 hours. Heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and finishing the reaction for 24 hours under mechanical stirring; the liquid in the reactor was filtered off with suction and washed with pure water. Cooling to room temperature, soaking in ethanol, washing with deionized water, and filtering to obtain the final product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 48 g of dioxane and 72 g of water are added; mechanically stirring for 0.5 hour, adding 40 g of dimethylethanolamine, raising and keeping the temperature of 65 ℃ for constant reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
Comparative example No. four
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 0.5 g of azobisisobutyronitrile, and the components are fully and uniformly mixed;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, and preserving the heat for 3 hours. Heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and terminating the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and finishing the reaction for 24 hours under mechanical stirring; the liquid in the reactor was filtered off with suction and washed with pure water. Cooling to room temperature, soaking in ethanol, washing with deionized water, and filtering to obtain the final product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 48 g of dioxane and 72 g of water are added; mechanically stirring for 0.5 hour, adding 40 g of dimethylethanolamine, raising and keeping the temperature of 65 ℃ for constant reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
Comparative example five
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of methylcyclohexane and 0.5 g of azobisisobutyronitrile, and the components are fully and uniformly mixed;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, preserving heat for 3 hours, heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and stopping the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 64 g of m-chloroperoxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and mechanically stirring to react for 24 hours; the liquid in the reactor was filtered off with suction and washed with pure water. Cooling to room temperature, soaking in ethanol, washing with deionized water, and filtering to obtain the final product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 48 g of dioxane and 72 g of water are added; mechanically stirring for 0.5 hour, adding 40 g of dimethylethanolamine, raising and keeping the temperature of 65 ℃ for constant reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
Comparative example six
The preparation method of the composite macroporous adsorption resin for removing perfluorinated compounds in water comprises the following specific steps:
the method comprises the following steps: suspension polymerization:
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; accurately weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of methylcyclohexane and 0.5 g of azobisisobutyronitrile, and the components are fully and uniformly mixed;
standing the water phase for 20 minutes, slowly adding the oil phase, adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes, heating to 75 ℃, preserving heat for 3 hours, heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, and stopping the reaction;
after suction filtration, boiling with hot water and repeatedly washing, removing a pore-forming agent in an extractor with ethanol, then washing residual ethanol in the resin with a large amount of deionized water, and drying to constant weight for later use;
step two: epoxidation of dangling double bonds
Accurately weighing 80 g of the dry resin base ball prepared in the step one in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, and ensuring that the resin is fully swelled; adding 36 g of peroxybenzoic acid into the reactor, controlling the reaction temperature to be kept at 5 ℃, and mechanically stirring to keep reacting for 24 hours to finish the reaction; the liquid in the reactor was filtered off with suction and washed with pure water. Cooling to room temperature, soaking in ethanol, washing with deionized water, and filtering to obtain the final product.
Step three: functionalization of epoxide groups
Taking 50 g of the resin intermediate obtained in the second step, soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water, and adding a mixed solvent, wherein 48 g of dioxane and 72 g of water are added; mechanically stirring for 0.5 hour, adding 40 g of dimethylethanolamine, raising and keeping the temperature of 65 ℃ for constant reaction for 24 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
Example-evaluation test:
evaluation of Perfluorooctanoic acid (salt) adsorption Performance in Water
Respectively and accurately weighing 0.1 g of eight different resins in the examples and four different resins in the comparative examples, placing the eight resins in a 125 ml polyethylene terephthalate plastic bottle, respectively adding 100 ml of 10ug/L perfluorooctanoic acid and potassium perfluorooctanoate sulfonate solution, placing the mixture in a shaking table, carrying out vibration for 100 hours at 25 ℃ and 150rpm, after the vibration is finished, taking 2 ml of the solution, carrying out high-speed centrifugation, and testing a sample by using LC-MS/MS (liquid chromatography-mass spectrometry/mass spectrometry), wherein relevant results are shown in the table. It can be known from the table that the composite resin which mainly takes the hydrophobic effect as the main part and takes the charge effect as well is prepared by suspending double bond epoxidation and then utilizing an amination reagent to carry out ring opening and grafting amino functional groups, and the removal effect of trace perfluorooctanoic acid (salt) in water is the best and reaches more than 99.3 percent.
Perfluorooctanoic acid (or salt) removing effect of resin prepared by different methods
Claims (18)
1. A composite macroporous adsorption resin for removing perfluorinated compounds in water is characterized in that: the resin has amino functional groups as follows: (R1R2) NH-, (R1R2R3) N-, (R1) NH2-, wherein R1 and R2 are the same or different straight chain or branched chain aliphatic hydrocarbons, R3 is C6 or lower hydrocarbons, the particle size distribution is 0.4-0.85mm, the specific surface area is not less than 500-550 m-2(ii)/g, average micropore diameter of 3-5 nm.
2. The composite macroporous absorption resin for removing the perfluorinated compounds in the water as claimed in claim 1, wherein the preparation process comprises the following steps:
preparing a polystyrene macroporous adsorption resin base ball, performing suspension double bond epoxidation, and performing ring-opening amination reaction on an epoxy group.
3. The preparation method of composite macroporous absorption resin for removing perfluorinated compounds in water as claimed in claim 2, comprising the following steps:
(1) preparing a polystyrene macroporous adsorption resin base sphere, taking styrene, divinylbenzene or polyvinyl benzene as monomers, adding a pore-foaming agent, performing suspension polymerization to obtain the macroporous adsorption resin base sphere, removing the pore-foaming agent, and drying for later use;
(2) performing epoxidation on the dangling double bonds, fully swelling the resin-based spheres (dried) obtained in the step (1), performing epoxidation on the dangling double bonds which do not participate in suspension polymerization reaction in molecular chains by using organic peroxyacid, and washing off a solvent and excessive reactants to obtain a resin intermediate;
(3) and (3) performing ring-opening amination reaction on an epoxy group, fully swelling the resin intermediate obtained in the step (2), performing ring-opening reaction on the epoxy group by using an amination nucleophilic reagent, and washing away the solvent to obtain the macroporous adsorption resin grafted with an amino functional group.
4. The method for preparing the composite macroporous absorption resin for removing the perfluorinated compounds in the water as claimed in claim 3, wherein in the step (1), the polyvinyl benzene monomer can be one or a mixture of styrene, divinylbenzene and divinylxylene; the pore-forming agent can be one or a mixture of more of toluene, gasoline, methylcyclohexane and n-butanol.
5. The method as claimed in claim 4, wherein in the step (1), the mass ratio of the pore-forming agent to the polyvinyl benzene monomer is 1-1.5: 1.
6. The method for preparing a composite macroporous adsorbent resin for removing perfluorinated compounds in water as claimed in claim 4, wherein divinylbenzene is removed polymerization inhibitor and has an isotactic ratio of not less than 80%.
7. The preparation method of composite macroporous absorption resin for removing perfluorinated compounds in water as claimed in claim 3, wherein the step (2) comprises the following steps:
accurately weighing the resin-based spheres (dried) prepared in the step (1) into a reactor, adding a solvent to ensure that the resin is fully swelled, adding organic peroxy acid into the reactor to react at a low temperature of 0-5 ℃, heating to room temperature after the reaction is finished, soaking and cleaning with ethanol, washing with deionized water, and filtering out a product to obtain a resin intermediate.
8. The method for preparing composite macroporous adsorbent resin for removing perfluorinated compounds in water as claimed in claim 7, wherein the solvent in step (2) is one or more selected from acetone, dichloroethane, toluene and xylene.
9. The preparation method of composite macroporous absorption resin for removing perfluorinated compounds in water as claimed in claim 8, wherein the mass ratio of the solvent to the resin-based spheres (dry) in the step (2) is 4-6.5: 1.
10. The preparation method of composite macroporous absorption resin for removing perfluorinated compounds in water as claimed in claim 7, wherein the organic peroxyacid in step (2) is one or more of m-chloroperoxybenzoic acid, peroxyacetic acid, peroxybenzoic acid and trifluoroperoxyacetic acid.
11. The preparation method of composite macroporous absorption resin for removing perfluorinated compounds in water as claimed in claim 10, wherein the mass ratio of the organic peroxyacid to the resin-based spheres (dry) in the step (2) is 0.45-0.65: 1.
12. The preparation method of composite macroporous absorption resin for removing perfluorinated compounds in water as claimed in claim 3, wherein the step (3) comprises the following steps:
taking the resin intermediate obtained in the step (2), soaking the resin by using ethanol to fully swell the resin, washing the resin by using deionized water or pure water, and adding a mixed solvent; mechanically stirring for 0.5-1 hour, adding an amination reagent, heating to 60-75 ℃, and reacting at constant temperature for 24-30 hours; and (4) filtering the solution by suction, and respectively washing the solution by pure water, ethanol and pure water to obtain the composite macroporous adsorption resin.
13. The method as claimed in claim 12, wherein the mixed solvent in step (3) is dioxane and water at a mass ratio of 0.5-1: 1.
14. The preparation method of composite macroporous adsorbent resin for removing perfluorinated compounds in water as claimed in claim 12, wherein in step (3), the mass ratio of the mixed solvent to the resin intermediate is 2-3: 1.
15. The method for preparing the composite macroporous adsorbent resin for removing the perfluorinated compounds in water according to claim 12, wherein in the step (3), the amination reagent is one or more of dimethylamine, dimethylethanolamine, trimethylamine, tri-n-butylamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
16. The method for preparing composite macroporous absorption resin for removing perfluorinated compounds in water as claimed in claim 15, wherein in the step (3), the mass ratio of the amination reagent to the resin intermediate (dry weight) is 0.25-0.5: 1.
17. The composite macroporous adsorbent resin for removing perfluorinated compounds in water as claimed in claim 1, wherein the content of perfluorinated compounds in the treated water is less than 70 ng/L.
18. The preparation method of the composite macroporous absorption resin for removing the perfluorinated compounds in the water according to claim 2 is characterized by comprising the following steps,
respectively and accurately weighing 500 g of deionized water and 4 g of polyvinyl alcohol in a reactor according to a water phase formula, heating to 40-50 ℃, and starting stirring to uniformly mix all the raw materials; weighing in a beaker according to the formula of the oil phase: 100 g of divinylbenzene, 120 g of toluene and 1 g of benzoyl peroxide, and fully and uniformly mixing; standing the water phase for 20 minutes, slowly adding the oil phase, and adjusting the stirring speed to ensure that the size of oil droplets is distributed in a range of 45-20 meshes; heating to 75 ℃, preserving heat for 3 hours, heating to 82 ℃, preserving heat for 4 hours, heating to 87 ℃, preserving heat for 4 hours, terminating the reaction, and removing the pore-foaming agent to obtain a resin-based ball; after drying, accurately weighing 80 g of resin-based balls (dry) in a reactor, adding 500 g of dichloroethane, stirring and swelling for 1 hour at room temperature, adding 64 g of m-chloroperoxybenzoic acid in the reactor, controlling the reaction temperature to be kept at 5 ℃, reacting for 24 hours under mechanical stirring, filtering out liquid in the reactor, adding pure water for washing, cooling to room temperature, soaking and cleaning with ethanol, washing with deionized water, and filtering out a product; taking 50 g of the obtained resin intermediate, swelling the resin intermediate by using ethanol, adding a mixed solvent, wherein 48 g of dioxane and 72 g of water are mechanically stirred for 0.5 hour, adding 40 g of dimethylethanolamine, heating to 65 ℃, reacting at a constant temperature for 24 hours, filtering out the solution, and respectively washing by using pure water, ethanol and pure water to obtain the composite macroporous adsorption resin, wherein the particle size is distributed between 0.4 and 0.8mm, and the specific surface area is not less than 500-550m2(ii)/g, average micropore diameter 3-5 nm;
the composite resin containing amino functional groups can be prepared by the method, PFOA and PFOS are respectively reduced to 0.027 and 0.025ug/L from 10ug/L of inlet concentration through the adsorption evaluation of perfluorinated compounds in water, the clearance rate is as high as 99.73 percent and 99.65 percent, and the final content of the perfluorinated compounds is lower than 70 ng/L.
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