CN115141303B - Preparation method of porous material capable of efficiently removing aromatic sulfonic acid compounds in water body - Google Patents
Preparation method of porous material capable of efficiently removing aromatic sulfonic acid compounds in water body Download PDFInfo
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Abstract
The invention discloses a preparation method of a porous material capable of efficiently removing aromatic sulfonic acid compounds in a water body, which comprises the following steps: 1) Preparing an aqueous phase; 2) Preparation of oil phase 3) synthetic porous resin: adding the oil phase into the water phase under stirring, introducing nitrogen, reacting under heating, filtering, cleaning, removing liquid, and vacuum drying the solid product to obtain porous resin; 4) And (5) resin functionalization treatment. The porous material capable of efficiently removing the aromatic sulfonic acid compounds in the water body is the crosslinked styrene-based porous resin with the polarity adjusted, and has excellent removal effect on the aromatic sulfonic acid compounds in the water body; in the resin, the rich pores and the large specific surface area endow the resin with good function of removing the aromatic sulfonic acid compound by physical adsorption; in the resin, metal ruthenium is introduced into the resin through silica microsphere loading, and the advanced oxidation of the metal ruthenium endows the resin with the function of chemically removing aromatic sulfonic acid compounds.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a preparation method of a porous material capable of efficiently removing aromatic sulfonic acid compounds in water.
Background
Aromatic sulfonic acid compounds are important chemical products, and are also important raw materials in the phenol compound preparation, dye and pharmaceutical industries, so that the aromatic sulfonic acid compounds have wide application. Aromatic sulfonic acid compounds are generally difficult to biodegrade, have poor biodegradability and high water solubility, so that the removal of the aromatic sulfonic acid compounds in water has great difficulty.
Resin adsorption is one of the common methods for removing organic pollutants in water, and the removal of the pollutants is mainly performed by physical adsorption of an adsorbent having a porous structure. The strong polarity of the aromatic sulfonic acid compound greatly reduces the adsorption removal effect of the conventional nonpolar resin; on the other hand, the traditional resin mainly removes pollutants through physical adsorption of an adsorbent with a porous structure, for example, an anion exchange resin for treating aromatic sulfonic acid wastewater and a preparation method thereof disclosed in patent CN103464223B have the defects of single removal effect, difficult improvement of adsorption capacity and the like.
Therefore, there is a need in the art to improve upon the prior art to provide a more reliable solution.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a porous material capable of efficiently removing aromatic sulfonic acid compounds in water aiming at the defects in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of a porous material capable of efficiently removing aromatic sulfonic acid compounds in a water body comprises the following steps:
1) Preparing an aqueous phase:
adding a dispersing agent and sodium chloride into water, and uniformly stirring to obtain a water phase;
2) Preparing an oil phase:
mixing styrene, divinylbenzene, glycidyl methacrylate, an initiator, a cross-linking agent and a pore-forming agent, and uniformly stirring to obtain an oil phase;
3) Synthetic porous resin:
adding the oil phase into the water phase under stirring, introducing nitrogen, reacting under heating, filtering, cleaning, removing liquid, and vacuum drying the solid product to obtain the porous resin, namely the porous organic material.
Preferably, the preparation method of the porous material capable of efficiently removing the aromatic sulfonic acid compound in the water body comprises the following steps:
1) Preparing an aqueous phase:
adding 1-4 parts of dispersing agent and 0.2-2 parts of sodium chloride into 80-90 parts of water according to parts by weight, and uniformly stirring to obtain a water phase;
2) Preparing an oil phase:
mixing 26-64 parts by weight of styrene, 22-76 parts by weight of divinylbenzene, 10-38 parts by weight of glycidyl methacrylate, 5-22 parts by weight of cross-linking agent, 0.2-3 parts by weight of initiator and 4-43 parts by weight of pore-forming agent, and uniformly stirring to obtain an oil phase;
3) Synthetic porous resin:
adding the oil phase into the water phase under stirring, introducing nitrogen, reacting for 2-7h at 68-85 ℃, then reacting for 2-5h at 85-95 ℃, filtering, washing with deionized water, then placing the mixture into a Soxhlet extractor for extraction for 4-10h, removing liquid, and vacuum drying the solid product to obtain the porous resin, namely the porous organic material.
Preferably, the preparation method of the porous material capable of efficiently removing the aromatic sulfonic acid compound in the water body further comprises the following step 4) resin functionalization treatment: adding the porous resin obtained in the step 3) into the dispersion liquid of the functionalization reagent, reacting for 3-16 hours under heating, then carrying out suction filtration and separation, and vacuum drying a solid product to obtain the functionalized porous resin, namely the porous organic material;
the functionalizing agent is a hydroxylation mesoporous silica microsphere grafted with ruthenium.
Preferably, the functionalizing agent is prepared by the following method:
i, preparing mesoporous silica microspheres;
II, hydroxylation modification of the surface of the mesoporous silica microsphere;
III, grafting metal ruthenium on the surface of the mesoporous silica microsphere.
Preferably, the step i specifically includes: adding dodecylamine into ethanol water solution, stirring until completely dissolving; then dripping ethyl orthosilicate into the obtained solution, stirring uniformly, and reacting for 2-6 hours; after the reaction is finished, centrifuging, washing a solid product, drying in vacuum, and calcining at 550-680 ℃ for 3-5h to obtain the mesoporous silica microspheres.
Preferably, the step ii specifically includes: adding mesoporous silica microspheres into deionized water, performing ultrasonic dispersion for 10-60min, then adding sodium hydroxide solution, continuously stirring, and performing constant-temperature reaction at 60-95 ℃ for 1-4 hours; cooling, filtering, washing with deionized water, and vacuum drying at 50-65deg.C to obtain mesoporous silica microsphere with hydroxylated surface.
Preferably, the step iii specifically includes: adding the mesoporous silica microspheres with the hydroxylated surfaces obtained in the step II into deionized water, performing ultrasonic dispersion for 10-30min, then dropwise adding an aqueous solution of ruthenium hexacarbonyl chloride in a stirring state, keeping continuous stirring after the dropwise adding is completed, reacting for 1-4h at 40-60 ℃, filtering, and washing a solid product to obtain the mesoporous silica microspheres grafted with the metal ruthenium.
Preferably, the step 4) specifically includes:
4-1) adding the functionalization reagent prepared in the step III into ethanol, stirring, and performing ultrasonic dispersion for 10-45min to obtain functionalization reagent dispersion;
4-2) adding the porous resin prepared in the step 3) into the functionalization reagent dispersion liquid, and reacting for 4-12 hours at 65-95 ℃ under stirring;
4-3) after the reaction is finished, filtering and separating, and vacuum drying the solid product to obtain the porous organic material product.
Preferably, the dispersing agent comprises gelatin and sodium carbonate in a mass ratio of 1:1.
Preferably, the initiator is azobisisobutyronitrile, the pore-forming agent is n-heptane or cyclohexane, and the crosslinking agent is one or more of divinylbenzene, divinyl ethylbenzene, ethylene glycol dimethacrylate, allyl methacrylate and allyl isocyanurate.
The beneficial effects of the invention are as follows:
the porous material capable of efficiently removing the aromatic sulfonic acid compounds in the water body is the crosslinked styrene-based porous resin with the polarity adjusted, and has excellent removal effect on the aromatic sulfonic acid compounds in the water body;
according to the invention, the mechanical strength and the service life of the porous structure of the crosslinked styrene-based porous resin can be effectively improved through the filling and strengthening effects of the silica microspheres on the porous structure of the crosslinked styrene-based porous resin; the mesoporous silica microspheres are mesoporous microspheres with rich pores, and the mesoporous silica microspheres can fill part of resin pores, but have the characteristics of multiple pores and high specific surface area, so that the modified resin has more rich pores and larger specific surface area, and the adsorption capacity can be improved; the rich pores and the large specific surface area endow the resin with good function of removing the aromatic sulfonic acid compound by physical adsorption;
according to the invention, the silicon dioxide microspheres are loaded with the metal ruthenium with strong oxidability, the oxidation potential is higher than that of ozone, the oxidation potential is stronger, and the aromatic sulfonic acid compounds can be decomposed into aromatic substances which are easier to biodegrade in a high-grade oxidation mode, so that the treatment effect on the aromatic sulfonic acid compounds in the water body can be improved; wherein, the metallic ruthenium can excite in the water body to generate hydroxyl free radical (OH), the hydroxyl free radical can destroy aromatic nucleus to form aliphatic compound with better biochemical degradation, and then the aliphatic compound is continuously converted into inorganic substance form (CO 2 +H 2 O); thereby imparting a function of chemically removing the aromatic sulfonic acid compound to the resin by the advanced oxidation of metallic ruthenium;
in the invention, the silicon dioxide microsphere not only plays a role in reinforcing mechanical performance, but also serves as a carrier of an active oxidant, so that the active oxide metal ruthenium can be uniformly dispersed in a water body, and the function of high-grade oxidative degradation of the aromatic sulfonic acid compound can be fully exerted.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The test methods used in the following examples are conventional methods unless otherwise specified. The material reagents and the like used in the following examples are commercially available unless otherwise specified. The following examples were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the specific conditions. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a preparation method of a porous material capable of efficiently removing aromatic sulfonic acid compounds in a water body, which comprises the following steps:
1) Preparing an aqueous phase:
adding 1-4 parts of dispersing agent and 0.2-2 parts of sodium chloride into 80-90 parts of water according to parts by weight, and uniformly stirring to obtain a water phase;
2) Preparing an oil phase:
mixing 26-64 parts by weight of styrene, 22-76 parts by weight of divinylbenzene, 10-38 parts by weight of glycidyl methacrylate, 5-22 parts by weight of cross-linking agent, 0.2-3 parts by weight of initiator and 4-43 parts by weight of pore-forming agent, and uniformly stirring to obtain an oil phase;
3) Synthetic porous resin:
adding the oil phase into the water phase under stirring, introducing nitrogen, reacting for 2-7h at 68-85 ℃, then reacting for 2-5h at 85-95 ℃, filtering, washing with deionized water, then placing the mixture into a Soxhlet extractor for extraction for 4-10h, removing liquid, and vacuum drying the solid product to obtain the porous resin, namely the porous organic material.
In a preferred embodiment, the dispersing agent comprises gelatin and sodium carbonate in a mass ratio of 1:1.
In a preferred embodiment, the initiator is azobisisobutyronitrile, the porogen is n-heptane or cyclohexane, and the crosslinker is one or more of divinylbenzene, divinylethylbenzene, ethylene glycol dimethacrylate, allyl methacrylate, allyl isocyanurate.
In the invention, the crosslinked styrene-based porous resin with polar groups is synthesized by adding the glycidyl methacrylate containing active epoxy groups into the resin system, and the polar of the resin is adjusted, so that the resin has good adsorption effect on polar aromatic sulfonic acid compounds.
In a preferred embodiment, the method for preparing the porous material capable of efficiently removing the aromatic sulfonic acid compound in the water body further comprises the following step 4) resin functionalization treatment:
4-1) adding the functionalization reagent prepared in the step III into ethanol, stirring, and performing ultrasonic dispersion for 10-45min to obtain functionalization reagent dispersion;
4-2) adding the porous resin prepared in the step 3) into the functionalization reagent dispersion liquid, and reacting for 4-12 hours at 65-95 ℃ under stirring;
4-3) after the reaction is finished, filtering and separating, and vacuum drying the solid product to obtain the porous organic material product.
Wherein the mass ratio of the functionalizing agent to the porous resin is 3.5-18:100.
The functionalization reagent is a ruthenium grafted hydroxylated mesoporous silica microsphere, and the functionalization reagent is prepared by the following method:
i, preparing mesoporous silica microspheres:
adding dodecylamine into ethanol water solution, stirring until completely dissolving; then dripping ethyl orthosilicate into the obtained solution, stirring uniformly, and reacting for 2-6 hours; after the reaction is finished, centrifuging, washing a solid product, drying in vacuum, and calcining at 550-680 ℃ for 3-5h to obtain the mesoporous silica microspheres.
II, hydroxylation modification of the surface of the mesoporous silica microsphere:
adding mesoporous silica microspheres into deionized water, performing ultrasonic dispersion for 10-60min, then adding sodium hydroxide solution, continuously stirring, and performing constant-temperature reaction at 60-95 ℃ for 1-4 hours; cooling, filtering, washing with deionized water, and vacuum drying at 50-65deg.C to obtain mesoporous silica microsphere with hydroxylated surface.
III, grafting metal ruthenium on the surface of the mesoporous silica microsphere:
adding the mesoporous silica microspheres with the hydroxylated surfaces obtained in the step II into deionized water, performing ultrasonic dispersion for 10-30min, then dropwise adding an aqueous solution of ruthenium hexacarbonyl chloride in a stirring state, keeping continuous stirring after the dropwise adding is completed, reacting for 1-4h at 40-60 ℃, filtering, and washing a solid product to obtain the mesoporous silica microspheres grafted with the metal ruthenium. Wherein the mass ratio of the ruthenium hexacarbonyl chloride to the hydroxylated mesoporous silica microsphere is 0.6-3.4:100.
In the invention, the functional reagent is adopted to treat the crosslinked styrene-based porous resin, so that the adsorption performance and mechanical strength of the resin can be effectively improved.
According to the invention, the mechanical strength and the service life of the porous structure of the crosslinked styrene-based porous resin can be effectively improved through the filling and strengthening effects of the silica microspheres on the porous structure of the crosslinked styrene-based porous resin; the surface of the silicon dioxide microsphere is modified with hydroxyl, and a part of hydroxyl is used for combining metal ruthenium through coordination so as to realize uniform grafting of ruthenium on the silicon dioxide microsphere; a large number of active epoxy groups are introduced into the crosslinked styryl porous resin through glycidyl methacrylate, and the rest part of hydroxyl groups can be subjected to condensation reaction with the active epoxy groups, so that the mesoporous silica microspheres grafted with ruthenium can be firmly and uniformly combined on the crosslinked styryl porous resin;
the mesoporous silica microspheres are mesoporous microspheres with rich pores, and the mesoporous silica microspheres can fill part of resin pores, but have the characteristics of multiple pores and high specific surface area, so that the modified resin has more rich pores and larger specific surface area, and the adsorption capacity can be improved; the rich pores and the large specific surface area endow the resin with good function of removing the aromatic sulfonic acid compound by physical adsorption.
In the invention, the silicon dioxide microspheres are loaded with the metal ruthenium with strong oxidability, the oxidation potential is higher than that of ozone, the metal ruthenium has stronger oxidability, and the aromatic sulfonic acid compounds can be decomposed into aromatic substances which are easier to be biologically degraded in a high-grade oxidation mode, so that the aromatic sulfonic acid compounds in the water body can be improvedThe main principle is as follows: the metallic ruthenium can excite in the water body to generate hydroxyl free radical (OH), the hydroxyl free radical can destroy aromatic nucleus to form aliphatic compound with better biochemical degradation, and then the aliphatic compound is continuously converted into inorganic substance form (CO 2 +H 2 O); thereby imparting the resin with a function of chemically removing the aromatic sulfonic acid compound by the advanced oxidation of metallic ruthenium.
In the invention, the silicon dioxide microsphere not only plays a role in reinforcing mechanical performance, but also serves as a carrier of an active oxidant, so that the active oxide metal ruthenium can be uniformly dispersed in a water body, and the function of high-grade oxidative degradation of the aromatic sulfonic acid compound can be fully exerted.
The foregoing is a general inventive concept and further examples and comparative examples are provided below on the basis thereof to fully illustrate the invention.
Example 1
A preparation method of a porous material capable of efficiently removing aromatic sulfonic acid compounds in a water body comprises the following steps:
1) Preparing an aqueous phase:
adding 2 parts of dispersing agent (1 part of gelatin and 1 part of sodium carbonate) and 1 part of sodium chloride into 85 parts of water according to parts by weight, and uniformly stirring to obtain a water phase;
2) Preparing an oil phase:
according to parts by weight, mixing 46 parts of styrene, 42 parts of divinylbenzene, 25 parts of glycidyl methacrylate, 16 parts of cross-linking agent, 0.8 part of initiator and 29 parts of pore-forming agent, and uniformly stirring to obtain an oil phase;
3) Synthetic porous resin:
adding the oil phase into the water phase under stirring, introducing nitrogen, reacting for 5 hours at 76 ℃, then reacting for 4 hours at 90 ℃, filtering, washing with deionized water, then placing the mixture into a Soxhlet extractor for extraction for 6 hours, removing liquid, and vacuum drying a solid product to obtain the porous resin, namely the porous organic material.
Wherein the initiator is azobisisobutyronitrile, the pore-forming agent is cyclohexane, and the crosslinking agent is divinylbenzene.
Example 2
A preparation method of a porous material capable of efficiently removing aromatic sulfonic acid compounds in a water body comprises the following steps:
1) Preparing an aqueous phase:
adding 2 parts of dispersing agent (1 part of gelatin and 1 part of sodium carbonate) and 1 part of sodium chloride into 85 parts of water according to parts by weight, and uniformly stirring to obtain a water phase;
2) Preparing an oil phase:
according to parts by weight, mixing 46 parts of styrene, 42 parts of divinylbenzene, 25 parts of glycidyl methacrylate, 16 parts of cross-linking agent, 0.8 part of initiator and 29 parts of pore-forming agent, and uniformly stirring to obtain an oil phase;
3) Synthetic porous resin:
adding the oil phase into the water phase under stirring, introducing nitrogen, reacting for 5 hours at 76 ℃, then reacting for 4 hours at 90 ℃, filtering, washing with deionized water, then placing the mixture into a Soxhlet extractor for extraction for 6 hours, removing liquid, and vacuum drying a solid product to obtain the porous resin, namely the porous organic material.
Wherein the initiator is azobisisobutyronitrile, the pore-forming agent is cyclohexane, and the crosslinking agent is divinylbenzene.
4) Resin functionalization treatment:
4-1) adding the functionalization reagent into ethanol, stirring, and performing ultrasonic dispersion for 10-45min to obtain functionalization reagent dispersion liquid;
4-2) adding the porous resin prepared in the step 3) into the functionalization reagent dispersion liquid, and reacting for 8 hours at 70 ℃ under stirring;
4-3) after the reaction is finished, filtering and separating, and vacuum drying the solid product to obtain the porous organic material product. Wherein the mass ratio of the functionalizing agent to the porous resin is 4.5:100.
The functionalization reagent is a ruthenium grafted hydroxylated mesoporous silica microsphere, and the functionalization reagent is prepared by the following method:
i, preparing mesoporous silica microspheres:
0.4g of dodecyl amine is added into 100mL of ethanol water solution (the volume ratio of ethanol to water is 1:1), and the mixture is stirred until the dodecyl amine is completely dissolved; then 2g of ethyl orthosilicate is added into the obtained solution, and the mixture is stirred uniformly and reacts for 4 hours; after the reaction is finished, centrifuging, washing a solid product, drying in vacuum, and calcining for 4 hours at 640 ℃ to obtain the mesoporous silica microspheres.
II, hydroxylation modification of the surface of the mesoporous silica microsphere:
adding mesoporous silica microspheres into deionized water, performing ultrasonic dispersion for 30min, then adding sodium hydroxide solution, continuously stirring, and performing constant-temperature reaction at 75 ℃ for 3 hours; cooling, filtering, washing with deionized water, and vacuum drying at 555 ℃ to obtain the mesoporous silica microsphere with the hydroxylated surface.
III, grafting metal ruthenium on the surface of the mesoporous silica microsphere:
and (3) adding the mesoporous silica microspheres with the hydroxylated surfaces obtained in the step (II) into deionized water, performing ultrasonic dispersion for 20min, then dropwise adding an aqueous solution of ruthenium hexacarbonyl chloride in a stirring state, keeping continuous stirring after the dropwise adding is completed, reacting for 3h at 45 ℃, filtering, and washing a solid product to obtain the mesoporous silica microspheres grafted with the metal ruthenium. Wherein the mass ratio of ruthenium hexacarbonyl chloride to hydroxylated mesoporous silica microspheres is 1.2:100.
Example 3
A preparation method of a porous material capable of efficiently removing aromatic sulfonic acid compounds in a water body comprises the following steps:
1) Preparing an aqueous phase:
adding 2 parts of dispersing agent (1 part of gelatin and 1 part of sodium carbonate) and 1 part of sodium chloride into 85 parts of water according to parts by weight, and uniformly stirring to obtain a water phase;
2) Preparing an oil phase:
according to parts by weight, mixing 46 parts of styrene, 42 parts of divinylbenzene, 25 parts of glycidyl methacrylate, 16 parts of cross-linking agent, 0.8 part of initiator and 29 parts of pore-forming agent, and uniformly stirring to obtain an oil phase;
3) Synthetic porous resin:
adding the oil phase into the water phase under stirring, introducing nitrogen, reacting for 5 hours at 76 ℃, then reacting for 4 hours at 90 ℃, filtering, washing with deionized water, then placing the mixture into a Soxhlet extractor for extraction for 6 hours, removing liquid, and vacuum drying a solid product to obtain the porous resin, namely the porous organic material.
Wherein the initiator is azobisisobutyronitrile, the pore-forming agent is cyclohexane, and the crosslinking agent is divinylbenzene.
4) Resin functionalization treatment:
4-1) adding the functionalization reagent into ethanol, stirring, and performing ultrasonic dispersion for 10-45min to obtain functionalization reagent dispersion liquid;
4-2) adding the porous resin prepared in the step 3) into the functionalization reagent dispersion liquid, and reacting for 8 hours at 70 ℃ under stirring;
4-3) after the reaction is finished, filtering and separating, and vacuum drying the solid product to obtain the porous organic material product. Wherein the mass ratio of the functionalizing agent to the porous resin is 6:100.
The functionalization reagent is a ruthenium grafted hydroxylated mesoporous silica microsphere, and the functionalization reagent is prepared by the following method:
i, preparing mesoporous silica microspheres:
0.4g of dodecyl amine is added into 100mL of ethanol water solution (the volume ratio of ethanol to water is 1:1), and the mixture is stirred until the dodecyl amine is completely dissolved; then 2g of ethyl orthosilicate is added into the obtained solution, and the mixture is stirred uniformly and reacts for 4 hours; after the reaction is finished, centrifuging, washing a solid product, drying in vacuum, and calcining for 4 hours at 640 ℃ to obtain the mesoporous silica microspheres.
II, hydroxylation modification of the surface of the mesoporous silica microsphere:
adding mesoporous silica microspheres into deionized water, performing ultrasonic dispersion for 30min, then adding sodium hydroxide solution, continuously stirring, and performing constant-temperature reaction at 75 ℃ for 3 hours; cooling, filtering, washing with deionized water, and vacuum drying at 555 ℃ to obtain the mesoporous silica microsphere with the hydroxylated surface.
III, grafting metal ruthenium on the surface of the mesoporous silica microsphere:
and (3) adding the mesoporous silica microspheres with the hydroxylated surfaces obtained in the step (II) into deionized water, performing ultrasonic dispersion for 20min, then dropwise adding an aqueous solution of ruthenium hexacarbonyl chloride in a stirring state, keeping continuous stirring after the dropwise adding is completed, reacting for 3h at 45 ℃, filtering, and washing a solid product to obtain the mesoporous silica microspheres grafted with the metal ruthenium. Wherein the mass ratio of ruthenium hexacarbonyl chloride to hydroxylated mesoporous silica microspheres is 1.2:100.
Example 4
A preparation method of a porous material capable of efficiently removing aromatic sulfonic acid compounds in a water body comprises the following steps:
1) Preparing an aqueous phase:
adding 2 parts of dispersing agent (1 part of gelatin and 1 part of sodium carbonate) and 1 part of sodium chloride into 85 parts of water according to parts by weight, and uniformly stirring to obtain a water phase;
2) Preparing an oil phase:
according to parts by weight, mixing 46 parts of styrene, 42 parts of divinylbenzene, 25 parts of glycidyl methacrylate, 16 parts of cross-linking agent, 0.8 part of initiator and 29 parts of pore-forming agent, and uniformly stirring to obtain an oil phase;
3) Synthetic porous resin:
adding the oil phase into the water phase under stirring, introducing nitrogen, reacting for 5 hours at 76 ℃, then reacting for 4 hours at 90 ℃, filtering, washing with deionized water, then placing the mixture into a Soxhlet extractor for extraction for 6 hours, removing liquid, and vacuum drying a solid product to obtain the porous resin, namely the porous organic material.
Wherein the initiator is azobisisobutyronitrile, the pore-forming agent is cyclohexane, and the crosslinking agent is divinylbenzene.
4) Resin functionalization treatment:
4-1) adding the functionalization reagent into ethanol, stirring, and performing ultrasonic dispersion for 10-45min to obtain functionalization reagent dispersion liquid;
4-2) adding the porous resin prepared in the step 3) into the functionalization reagent dispersion liquid, and reacting for 8 hours at 70 ℃ under stirring;
4-3) after the reaction is finished, filtering and separating, and vacuum drying the solid product to obtain the porous organic material product. Wherein the mass ratio of the functionalizing agent to the porous resin is 7.5:100.
The functionalization reagent is a ruthenium grafted hydroxylated mesoporous silica microsphere, and the functionalization reagent is prepared by the following method:
i, preparing mesoporous silica microspheres:
0.4g of dodecyl amine is added into 100mL of ethanol water solution (the volume ratio of ethanol to water is 1:1), and the mixture is stirred until the dodecyl amine is completely dissolved; then 2g of ethyl orthosilicate is added into the obtained solution, and the mixture is stirred uniformly and reacts for 4 hours; after the reaction is finished, centrifuging, washing a solid product, drying in vacuum, and calcining for 4 hours at 640 ℃ to obtain the mesoporous silica microspheres.
II, hydroxylation modification of the surface of the mesoporous silica microsphere:
adding mesoporous silica microspheres into deionized water, performing ultrasonic dispersion for 30min, then adding sodium hydroxide solution, continuously stirring, and performing constant-temperature reaction at 75 ℃ for 3 hours; cooling, filtering, washing with deionized water, and vacuum drying at 555 ℃ to obtain the mesoporous silica microsphere with the hydroxylated surface.
III, grafting metal ruthenium on the surface of the mesoporous silica microsphere:
and (3) adding the mesoporous silica microspheres with the hydroxylated surfaces obtained in the step (II) into deionized water, performing ultrasonic dispersion for 20min, then dropwise adding an aqueous solution of ruthenium hexacarbonyl chloride in a stirring state, keeping continuous stirring after the dropwise adding is completed, reacting for 3h at 45 ℃, filtering, and washing a solid product to obtain the mesoporous silica microspheres grafted with the metal ruthenium. Wherein the mass ratio of ruthenium hexacarbonyl chloride to hydroxylated mesoporous silica microspheres is 1.2:100.
Example 5
A preparation method of a porous material capable of efficiently removing aromatic sulfonic acid compounds in a water body comprises the following steps:
1) Preparing an aqueous phase:
adding 2 parts of dispersing agent (1 part of gelatin and 1 part of sodium carbonate) and 1 part of sodium chloride into 85 parts of water according to parts by weight, and uniformly stirring to obtain a water phase;
2) Preparing an oil phase:
according to parts by weight, mixing 46 parts of styrene, 42 parts of divinylbenzene, 25 parts of glycidyl methacrylate, 16 parts of cross-linking agent, 0.8 part of initiator and 29 parts of pore-forming agent, and uniformly stirring to obtain an oil phase;
3) Synthetic porous resin:
adding the oil phase into the water phase under stirring, introducing nitrogen, reacting for 5 hours at 76 ℃, then reacting for 4 hours at 90 ℃, filtering, washing with deionized water, then placing the mixture into a Soxhlet extractor for extraction for 6 hours, removing liquid, and vacuum drying a solid product to obtain the porous resin, namely the porous organic material.
Wherein the initiator is azobisisobutyronitrile, the pore-forming agent is cyclohexane, and the crosslinking agent is divinylbenzene.
4) Resin functionalization treatment:
4-1) adding the functionalization reagent into ethanol, stirring, and performing ultrasonic dispersion for 10-45min to obtain functionalization reagent dispersion liquid;
4-2) adding the porous resin prepared in the step 3) into the functionalization reagent dispersion liquid, and reacting for 8 hours at 70 ℃ under stirring;
4-3) after the reaction is finished, filtering and separating, and vacuum drying the solid product to obtain the porous organic material product. Wherein the mass ratio of the functionalizing agent to the porous resin is 7.5:100.
The functionalization reagent is a ruthenium grafted hydroxylated mesoporous silica microsphere, and the functionalization reagent is prepared by the following method:
i, preparing mesoporous silica microspheres:
0.4g of dodecyl amine is added into 100mL of ethanol water solution (the volume ratio of ethanol to water is 1:1), and the mixture is stirred until the dodecyl amine is completely dissolved; then 2g of ethyl orthosilicate is added into the obtained solution, and the mixture is stirred uniformly and reacts for 4 hours; after the reaction is finished, centrifuging, washing a solid product, drying in vacuum, and calcining for 4 hours at 640 ℃ to obtain the mesoporous silica microspheres.
II, hydroxylation modification of the surface of the mesoporous silica microsphere:
adding mesoporous silica microspheres into deionized water, performing ultrasonic dispersion for 30min, then adding sodium hydroxide solution, continuously stirring, and performing constant-temperature reaction at 75 ℃ for 3 hours; cooling, filtering, washing with deionized water, and vacuum drying at 555 ℃ to obtain the mesoporous silica microsphere with the hydroxylated surface.
III, grafting metal ruthenium on the surface of the mesoporous silica microsphere:
and (3) adding the mesoporous silica microspheres with the hydroxylated surfaces obtained in the step (II) into deionized water, performing ultrasonic dispersion for 20min, then dropwise adding an aqueous solution of ruthenium hexacarbonyl chloride in a stirring state, keeping continuous stirring after the dropwise adding is completed, reacting for 3h at 45 ℃, filtering, and washing a solid product to obtain the mesoporous silica microspheres grafted with the metal ruthenium. Wherein the mass ratio of ruthenium hexacarbonyl chloride to hydroxylated mesoporous silica microspheres is 1.8:100.
Comparative example 1
This example is substantially identical to example 4, except that: the functionalizing agent in this example is a hydroxylated mesoporous silica microsphere, which is prepared by the following method:
i, preparing mesoporous silica microspheres:
0.4g of dodecyl amine is added into 100mL of ethanol water solution (the volume ratio of ethanol to water is 1:1), and the mixture is stirred until the dodecyl amine is completely dissolved; then 2g of ethyl orthosilicate is added into the obtained solution, and the mixture is stirred uniformly and reacts for 4 hours; after the reaction is finished, centrifuging, washing a solid product, drying in vacuum, and calcining for 4 hours at 640 ℃ to obtain the mesoporous silica microspheres.
II, hydroxylation modification of the surface of the mesoporous silica microsphere:
adding mesoporous silica microspheres into deionized water, performing ultrasonic dispersion for 30min, then adding sodium hydroxide solution, continuously stirring, and performing constant-temperature reaction at 75 ℃ for 3 hours; cooling, filtering, washing with deionized water, and vacuum drying at 555 ℃ to obtain the mesoporous silica microsphere with the hydroxylated surface.
Comparative example 2
A preparation method of a porous material capable of efficiently removing aromatic sulfonic acid compounds in a water body comprises the following steps:
1) Preparing an aqueous phase:
adding 2 parts of dispersing agent (1 part of gelatin and 1 part of sodium carbonate) and 1 part of sodium chloride into 85 parts of water according to parts by weight, and uniformly stirring to obtain a water phase;
2) Preparing an oil phase:
according to parts by weight, mixing 46 parts of styrene, 42 parts of divinylbenzene, 25 parts of glycidyl methacrylate, 16 parts of cross-linking agent, 0.8 part of initiator and 29 parts of pore-forming agent, and uniformly stirring to obtain an oil phase;
3) Synthetic porous resin:
adding the oil phase into the water phase under stirring, introducing nitrogen, reacting for 5 hours at 76 ℃, then reacting for 4 hours at 90 ℃, filtering, washing with deionized water, then placing the mixture into a Soxhlet extractor for extraction for 6 hours, removing liquid, and vacuum drying a solid product to obtain the porous resin, namely the porous organic material.
Wherein the initiator is azobisisobutyronitrile, the pore-forming agent is cyclohexane, and the crosslinking agent is divinylbenzene.
4) Resin functionalization treatment:
adding the porous resin prepared in the step 3) into an aqueous solution of ruthenium hexacarbonyl chloride, and reacting for 8 hours at 70 ℃ under stirring;
4-3) after the reaction is finished, filtering and separating, and vacuum drying the solid product to obtain the porous organic material product. Wherein the mass ratio of ruthenium hexacarbonyl chloride to the porous resin is 0.2:100.
The porous materials prepared in examples 1 to 5 and comparative examples 1 to 2 were subjected to adsorption experiments to further illustrate the present invention.
The experimental method comprises the following steps:
1. preparing a benzenesulfonic acid solution with the concentration of 400 mg/L;
2. weighing 0.2g of porous polymer material, soaking in deionized water for 6 hours, removing free water to obtain pretreated wet resin, adding the wet resin into a 100ml conical flask with a plug, adding 30ml of benzenesulfonic acid solution, plugging the bottle stopper, oscillating at 25 ℃, measuring the concentration of the solution once every 10 minutes until the concentration of the solution is not changed, and measuring the adsorption balance time and the equilibrium adsorption quantity of the porous polymer material on aniline and benzenesulfonic acid in a single-component solution;
wherein, the concentration of the benzenesulfonic acid is measured by an ultraviolet spectrophotometer, and the calculation formula of the equilibrium adsorption quantity is as follows:
wherein Q is e (mg/g) is the amount of contaminant adsorbed per gram of adsorbent material, C i (mg/g) and C 0 (mg/g) is the initial concentration and adsorption equilibrium concentration of the contaminant, respectively, W (g) is the dry weight of the adsorbent material, and V (L) is the volume of the contaminant solution.
(1) The experimental results of benzenesulfonic acid adsorption are shown in table 1 below:
TABLE 1
From the results of examples 1 and examples 2 to 5, it is apparent that the porous materials obtained when the crosslinked styryl porous resin was treated without the functionalizing agent (example 1) had significantly inferior adsorption removal performance to benzenesulfonic acid than the porous materials obtained with the functionalizing agent (examples 2 to 5); as can be seen from comparison of the results of comparative example 1 and example 4, the functionalized modifier of comparative example 1 does not incorporate ruthenium hexacarbonyl chloride, but does not have the function of degrading benzenesulfonic acid by advanced oxidation, and the adsorption removal performance of benzenesulfonic acid is also significantly reduced; as can be seen from comparison of the results of comparative example 2 and example 4, ruthenium hexacarbonyl chloride added in comparative example 2 is difficult to uniformly disperse into a resin system, so that it is difficult to exert the function of oxidative degradation of benzenesulfonic acid.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (9)
1. The preparation method of the porous material capable of efficiently removing the aromatic sulfonic acid compound in the water body is characterized by comprising the following steps of:
1) Preparing an aqueous phase:
adding a dispersing agent and sodium chloride into water, and uniformly stirring to obtain a water phase;
2) Preparing an oil phase:
mixing styrene, divinylbenzene, glycidyl methacrylate, an initiator, a cross-linking agent and a pore-forming agent, and uniformly stirring to obtain an oil phase;
3) Synthetic porous resin:
adding the oil phase into the water phase under stirring, introducing nitrogen, reacting under heating, filtering, cleaning, removing liquid, and vacuum drying the solid product to obtain porous resin, namely the porous organic material;
step 4) resin functionalization treatment: adding the porous resin obtained in the step 3) into the dispersion liquid of the functionalization reagent, reacting for 3-16 hours under heating, then carrying out suction filtration and separation, and vacuum drying a solid product to obtain the functionalized porous resin, namely the porous organic material;
the functionalizing agent is a hydroxylation mesoporous silica microsphere grafted with ruthenium.
2. The method for preparing the porous material capable of efficiently removing the aromatic sulfonic acid compound from the water body according to claim 1, comprising the following steps:
1) Preparing an aqueous phase:
adding 1-4 parts of dispersing agent and 0.2-2 parts of sodium chloride into 80-90 parts of water according to parts by weight, and uniformly stirring to obtain a water phase;
2) Preparing an oil phase:
mixing 26-64 parts by weight of styrene, 22-76 parts by weight of divinylbenzene, 10-38 parts by weight of glycidyl methacrylate, 5-22 parts by weight of cross-linking agent, 0.2-3 parts by weight of initiator and 4-43 parts by weight of pore-forming agent, and uniformly stirring to obtain an oil phase;
3) Synthetic porous resin:
adding the oil phase into the water phase under stirring, introducing nitrogen, reacting for 2-7h at 68-85 ℃, then reacting for 2-5h at 85-95 ℃, filtering, washing with deionized water, then placing the mixture into a Soxhlet extractor for extraction for 4-10h, removing liquid, and vacuum drying the solid product to obtain porous resin, namely the porous organic material;
step 4) resin functionalization treatment: adding the porous resin obtained in the step 3) into the dispersion liquid of the functionalization reagent, reacting for 3-16 hours under heating, then carrying out suction filtration and separation, and vacuum drying a solid product to obtain the functionalized porous resin, namely the porous organic material;
the functionalizing agent is a hydroxylation mesoporous silica microsphere grafted with ruthenium.
3. The method for preparing the porous material capable of efficiently removing the aromatic sulfonic acid compound in the water body according to claim 2, wherein the functionalizing agent is prepared by the following method:
i, preparing mesoporous silica microspheres;
II, hydroxylation modification of the surface of the mesoporous silica microsphere;
III, grafting metal ruthenium on the surface of the mesoporous silica microsphere.
4. The method for preparing the porous material capable of efficiently removing the aromatic sulfonic acid compound in the water body according to claim 3, wherein the step i is specifically: adding dodecylamine into ethanol water solution, stirring until completely dissolving; then dripping tetraethoxysilane into the obtained solution, uniformly stirring, and reacting for 2-6 hours; after the reaction is finished, centrifuging, washing a solid product, drying in vacuum, and calcining at 550-680 ℃ for 3-5h to obtain the mesoporous silica microspheres.
5. The method for preparing the porous material capable of efficiently removing the aromatic sulfonic acid compound in the water body according to claim 4, wherein the step ii is specifically: adding mesoporous silica microspheres into deionized water, performing ultrasonic dispersion for 10-60min, then adding sodium hydroxide solution, continuously stirring, and performing constant-temperature reaction at 60-95 ℃ for 1-4 hours; cooling, filtering, washing with deionized water, and vacuum drying at 50-65deg.C to obtain mesoporous silica microsphere with hydroxylated surface.
6. The method for preparing the porous material capable of efficiently removing the aromatic sulfonic acid compound in the water body according to claim 5, wherein the step iii is specifically: adding the mesoporous silica microspheres with the hydroxylated surfaces obtained in the step II into deionized water, performing ultrasonic dispersion for 10-30min, then dropwise adding an aqueous solution of ruthenium hexacarbonyl chloride in a stirring state, keeping continuous stirring after the dropwise adding is completed, reacting for 1-4h at 40-60 ℃, filtering, and washing a solid product to obtain the mesoporous silica microspheres grafted with the metal ruthenium.
7. The method for preparing the porous material capable of efficiently removing the aromatic sulfonic acid compound from the water body according to claim 6, wherein the step 4) is specifically:
4-1) adding the functionalization reagent prepared in the step III into ethanol, stirring, and performing ultrasonic dispersion for 10-45min to obtain functionalization reagent dispersion;
4-2) adding the porous resin prepared in the step 3) into the functionalization reagent dispersion liquid, and reacting for 4-12 hours at 65-95 ℃ under stirring;
4-3) after the reaction is finished, filtering and separating, and vacuum drying the solid product to obtain the porous organic material product.
8. The method for preparing the porous material capable of efficiently removing the aromatic sulfonic acid compound in the water body according to claim 1, wherein the dispersing agent comprises gelatin and sodium carbonate in a mass ratio of 1:1.
9. The method for preparing the porous material capable of efficiently removing the aromatic sulfonic acid compound in the water body according to claim 1, wherein the initiator is azobisisobutyronitrile, the pore-forming agent is n-heptane or cyclohexane, and the crosslinking agent is one or more of divinylbenzene, ethylene glycol dimethacrylate, allyl methacrylate and allyl isocyanate.
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| US5880240A (en) * | 1996-04-03 | 1999-03-09 | Arakawa Chemical Industries, Ltd. | Alkyl-containing porous resin, process for its preparation and its use |
| CN105111365A (en) * | 2015-09-10 | 2015-12-02 | 南京师范大学 | Amino-modifying interpenetrating resin adsorbent and preparing method thereof |
| CN107617437A (en) * | 2017-08-25 | 2018-01-23 | 浙江工业大学 | A kind of ruthenium carried titanium dioxide hollow ball embeds Nano particles of silicon dioxide catalyst and its preparation method and application |
| CN114682229A (en) * | 2022-03-29 | 2022-07-01 | 西安蓝深新材料科技有限公司 | Boron adsorption resin and preparation method and application thereof |
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| US5880240A (en) * | 1996-04-03 | 1999-03-09 | Arakawa Chemical Industries, Ltd. | Alkyl-containing porous resin, process for its preparation and its use |
| CN105111365A (en) * | 2015-09-10 | 2015-12-02 | 南京师范大学 | Amino-modifying interpenetrating resin adsorbent and preparing method thereof |
| CN107617437A (en) * | 2017-08-25 | 2018-01-23 | 浙江工业大学 | A kind of ruthenium carried titanium dioxide hollow ball embeds Nano particles of silicon dioxide catalyst and its preparation method and application |
| CN114682229A (en) * | 2022-03-29 | 2022-07-01 | 西安蓝深新材料科技有限公司 | Boron adsorption resin and preparation method and application thereof |
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