CN110860280A - Composite hybrid hydrogel with high adsorption capacity and preparation method and application thereof - Google Patents
Composite hybrid hydrogel with high adsorption capacity and preparation method and application thereof Download PDFInfo
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- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a composite hybrid hydrogel with high adsorption capacity, and a preparation method and application thereof, belonging to the technical field of preparation of environment-friendly materials. The composite hybrid hydrogel comprises: 2-10 parts of polymer, 2-50 parts of mesoporous nano particles, 2-30 parts of adsorption aid and 90-98 parts of solvent. Is prepared by freezing-thawing method. The composite hybrid hydrogel provided by the invention has higher adsorption capacity to organic industrial dyes, and is a high-efficiency adsorption material.
Description
Technical Field
The invention belongs to the technical field of preparation of environment-friendly materials, and particularly relates to a composite hybrid hydrogel with high adsorption capacity, and a preparation method and application thereof.
Background
The problem of water pollution is always the most important of the environmental pollution problems in China. Organic dyes in industrial wastewater are pollutants with a high proportion, such as methylene blue, methyl orange, malachite green, rhodamine B and the like. These dyes contain an aromatic ring structure in many cases, have high carcinogenicity, and are not easily decomposed. At present, some conventional treatment methods for organic dye wastewater mainly comprise: coagulating sedimentation method, air floatation method, adsorption method, etc. Among them, the adsorption method is considered to be the simplest and most efficient method.
However, the organic polymer network of the hydrogel contains a few adsorbable sites and has limited ability of interacting with guest molecules, so that the capacity of adsorbing pollutants is poor, and on the other hand, the adsorption of the adsorption material on the guest molecules is mostly non-covalent bond action, such as hydrogen bond action, electrostatic action, п - п interaction and the like.
Disclosure of Invention
The invention aims to provide a composite hybrid hydrogel with high adsorption capacity, a preparation method and application thereof, and the specific technical scheme is as follows:
a composite hybrid hydrogel with high adsorption capacity comprises: 2-10 parts of polymer, 2-50 parts of mesoporous nano particles, 2-30 parts of adsorption aid and 90-98 parts of solvent.
The molecular weight of the polymer is 70000-200000 g/mol; the polymer is one or more of polyvinyl alcohol 1750, polyvinyl alcohol 1788, polyvinyl alcohol 1799, polyvinyl alcohol 2099 and polyvinyl alcohol 2699.
The mesoporous nano-particles have a through-hole structure and the volume weight of the mesoporous nano-particles is 40-200kg/m3The diameter is 100-300nm, the specific surface area is 200-1600m2/g, preferably 1400-2/g。
The mesoporous nano-particles are preferably one or more of silicon dioxide, titanium dioxide, aluminum oxide and zirconium oxide.
The adsorption auxiliary agent has a conjugated structure, preferably a pi-pi conjugated structure, and the volume weight of the adsorption auxiliary agent is 800-1500kg/m3The specific surface area is 5-80m2/g。
The adsorption auxiliary agent is preferably one or more of carbon nano tube, carbon powder and graphite powder; the solvent is water.
The preparation method of the composite hybrid hydrogel comprises the steps of mixing and heating a macromolecule, mesoporous nano particles, an adsorption aid and a solvent, and performing freezing-unfreezing cycle for more than 3 times to prepare the composite hybrid hydrogel.
The mesoporous nano-particles have a through-hole structure, 10-30g of water, 5-10g of ethanol, 0.01-0.07g of hexadecyl trimethyl ammonium bromide, 30-50mg of ammonia water and 40-50mg of precursor molecules are mixed, stirred at normal temperature for 2-4 hours, and then the product is separated and washed; finally, sintering the product in a muffle furnace at 550 ℃ for 6 hours.
The heating temperature is 95-100 ℃, and the heating time is 6-10 hours; the freezing time is 12 hours, and the freezing temperature is-25 ℃ to 0 ℃; the thawing time is 2-4 hours, and the thawing is carried out at room temperature.
The application of the composite hybrid hydrogel or the composite hybrid hydrogel prepared by the preparation method is as follows: the composite hybrid hydrogel is used for adsorbing organic dyes in wastewater.
The organic dye is methylene blue, methyl orange, malachite green or rhodamine B.
The invention has the beneficial effects that:
(1) the composite hybrid hydrogel provided by the invention has the characteristics of light weight, multifunctional groups and high specific surface area. The mesoporous nano particles used in the invention have uniform particle size distribution, rich internal pore channels and specific surface area of 1400-1600m2The methylene blue is adsorbed by 263mg/g (the specific surface area and the adsorption effect are higher than those of the commercially available mesoporous silica); the effect of adsorbing methylene blue by the multi-walled carbon nano tube used in the invention reaches 152mg/g, the effect of adsorbing methylene blue by the multi-walled carbon nano tube, the multi-walled carbon nano tube and the multi-walled carbon nano tube through a synergistic effect can reach 467mg/g, and the multi-walled carbon nano tube has the characteristic of efficiently adsorbing methylene blue dye.
(2) Compared with the defects of weak adsorption capacity, complex preparation process, difficult cleaning and recovery and the like of the existing material, the composite hybrid hydrogel provided by the invention has the advantages of high adsorption capacity, simple and efficient preparation process, easy cleaning and recovery, easy industrial production and the like.
Drawings
FIG. 1 is a TEM image of mesoporous silica having a through-pore structure according to the present invention;
FIG. 2 is a photograph showing a comparison between the hydrogels obtained in comparative example 1, comparative example 2 and example 1 before and after adsorbing methylene blue; wherein 2-a is a photo before the hydrogel absorbs methylene blue, and 2-b is a photo after the hydrogel absorbs methylene blue.
Detailed Description
The invention provides a composite hybrid hydrogel with high adsorption capacity, a preparation method and application thereof, and the invention is further explained by combining an embodiment and a drawing.
The mesoporous nano particle with the through hole structure is prepared by mixing 10-30g of water, 5-10g of ethanol, 0.01-0.07g of hexadecyl trimethyl ammonium bromide, 30-50mg of ammonia water and 40-50mg of precursor molecules (precursor molecules of the nano particle), stirring at normal temperature for 2-4 hours, and then separating and washing the product; finally, sintering the product in a muffle furnace at 550 ℃ for 6 hours. FIG. 1 shows a TEM image of mesoporous silica having a through-pore structure according to the present invention.
Comparative example 1
2 parts by weight of a polyvinyl alcohol polymer was weighed, dissolved in 94 parts by weight of a solvent, and heated at 95 ℃ for 6 hours. The mixed solution was poured into a mold and left in a freezer of a refrigerator for 12 hours. Subsequently, the sample was thawed at room temperature for 2 hours. After this process was repeated three times, the hydrogel thus produced was taken out of the mold and used.
0.5g of the composite hybrid hydrogel obtained in comparative example 1 was weighed and immersed in 30mg/L of methylene blue aqueous solution. The system was placed in a shaker and thermostatted overnight at 35 ℃. And after the adsorption test is finished, taking the system clear liquid, carrying out ultraviolet-visible spectrophotometer test, observing the absorption intensity of the solution at 660nm, and calculating the concentration of the methylene blue aqueous solution after adsorption to be 25.2mg/L by comparing with a standard curve of the methylene blue.
Comparative example 2
Weighing 5 parts by weight of polyvinyl alcohol polymer and 5 parts by weight of MCM-41 mesoporous nano particles, dissolving in 90 parts by weight of solvent, and heating at 95 ℃ for 6 hours. The mixed solution was poured into a mold and left in a freezer of a refrigerator for 12 hours. Subsequently, the sample was thawed at room temperature for 2 hours. After this process was repeated three times, the hydrogel thus produced was taken out of the mold and used.
0.5g of the composite hybrid hydrogel obtained in comparative example 2 was weighed and immersed in 30mg/L of methylene blue aqueous solution. The system was placed in a shaker and thermostatted overnight at 35 ℃. And after the adsorption test is finished, taking the system clear liquid, carrying out ultraviolet-visible spectrophotometer test, observing the absorption intensity of the solution at 660nm, and calculating the concentration of the methylene blue aqueous solution after adsorption to be 15.9mg/L by comparing with a standard curve of the methylene blue.
Example 1
30g of water, 10g of ethanol, 0.07g of cetyltrimethylammonium bromide, 50mg of ammonia water and 50mg of ethyl orthosilicate were mixed. After stirring at room temperature for 2 hours, the product was separated and washed. Subsequently, the product was sintered at 550 ℃ for 6 hours in a muffle furnace to obtain mesoporous silica particles having through pores.
Weighing 5 parts by weight of polyvinyl alcohol macromolecules, 5 parts by weight of through-hole mesoporous silica particles and 2 parts by weight of multi-wall carbon nano tube adsorption auxiliary agent, dissolving in 92 parts by weight of solvent, and heating at 95 ℃ for 6 hours. The mixed solution was poured into a mold and left in a freezer of a refrigerator for 12 hours. Subsequently, the sample was thawed at room temperature for 2 hours. After this process was repeated three times, the hydrogel thus produced was taken out of the mold and used.
0.5g of the hybrid hydrogel obtained in example 1 was weighed and immersed in 30mg/L methylene blue aqueous solution. The system was placed in a shaker and thermostatted overnight at 35 ℃. And after the adsorption test is finished, taking the system clear liquid, carrying out ultraviolet-visible spectrophotometer test, observing the absorption intensity of the solution at 660nm, and calculating the concentration of the methylene blue aqueous solution after adsorption to be 8.1mg/L by comparing with a standard curve of the methylene blue.
The photographs of the hydrogels obtained in comparative example 1, comparative example 2 and example 1 before and after adsorbing methylene blue as shown in FIG. 2 were compared; wherein 2-a is a photo before the hydrogel adsorbs methylene blue, and the photo is a comparative example 1, a comparative example 2 and an example 1 from left to right in sequence; 2-b is a photograph of the hydrogel after adsorbing methylene blue, and is shown as comparative example 1, comparative example 2 and example 1 from left to right.
Example 2
25g of water, 5g of ethanol, 0.07g of cetyltrimethylammonium bromide, 50mg of ammonia water and 50mg of ethyl orthosilicate were mixed. After stirring at room temperature for 2 hours, the product was separated and washed. Subsequently, the product was sintered at 550 ℃ for 6 hours in a muffle furnace to obtain mesoporous silica particles having through pores.
Weighing 2 parts by weight of polyvinyl alcohol polymer, 5 parts by weight of through-hole mesoporous silica particles and 3 parts by weight of multi-wall carbon nano tube adsorption auxiliary agent, dissolving in 90 parts by weight of solvent, and heating at 95 ℃ for 6 hours. The mixed solution was poured into a mold and left in a freezer of a refrigerator for 12 hours. Subsequently, the sample was thawed at room temperature for 2 hours. After this process was repeated three times, the hydrogel thus produced was taken out of the mold and used.
0.5g of the hybrid hydrogel obtained in example 2 was weighed and immersed in 30mg/L methylene blue aqueous solution. The system was placed in a shaker and thermostatted overnight at 35 ℃. And after the adsorption test is finished, taking the system clear liquid, carrying out ultraviolet-visible spectrophotometer test, observing the absorption intensity of the solution at 660nm, and calculating the concentration of the solution after adsorption by comparing with a standard curve of methylene blue.
Example 3
25g of water, 10g of ethanol, 0.05g of cetyltrimethylammonium bromide, 50mg of ammonia water and 50mg of ethyl orthosilicate were mixed. After stirring at room temperature for 2 hours, the product was separated and washed. Subsequently, the product was sintered at 550 ℃ for 6 hours in a muffle furnace to obtain mesoporous silica particles having through pores.
Weighing 2 parts by weight of polyvinyl alcohol macromolecules, 6 parts by weight of through-hole mesoporous silica particles and 2 parts by weight of multi-wall carbon nano tube adsorption auxiliary agent, dissolving in 90 parts by weight of solvent, and heating at 95 ℃ for 6 hours. The mixed solution was poured into a mold and left in a freezer of a refrigerator for 12 hours. Subsequently, the sample was thawed at room temperature for 2 hours. After this process was repeated three times, the hydrogel thus produced was taken out of the mold and used.
0.5g of the hybrid hydrogel obtained in example 3 was weighed and immersed in 30mg/L methylene blue aqueous solution. The system was placed in a shaker and thermostatted overnight at 35 ℃. And after the adsorption test is finished, taking the system clear liquid, carrying out ultraviolet-visible spectrophotometer test, observing the absorption intensity of the solution at 660nm, and calculating the concentration of the solution after adsorption by comparing with a standard curve of methylene blue.
Example 4
30g of water, 8g of ethanol, 0.04g of cetyltrimethylammonium bromide, 50mg of ammonia water and 50mg of ethyl orthosilicate were mixed. After stirring at room temperature for 2 hours, the product was separated and washed. Subsequently, the product was sintered at 550 ℃ for 6 hours in a muffle furnace to obtain mesoporous silica particles having through pores.
Weighing 2 parts by weight of polyvinyl alcohol macromolecules, 2 parts by weight of through-hole mesoporous silica particles and 6 parts by weight of multi-wall carbon nano tube adsorption auxiliary agent, dissolving in 90 parts by weight of solvent, and heating at 95 ℃ for 6 hours. The mixed solution was poured into a mold and left in a freezer of a refrigerator for 12 hours. Subsequently, the sample was thawed at room temperature for 2 hours. After this process was repeated three times, the hydrogel thus produced was taken out of the mold and used.
0.5g of the hybrid hydrogel obtained in example 4 was weighed and soaked in 30mg/L aqueous solution of malachite green. The system was placed in a shaker and thermostatted overnight at 35 ℃. And after the adsorption test is finished, taking the clear liquid of the system, carrying out an ultraviolet-visible spectrophotometer test, observing the absorption intensity at 617nm of the solution, and calculating the concentration of the adsorbed solution to be 11.7mg/L by comparing with a standard curve of malachite green.
Example 5
30g of water, 10g of ethanol, 0.05g of cetyltrimethylammonium bromide, 50mg of ammonia water and 50mg of ethyl orthosilicate were mixed. After stirring at room temperature for 2 hours, the product was separated and washed. Subsequently, the product was sintered at 550 ℃ for 6 hours in a muffle furnace to obtain mesoporous silica particles having through pores.
Weighing 4 parts by weight of polyvinyl alcohol polymer, 2 parts by weight of through-hole mesoporous silica particles and 3 parts by weight of multi-wall carbon nano tube adsorption auxiliary agent, dissolving in 91 parts by weight of solvent, and heating at 95 ℃ for 6 hours. The mixed solution was poured into a mold and left in a freezer of a refrigerator for 12 hours. Subsequently, the sample was thawed at room temperature for 2 hours. After this process was repeated three times, the hydrogel thus produced was taken out of the mold and used.
0.5g of the hybrid hydrogel obtained in example 5 was weighed and soaked in 30mg/L aqueous solution of malachite green. The system was placed in a shaker and thermostatted overnight at 35 ℃. And after the adsorption test is finished, taking the clear liquid of the system, carrying out an ultraviolet-visible spectrophotometer test, observing the absorption intensity at 617nm of the solution, and calculating the concentration of the solution after adsorption to be 13.4mg/L by comparing with a standard curve of malachite green.
Example 6
30g of water, 8g of ethanol, 0.07g of cetyltrimethylammonium bromide, 50mg of ammonia water and 50mg of ethyl orthosilicate were mixed. After stirring at room temperature for 2 hours, the product was separated and washed. Subsequently, the product was sintered at 550 ℃ for 6 hours in a muffle furnace to obtain mesoporous silica particles having through pores.
Weighing 5 parts by weight of polyvinyl alcohol macromolecules, 2 parts by weight of through-hole mesoporous silica particles and 3 parts by weight of multi-wall carbon nano tube adsorption auxiliary agent, dissolving in 90 parts by weight of solvent, and heating at 95 ℃ for 6 hours. The mixed solution was poured into a mold and left in a freezer of a refrigerator for 12 hours. Subsequently, the sample was thawed at room temperature for 2 hours. After this process was repeated three times, the hydrogel thus produced was taken out of the mold and used.
0.5g of the composite hybrid hydrogel obtained in example 6 was weighed and soaked in 30mg/L methyl orange aqueous solution. The system was placed in a shaker and thermostatted overnight at 35 ℃. And after the adsorption test is finished, taking the system clear liquid, carrying out ultraviolet-visible spectrophotometer test, observing the absorption intensity of the 460nm position of the solution, and calculating the concentration of the solution after adsorption to be 21mg/L by comparing with a standard curve of methyl orange.
Example 7
20g of water, 10g of ethanol, 0.07g of cetyltrimethylammonium bromide, 50mg of ammonia water and 50mg of ethyl orthosilicate were mixed. After stirring at room temperature for 2 hours, the product was separated and washed. Subsequently, the product was sintered at 550 ℃ for 6 hours in a muffle furnace to obtain mesoporous silica particles having through pores.
3 parts by weight of polyvinyl alcohol polymer, 5 parts by weight of through-hole mesoporous silica particles and 2 parts by weight of multi-wall carbon nano tube adsorption auxiliary agent are weighed, dissolved in 90 parts by weight of solvent, and heated at 95 ℃ for 6 hours. The mixed solution was poured into a mold and left in a freezer of a refrigerator for 12 hours. Subsequently, the sample was thawed at room temperature for 2 hours. After this process was repeated three times, the hydrogel thus produced was taken out of the mold and used.
0.5g of the composite hybrid hydrogel obtained in example 7 was weighed and soaked in 30mg/L methyl orange aqueous solution. The system was placed in a shaker and thermostatted overnight at 35 ℃. And after the adsorption test is finished, taking the clear liquid of the system, carrying out an ultraviolet-visible spectrophotometer test, observing the absorption intensity of the 460nm position of the solution, and calculating the concentration of the solution after adsorption to be 20.6mg/L by comparing with a standard curve of methyl orange.
Claims (10)
1. A composite hybrid hydrogel with high adsorption capacity, which is characterized by comprising: 2-10 parts of polymer, 2-50 parts of mesoporous nano particles, 2-30 parts of adsorption aid and 90-98 parts of solvent.
2. The composite hybrid hydrogel according to claim 1, wherein the molecular weight of the polymer is 70000-200000 g/mol; the polymer is one or more of polyvinyl alcohol 1750, polyvinyl alcohol 1788, polyvinyl alcohol 1799, polyvinyl alcohol 2099 and polyvinyl alcohol 2699.
3. The composite hybrid hydrogel according to claim 1, wherein the mesoporous nanoparticles have a through-pore structure with a volume weight of 40-200kg/m3The diameter is 100-300nm, the specific surface area is 200-1600m2/g。
4. The composite hybrid hydrogel according to claim 1, wherein the mesoporous nanoparticle has a specific surface area of 1400-1600m2The mesoporous nano particles are one or more of silicon dioxide, titanium dioxide, aluminum oxide and zirconium oxide.
5. The composite hybrid hydrogel as claimed in claim 1, wherein the adsorption assistant has a conjugated structure with a bulk density of 800-1500kg/m3The specific surface area is 5-80m2/g。
6. The composite hybrid hydrogel according to claim 1, wherein the adsorption aid has a pi-pi conjugated structure, and is one or more of carbon nanotubes, carbon powder and graphite powder; the solvent is water.
7. The preparation method of the composite hybrid hydrogel as claimed in any one of claims 1 to 6, which comprises the steps of mixing and heating the macromolecule, the mesoporous nanoparticle, the adsorption aid and the solvent, and performing freeze-thaw cycle for more than 3 times to obtain the composite hybrid hydrogel.
8. The preparation method according to claim 7, wherein the mesoporous nanoparticles have a through-hole structure, and the method comprises mixing 10-30g of water, 5-10g of ethanol, 0.01-0.07g of hexadecyl trimethyl ammonium bromide, 30-50mg of ammonia water and 40-50mg of precursor molecules, stirring at normal temperature for 2-4 hours, and separating and washing the product; finally, sintering the product in a muffle furnace at 550 ℃ for 6 hours to obtain the product;
the heating temperature is 95-100 ℃, and the heating time is 6-10 hours; the freezing time is 12 hours, and the freezing temperature is-25 ℃ to 0 ℃; the thawing time is 2-4 hours, and the thawing is carried out at room temperature.
9. Use of the hybrid hydrogel according to any one of claims 1 to 6 or the hybrid hydrogel prepared by the preparation method according to claim 7 or 8 for adsorbing organic dyes in wastewater.
10. Use according to claim 9, wherein the organic dye is methylene blue, methyl orange, malachite green or rhodamine B.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111468082A (en) * | 2020-04-17 | 2020-07-31 | 李桂梅 | Environment-friendly composite hydrogel and preparation method and application thereof |
| CN111607115A (en) * | 2020-06-17 | 2020-09-01 | 大连理工大学 | Preparation method of high-strength hydrogel film capable of continuously treating dyeing sewage |
| CN112191231A (en) * | 2020-09-25 | 2021-01-08 | 深圳市圳力液体分离科技有限公司 | Hydrogel coated adsorbent material, preparation method and application |
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