CN112516974B - Water treatment nano material composite film - Google Patents

Water treatment nano material composite film Download PDF

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CN112516974B
CN112516974B CN202011113184.4A CN202011113184A CN112516974B CN 112516974 B CN112516974 B CN 112516974B CN 202011113184 A CN202011113184 A CN 202011113184A CN 112516974 B CN112516974 B CN 112516974B
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史逸尘
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Henan Licheng Environmental Technology Co ltd
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Deng Mingli
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—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
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • 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
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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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
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
    • 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
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    • C02F2101/20—Heavy metals or heavy metal compounds

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Abstract

The invention discloses a water treatment nano material composite membrane, and belongs to the technical field of sewage treatment. The invention firstly oxidizes dextran with potassium periodate to prepare oxidized dextran, then uses polyacrylic acid and diethylenetriamine to treat carbon nano tube to prepare modified carbon nano tube, secondly mixes oxidized dextran with polyallylamine hydrochloride and modified carbon nano tube to react to prepare microgel, then mixes microgel with tetrabutyl titanate, hydrolyzes and filters to prepare modified microgel, finally mixes the modified microgel with polyvinylidene fluoride and polyvinylpyrrolidone to prepare film forming liquid, and then forms film on a glass plate, and then uncovers the film, washes and dries to prepare the water treatment nano material composite film. The water treatment nano material composite membrane prepared by the invention has good treatment capacity on water polluted by metal ions and organic matters.

Description

Water treatment nano material composite film
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a water treatment nano material composite membrane.
Background
With the development of industry, heavy metal pollution is more and more serious, and the transmission of heavy metal wastewater pollution through food chains can have profound influence on the environment, so that the heavy metal wastewater pollution is also gradually becoming a global research topic. At present, the water heavy metal pollution remediation and treatment adopts the following two basic approaches: firstly, the bioavailability of heavy metals and the migration capability in a water body are reduced; and secondly, thoroughly removing heavy metals from polluted water, wherein the heavy metals mainly comprise the following three types: chemical, physicochemical, and biological processes.
In heavy metal sewage treatment, an adsorption method in a physical method is the most commonly used technical method, and mainly uses porous solid substances to adsorb pollutants in water to treat wastewater. The traditional adsorbent comprises active carbon, zeolite, vermiculite, sepiolite, diatomite, ceramic particles and the like, wherein the ceramic particles are a cheaper product for wastewater treatment, the existing research ceramic particles are generally prepared by adopting a sintering method and a baking-free method, but the traditional adsorbent cannot meet the requirements of high-efficiency environment-friendly development, and particularly the surface of phosphogypsum products has poor overall performance due to higher content of soluble impurities in phosphogypsum, so that the research on phosphogypsum products for adsorbing heavy metal ions is valued by researchers.
The surface of phosphogypsum product for heavy metal sewage adsorption treatment in the prior art has the problems that the surface is pulverized, the strength and toughness of phosphogypsum composite film product are further reduced, the quality of phosphogypsum product is poor, the weather resistance and corrosion resistance of the product are poor, the service life is short and the like due to the fact that the content of soluble impurities in phosphogypsum is high, especially the content of sodium is high.
The traditional sewage treatment method has the problems of high cost, low efficiency, secondary pollution and the like. Research shows that the semiconductor nano-scale oxide with photocatalysis can degrade various pollutants by utilizing ultraviolet rays, can oxidize and decompose hydrocarbons, surfactants, organic dyes, nitrogen-containing organic matters, organophosphorus pesticides, wood preservatives and the like in water, and can be used for sewage treatment. When the composite membrane prepared from the powder photocatalytic oxide is used for sewage treatment, the problems that the powder is difficult to recover, the light transmittance is affected by suspended powder and the like exist; therefore, titanium dioxide films are mostly adopted for photocatalysis in recent years, but the problems of small contact area, low catalytic efficiency, short film service life and the like caused by nano titanium dioxide agglomeration exist.
Disclosure of Invention
The invention aims to provide a water treatment nano material composite membrane and a preparation method thereof, which are used for solving the problems in the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the water treatment nano material composite membrane is characterized by mainly comprising the following raw material components in parts by weight: 40-70 parts of polyvinylidene fluoride, 4-10 parts of polyvinylpyrrolidone and 5-12 parts of nano titanium dioxide.
The water treatment nano material composite film is characterized by further comprising the following raw material components in parts by weight: 10-20 parts of microgel.
Preferably, the microgel is prepared from polyallylamine hydrochloride, modified carbon nano-tubes and oxidized dextran; the oxidized dextran is prepared by treating dextran with potassium periodate; the modified carbon nano tube is prepared by modifying a carbon nano tube by polyacrylic acid and diethylenetriamine.
As optimization, the water treatment nano material composite film mainly comprises the following raw material components in parts by weight: 65 parts of polyvinylidene fluoride, 8 parts of polyvinylpyrrolidone, 8 parts of nano titanium dioxide and 12 parts of microgel.
As optimization, the preparation method of the water treatment nano material composite film mainly comprises the following preparation steps:
(1) Reacting dextran with potassium periodate, purifying to obtain oxidized dextran, and reacting oxidized dextran with polyallylamine hydrochloride and modified carbon nano tube to obtain microgel;
(2) Mixing the microgel obtained in the step (1) with tetrabutyl titanate, adding chloroform and dilute nitric acid, stirring for reaction, filtering, and drying to obtain modified microgel;
(3) Mixing the modified microgel obtained in the step (2) with a dimethylacetamide solution, adding polyvinylidene fluoride and polyvinylpyrrolidone, and stirring and mixing to obtain a film forming solution;
(4) The film forming liquid obtained in the step (3) is coated on a glass plate by a scraper in a scraping way, and is immersed in a gel bath, after standing, the glass plate is taken out, film is uncovered, and the water treatment nano material composite film is obtained after washing and drying;
(5) And (3) performing index analysis on the water treatment nano material composite film obtained in the step (4).
As optimization, the preparation method of the water treatment nano material composite film mainly comprises the following preparation steps:
(1) Dextran and water are mixed according to the mass ratio of 1:25, adding potassium periodate with the mass of 0.9 times of that of dextran, stirring and reacting in a nitrogen atmosphere to obtain oxidized dextran mixed solution, and mixing the oxidized dextran mixed solution with a barium chloride solution with the mass fraction of 15% according to the mass ratio of 1:1.5, mixing, stirring and reacting, filtering, removing sediment to obtain a pretreated oxidized dextran mixed solution, and mixing the pretreated oxidized dextran mixed solution with a sodium sulfate solution with the mass fraction of 15% according to the mass ratio of 1:1.6, mixing, stirring, reacting, filtering to obtain oxidized dextran dispersion liquid, and mixing polyallylamine hydrochloride and water according to the mass ratio of 1:180, adding modified carbon nano tubes with the mass of 1-2 times of that of polyallylamine hydrochloride, stirring and dispersing, and then adjusting the pH value to 9.8 to obtain mixed dispersion liquid, and mixing the mixed dispersion liquid and oxidized dextran dispersion liquid according to the volume ratio of 1:1, mixing, controlling the adding rate of oxidized dextran dispersion liquid to be 5-8 mL/min, stirring and reacting in a nitrogen atmosphere, and carrying out suction filtration and drying to obtain microgel;
(2) Mixing the microgel obtained in the step (1) with chloroform according to a mass ratio of 1:20, adding tetrabutyl titanate with the mass of 2-4 times of that of the microgel, stirring and mixing to obtain a microgel mixed solution, mixing the microgel mixed solution with 10 mass percent nitric acid according to the mass ratio of 8:1, stirring and hydrolyzing, filtering and drying to obtain modified microgel;
(3) Mixing the modified microgel obtained in the step (2) with 80% of dimethylacetamide solution according to the mass ratio of 1:20, adding polyvinylidene fluoride with the mass 3-4 times of that of the modified microgel and polyvinylpyrrolidone with the mass 0.3-0.4 times of that of the modified microgel, and stirring and mixing to obtain film forming liquid;
(4) The film forming liquid obtained in the step (3) is coated on a glass plate by a scraper with the thickness of 200 mu m, and is immersed in a gel bath, and after standing for 2min at the temperature of 20 ℃, the glass plate is taken out, taken off, washed and dried to obtain the water treatment nano material composite film;
(5) And (3) performing index analysis on the water treatment nano material composite film obtained in the step (4).
As optimization, the modified carbon nanotubes in the step (1) are prepared by mixing carbon nanotubes with a mixed acid solution according to a mass ratio of 1:40, mixing, stirring, reacting, filtering, drying to obtain an acidified carbon nano tube, and mixing dicyclohexylcarbodiimide and 4-dimethylaminopyridine according to a mass ratio of 11:1, mixing, adding N.N-dimethylformamide which is 60-80 times of dicyclohexylcarbodiimide in mass and acidified carbon nanotubes which are 0.2 times of dicyclohexylcarbodiimide in mass, stirring and dispersing to obtain a carbon nanotube dispersion liquid, and mixing the carbon nanotube dispersion liquid and polyacrylic acid according to a mass ratio of 60:1, mixing, stirring and reacting under nitrogen atmosphere, filtering, drying to obtain a pre-modified carbon nano tube, and mixing the pre-modified carbon nano tube with N.N-dimethylformamide according to the mass ratio of 1:50, adding diethylenetriamine with the mass of 10 times of that of the pre-modified carbon nano tube, stirring for reaction, filtering and drying to obtain the modified carbon nano tube.
Preferably, the gel bath in the step (4) is deionized water.
Compared with the prior art, the invention has the beneficial effects that:
the invention adds microgel in the preparation of the water treatment nano material composite membrane, and combines the microgel with titanium dioxide; firstly, oxidized dextran is reacted with modified carbon nano tube and polyallylamine hydrochloride together when the microgel is prepared, because the dextran can convert adjacent hydroxyl groups on a dextran molecular chain into aldehyde groups after oxidation, and the modified carbon nano tube and polyallylamine hydrochloride molecular chain are provided with primary amino groups, after the oxidized dextran is mixed with the oxidized dextran, the primary amino groups on the modified carbon nano tube and polyallylamine hydrochloride molecular chain can be crosslinked with the aldehyde groups to form a microgel structure, because the crosslinked structure of the amino groups and the aldehyde groups has good adsorption performance on metal ions, and ammonium ions are remained on the polyallylamine hydrochloride in the microgel structure, the dye with negative charges has better adsorptivity, so that the microgel can adsorb the metal ions and organic macromolecules with negative charges, the contact area of pollutants and titanium dioxide is further increased, the degradation efficiency of the product is improved, and secondly, the microgel structure is added in the hydrolysis process of tetrabutyl titanate, because the microgel structure is easy to form a film on the surface of inorganic matters, the microgel structure can be formed in the nano-forming process, and the film-forming efficiency of the titanium dioxide is further improved, and the film-forming efficiency of the titanium dioxide is not greatly influenced in the nano-catalytic process when the nano-catalytic film-forming process is further, and the nano-forming property of the titanium dioxide is greatly coated on the transparent product.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the detailed description, and the test methods of each index of the water treatment nano material composite film manufactured in the following examples are as follows:
degradation performance: the water treatment nano material composite membrane obtained in each example and the comparative example simulate the degradation rate of wastewater to 20mg/L methyl orange under the irradiation of visible light with the light intensity of 100mW/cm < 2 >.
Metal ion adsorption: the water treatment nano material composite membrane obtained in each example and the comparative example are placed in water with the lead ion concentration of 5mg/L, and after standing for 90min, the lead ion concentration in the water is measured.
Example 1
The water treatment nanometer material composite film mainly comprises the following components in parts by weight: 65 parts of polyvinylidene fluoride, 8 parts of polyvinylpyrrolidone, 8 parts of nano titanium dioxide and 12 parts of microgel.
The preparation method of the water treatment nano material composite film mainly comprises the following preparation steps:
(1) Dextran and water are mixed according to the mass ratio of 1:25, adding potassium periodate with the mass of 0.9 times of that of dextran into the flask, introducing nitrogen into the flask at the rate of 45mL/min, and stirring and reacting for 12 hours at the temperature of 35 ℃ in a dark place to obtain a dextran oxide mixed solution, wherein the mass ratio of the dextran oxide mixed solution to the barium chloride solution with the mass fraction of 15% is (1): 1.5, mixing, stirring and reacting for 50min at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering, removing sediment to obtain a pretreated oxidized dextran mixed solution, and mixing the pretreated oxidized dextran mixed solution with a sodium sulfate solution with the mass fraction of 15% according to the mass ratio of 1:1.6, stirring and reacting for 40min at 35 ℃ and the rotating speed of 400r/min, filtering to obtain oxidized dextran dispersion liquid, and mixing polyallylamine hydrochloride and water according to the mass ratio of 1:180, adding modified carbon nano tubes with the mass of polyallylamine hydrochloride being 2 times into a beaker, stirring and dispersing for 30min at the rotating speed of 600r/min, regulating the pH value of materials in the beaker to 9.8 to obtain mixed dispersion liquid, and mixing the mixed dispersion liquid and oxidized dextran dispersion liquid according to the volume ratio of 1:1, mixing the mixture in a three-neck flask, controlling the adding rate of oxidized dextran dispersion liquid to be 8mL/min, introducing nitrogen into the three-neck flask at the rate of 50mL/min, stirring the mixture at the temperature of 45 ℃ and the rotating speed of 320r/min for reaction for 2 hours, performing suction filtration to obtain a microgel blank, and drying the microgel blank at the temperature of 75 ℃ for 2 hours to obtain microgel;
(2) Mixing the microgel obtained in the step (1) with chloroform according to a mass ratio of 1:20, adding tetrabutyl titanate which is 3 times of the mass of the microgel into the mixture of the microgel and the chloroform, stirring and mixing to obtain a microgel mixed solution, and mixing the microgel mixed solution and nitric acid with the mass fraction of 10 percent according to the mass ratio of 8:1, mixing, stirring and hydrolyzing for 2 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering to obtain a modified microgel blank, and drying the modified microgel blank for 2 hours at the temperature of 70 ℃ to obtain the modified microgel;
(3) Mixing the modified microgel obtained in the step (2) with 80% of dimethylacetamide solution according to the mass ratio of 1:20, mixing the mixture in a stirrer, adding polyvinylidene fluoride with the mass 3 times of that of the modified microgel and polyvinylpyrrolidone with the mass 0.4 time of that of the modified microgel into the stirrer, and stirring and mixing the mixture to obtain film forming liquid;
(4) The film forming liquid obtained in the step (3) is coated on a glass plate by a scraper with the thickness of 200 mu m, and is immersed in a gel bath, the glass plate is taken out after standing for 2min at the temperature of 20 ℃, the film is uncovered, the water treatment nano material composite film blank is obtained, the water treatment nano material composite film blank is washed by deionized water for 8 times, and the water treatment nano material composite film is obtained after drying for 3h at the temperature of 60 ℃;
(5) And (3) performing index analysis on the water treatment nano material composite film obtained in the step (4).
As optimization, the modified carbon nanotubes in the step (1) are prepared by mixing carbon nanotubes with a mixed acid solution according to a mass ratio of 1:40, mixing, stirring, reacting, filtering, drying to obtain an acidified carbon nano tube, and mixing dicyclohexylcarbodiimide and 4-dimethylaminopyridine according to a mass ratio of 11:1, adding N.N-dimethylformamide with the mass of dicyclohexylcarbodiimide being 80 times and acidified carbon nanotubes with the mass of dicyclohexylcarbodiimide being 0.2 times, stirring and dispersing to obtain a carbon nanotube dispersion liquid, and mixing the carbon nanotube dispersion liquid and polyacrylic acid according to the mass ratio of 60:1, mixing, stirring and reacting under nitrogen atmosphere, filtering, drying to obtain a pre-modified carbon nano tube, and mixing the pre-modified carbon nano tube with N.N-dimethylformamide according to the mass ratio of 1:50, adding diethylenetriamine with the mass of 10 times of that of the pre-modified carbon nano tube, stirring for reaction, filtering and drying to obtain the modified carbon nano tube.
Preferably, the gel bath in the step (4) is deionized water.
Example 2
The water treatment nanometer material composite film mainly comprises the following components in parts by weight: 65 parts of polyvinylidene fluoride, 8 parts of polyvinylpyrrolidone, 8 parts of nano titanium dioxide and 12 parts of microgel.
The preparation method of the water treatment nano material composite film mainly comprises the following preparation steps:
(1) Dextran and water are mixed according to the mass ratio of 1:25, adding potassium periodate with the mass of 0.9 times of that of dextran into the flask, introducing nitrogen into the flask at the rate of 45mL/min, and stirring and reacting for 12 hours at the temperature of 35 ℃ in a dark place to obtain a dextran oxide mixed solution, wherein the mass ratio of the dextran oxide mixed solution to the barium chloride solution with the mass fraction of 15% is (1): 1.5, mixing, stirring and reacting for 50min at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering, removing sediment to obtain a pretreated oxidized dextran mixed solution, and mixing the pretreated oxidized dextran mixed solution with a sodium sulfate solution with the mass fraction of 15% according to the mass ratio of 1:1.6, stirring and reacting for 40min at 35 ℃ and the rotating speed of 400r/min, filtering to obtain oxidized dextran dispersion liquid, and mixing polyallylamine hydrochloride and water according to the mass ratio of 1:180 are mixed in a beaker, stirred and dispersed for 30min under the condition of 400r/min of rotating speed, the pH value of materials in the beaker is regulated to 9.8, mixed dispersion liquid is obtained, and the mixed dispersion liquid and oxidized dextran dispersion liquid are mixed according to the volume ratio of 1:1, mixing the mixture in a three-neck flask, controlling the adding rate of oxidized dextran dispersion liquid to be 8mL/min, introducing nitrogen into the three-neck flask at the rate of 50mL/min, stirring the mixture at the temperature of 45 ℃ and the rotating speed of 320r/min for reaction for 2 hours, performing suction filtration to obtain a microgel blank, and drying the microgel blank at the temperature of 75 ℃ for 2 hours to obtain microgel;
(2) Mixing the microgel obtained in the step (1) with chloroform according to a mass ratio of 1:20, adding tetrabutyl titanate which is 3 times of the mass of the microgel into the mixture of the microgel and the chloroform, stirring and mixing to obtain a microgel mixed solution, and mixing the microgel mixed solution and nitric acid with the mass fraction of 10 percent according to the mass ratio of 8:1, mixing, stirring and hydrolyzing for 2 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering to obtain a modified microgel blank, and drying the modified microgel blank for 2 hours at the temperature of 70 ℃ to obtain the modified microgel;
(3) Mixing the modified microgel obtained in the step (2) with 80% of dimethylacetamide solution according to the mass ratio of 1:20, mixing the mixture in a stirrer, adding polyvinylidene fluoride with the mass 3 times of that of the modified microgel and polyvinylpyrrolidone with the mass 0.4 time of that of the modified microgel into the stirrer, and stirring and mixing the mixture to obtain film forming liquid;
(4) The film forming liquid obtained in the step (3) is coated on a glass plate by a scraper with the thickness of 200 mu m, and is immersed in a gel bath, the glass plate is taken out after standing for 2min at the temperature of 20 ℃, the film is uncovered, the water treatment nano material composite film blank is obtained, the water treatment nano material composite film blank is washed by deionized water for 8 times, and the water treatment nano material composite film is obtained after drying for 3h at the temperature of 60 ℃;
(5) And (3) performing index analysis on the water treatment nano material composite film obtained in the step (4).
As optimization, the modified carbon nanotubes in the step (1) are prepared by mixing carbon nanotubes with a mixed acid solution according to a mass ratio of 1:40, mixing, stirring, reacting, filtering, drying to obtain an acidified carbon nano tube, and mixing dicyclohexylcarbodiimide and 4-dimethylaminopyridine according to a mass ratio of 11:1, adding N.N-dimethylformamide with the mass of dicyclohexylcarbodiimide being 80 times and acidified carbon nanotubes with the mass of dicyclohexylcarbodiimide being 0.2 times, stirring and dispersing to obtain a carbon nanotube dispersion liquid, and mixing the carbon nanotube dispersion liquid and polyacrylic acid according to the mass ratio of 60:1, mixing, stirring and reacting under nitrogen atmosphere, filtering, drying to obtain a pre-modified carbon nano tube, and mixing the pre-modified carbon nano tube with N.N-dimethylformamide according to the mass ratio of 1:50, adding diethylenetriamine with the mass of 10 times of that of the pre-modified carbon nano tube, stirring for reaction, filtering and drying to obtain the modified carbon nano tube.
Preferably, the gel bath in the step (4) is deionized water.
Example 3
The water treatment nanometer material composite film mainly comprises the following components in parts by weight: 65 parts of polyvinylidene fluoride, 8 parts of polyvinylpyrrolidone, 8 parts of nano titanium dioxide and 12 parts of microgel.
The preparation method of the water treatment nano material composite film mainly comprises the following preparation steps:
(1) Dextran and water are mixed according to the mass ratio of 1:25, adding potassium periodate with the mass of 0.9 times of that of dextran into the flask, introducing nitrogen into the flask at the rate of 45mL/min, and stirring and reacting for 12 hours at the temperature of 35 ℃ in a dark place to obtain a dextran oxide mixed solution, wherein the mass ratio of the dextran oxide mixed solution to the barium chloride solution with the mass fraction of 15% is (1): 1.5, mixing, stirring and reacting for 50min at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering, removing sediment to obtain a pretreated oxidized dextran mixed solution, and mixing the pretreated oxidized dextran mixed solution with a sodium sulfate solution with the mass fraction of 15% according to the mass ratio of 1:1.6, stirring and reacting for 40min at 35 ℃ and the rotating speed of 400r/min, filtering to obtain oxidized dextran dispersion liquid, and mixing polyallylamine hydrochloride and water according to the mass ratio of 1:180, adding modified carbon nano tubes with the mass of polyallylamine hydrochloride being 2 times into a beaker, stirring and dispersing for 30min at the rotating speed of 600r/min, regulating the pH value of materials in the beaker to 9.8 to obtain mixed dispersion liquid, and mixing the mixed dispersion liquid and oxidized dextran dispersion liquid according to the volume ratio of 1:1, mixing the mixture in a three-neck flask, controlling the adding rate of oxidized dextran dispersion liquid to be 8mL/min, introducing nitrogen into the three-neck flask at the rate of 50mL/min, stirring the mixture at the temperature of 45 ℃ and the rotating speed of 320r/min for reaction for 2 hours, performing suction filtration to obtain a microgel blank, and drying the microgel blank at the temperature of 75 ℃ for 2 hours to obtain microgel;
(2) Tetrabutyl titanate and chloroform are mixed according to the mass ratio of 3:20, stirring and mixing to obtain tetrabutyl titanate mixed liquor, and mixing the tetrabutyl titanate mixed liquor with 10 mass percent nitric acid according to the mass ratio of 8:1, mixing, stirring and hydrolyzing for 2 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering to obtain a nano titanium dioxide blank, and drying the nano titanium dioxide blank for 2 hours at the temperature of 70 ℃ to obtain nano titanium dioxide;
(3) Mixing the microgel obtained in the step (1) with 80% of dimethylacetamide solution according to the mass ratio of 1:20, mixing the mixture in a stirrer, adding polyvinylidene fluoride with 3 times of the mass of the microgel into the stirrer, and stirring and mixing the nano titanium dioxide obtained in the step (2) with 0.3 times of the mass of the microgel and polyvinylpyrrolidone with 0.4 times of the mass of the microgel to obtain a film forming liquid;
(4) The film forming liquid obtained in the step (3) is coated on a glass plate by a scraper with the thickness of 200 mu m, and is immersed in a gel bath, the glass plate is taken out after standing for 2min at the temperature of 20 ℃, the film is uncovered, the water treatment nano material composite film blank is obtained, the water treatment nano material composite film blank is washed by deionized water for 8 times, and the water treatment nano material composite film is obtained after drying for 3h at the temperature of 60 ℃;
(5) And (3) performing index analysis on the water treatment nano material composite film obtained in the step (4).
As optimization, the modified carbon nanotubes in the step (1) are prepared by mixing carbon nanotubes with a mixed acid solution according to a mass ratio of 1:40, mixing, stirring, reacting, filtering, drying to obtain an acidified carbon nano tube, and mixing dicyclohexylcarbodiimide and 4-dimethylaminopyridine according to a mass ratio of 11:1, adding N.N-dimethylformamide with the mass of dicyclohexylcarbodiimide being 80 times and acidified carbon nanotubes with the mass of dicyclohexylcarbodiimide being 0.2 times, stirring and dispersing to obtain a carbon nanotube dispersion liquid, and mixing the carbon nanotube dispersion liquid and polyacrylic acid according to the mass ratio of 60:1, mixing, stirring and reacting under nitrogen atmosphere, filtering, drying to obtain a pre-modified carbon nano tube, and mixing the pre-modified carbon nano tube with N.N-dimethylformamide according to the mass ratio of 1:50, adding diethylenetriamine with the mass of 10 times of that of the pre-modified carbon nano tube, stirring for reaction, filtering and drying to obtain the modified carbon nano tube.
Preferably, the gel bath in the step (4) is deionized water.
Example 4
The water treatment nanometer material composite film mainly comprises the following components in parts by weight: 65 parts of polyvinylidene fluoride, 8 parts of polyvinylpyrrolidone, 8 parts of nano titanium dioxide and 12 parts of modified carbon nano tubes.
The preparation method of the water treatment nano material composite film mainly comprises the following preparation steps:
(1) The modified carbon nano tube and chloroform are mixed according to the mass ratio of 1:20, adding tetrabutyl titanate with the mass 3 times of that of the modified carbon nano tube into the mixture of the microgel and the chloroform, stirring and mixing to obtain a modified carbon nano tube mixed solution, and mixing the modified carbon nano tube mixed solution with nitric acid with the mass fraction of 10 percent according to the mass ratio of 8:1, mixing, stirring and hydrolyzing for 2 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering to obtain an additive blank, and drying the additive blank for 2 hours at the temperature of 70 ℃ to obtain the additive;
(2) Mixing the additive obtained in the step (1) with 80% of dimethylacetamide solution according to the mass ratio of 1:20, mixing the mixture in a stirrer, adding polyvinylidene fluoride with the mass 3 times of that of the additive and polyvinylpyrrolidone with the mass 0.4 times of that of the additive into the stirrer, and stirring and mixing the mixture to obtain film forming liquid;
(3) The film forming liquid obtained in the step (2) is coated on a glass plate by a scraper with the thickness of 200 mu m, and is immersed in a gel bath, the glass plate is taken out after standing for 2min at the temperature of 20 ℃, the film is uncovered, the water treatment nano material composite film blank is obtained, the water treatment nano material composite film blank is washed by deionized water for 8 times, and the water treatment nano material composite film is obtained after drying for 3h at the temperature of 60 ℃;
(4) And (3) performing index analysis on the water treatment nano material composite film obtained in the step (3).
Preferably, the gel bath in the step (4) is deionized water.
Comparative example
The water treatment nanometer material composite film mainly comprises the following components in parts by weight: 65 parts of polyvinylidene fluoride, 8 parts of polyvinylpyrrolidone and 8 parts of nano titanium dioxide.
The preparation method of the water treatment nano material composite film mainly comprises the following preparation steps:
(1) Tetrabutyl titanate and chloroform are mixed according to the mass ratio of 3:20, stirring and mixing to obtain tetrabutyl titanate mixed liquor, and mixing the tetrabutyl titanate mixed liquor with 10 mass percent nitric acid according to the mass ratio of 8:1, mixing, stirring and hydrolyzing for 2 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering to obtain a nano titanium dioxide blank, and drying the nano titanium dioxide blank for 2 hours at the temperature of 70 ℃ to obtain nano titanium dioxide;
(2) Mixing the nano titanium dioxide obtained in the step (1) with 80% of dimethylacetamide solution according to the mass ratio of 1:50, mixing in a stirrer, adding polyvinylidene fluoride with the mass which is 8 times of that of the nano titanium dioxide and polyvinylpyrrolidone with the mass which is 2 times of that of the nano titanium dioxide into the stirrer, and stirring and mixing to obtain film forming liquid;
(3) The film forming liquid obtained in the step (2) is coated on a glass plate by a scraper with the thickness of 200 mu m, and is immersed in a gel bath, the glass plate is taken out after standing for 2min at the temperature of 20 ℃, the film is uncovered, the water treatment nano material composite film blank is obtained, the water treatment nano material composite film blank is washed by deionized water for 8 times, and the water treatment nano material composite film is obtained after drying for 3h at the temperature of 60 ℃;
(4) And (3) performing index analysis on the water treatment nano material composite film obtained in the step (3).
Preferably, the gel bath in the step (1) is deionized water.
Effect example
The following table 1 gives the analysis results of the water treatment nanomaterial composite film using examples 1 to 4 of the present invention and comparative example.
TABLE 1
Figure DEST_PATH_IMAGE001
From comparison of experimental data of example 1 with comparative example, it can be found that the addition of microgel can effectively improve the treatment effect of the product on polluted water when preparing the water treatment nanomaterial composite film, from comparison of experimental data of example 1 with example 2, it can be found that schiff base structure having adsorption performance on metal ions in microgel is reduced when not adding modified carbon nanotube when preparing microgel, thereby reducing adsorption effect of the product on metal ions, from comparison of experimental data of example 1 with example 3, when microgel is not mixed with nano titanium dioxide, nano titanium dioxide is not dispersed well when directly added into the product, thereby resulting in degradation performance of the product on organic matters is reduced, and from comparison of experimental data of example 1 with example 4, it can be found that no microgel is added when preparing the water treatment nanomaterial composite film, nano titanium dioxide is not dispersed well, thereby resulting in poor treatment effect of the product on metal ions and organic matters.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (1)

1. A water treatment nano material composite film is characterized in that: mainly comprises the following raw material components in parts by weight: 65 parts of polyvinylidene fluoride, 8 parts of polyvinylpyrrolidone, 8 parts of nano titanium dioxide and 12 parts of microgel;
the composite film mainly comprises the following preparation steps:
(1) Dextran and water are mixed according to the mass ratio of 1:25, adding potassium periodate with the mass of 0.9 times of that of dextran into the flask, introducing nitrogen into the flask at the rate of 45mL/min, and stirring and reacting for 12 hours at the temperature of 35 ℃ in a dark place to obtain a dextran oxide mixed solution, wherein the mass ratio of the dextran oxide mixed solution to the barium chloride solution with the mass fraction of 15% is (1): 1.5, mixing, stirring and reacting for 50min at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering, removing sediment to obtain a pretreated oxidized dextran mixed solution, and mixing the pretreated oxidized dextran mixed solution with a sodium sulfate solution with the mass fraction of 15% according to the mass ratio of 1:1.6, stirring and reacting for 40min at 35 ℃ and the rotating speed of 400r/min, filtering to obtain oxidized dextran dispersion liquid, and mixing polyallylamine hydrochloride and water according to the mass ratio of 1:180, adding modified carbon nano tubes with the mass of polyallylamine hydrochloride being 2 times into a beaker, stirring and dispersing for 30min at the rotating speed of 600r/min, regulating the pH value of materials in the beaker to 9.8 to obtain mixed dispersion liquid, and mixing the mixed dispersion liquid and oxidized dextran dispersion liquid according to the volume ratio of 1:1, mixing the mixture in a three-neck flask, controlling the adding rate of oxidized dextran dispersion liquid to be 8mL/min, introducing nitrogen into the three-neck flask at the rate of 50mL/min, stirring the mixture at the temperature of 45 ℃ and the rotating speed of 320r/min for reaction for 2 hours, performing suction filtration to obtain a microgel blank, and drying the microgel blank at the temperature of 75 ℃ for 2 hours to obtain microgel;
(2) Mixing the microgel obtained in the step (1) with chloroform according to a mass ratio of 1:20, adding tetrabutyl titanate which is 3 times of the mass of the microgel into the mixture of the microgel and the chloroform, stirring and mixing to obtain a microgel mixed solution, and mixing the microgel mixed solution and nitric acid with the mass fraction of 10 percent according to the mass ratio of 8:1, mixing, stirring and hydrolyzing for 2 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering to obtain a modified microgel blank, and drying the modified microgel blank for 2 hours at the temperature of 70 ℃ to obtain the modified microgel;
(3) Mixing the modified microgel obtained in the step (2) with 80% of dimethylacetamide solution according to the mass ratio of 1:20, mixing the mixture in a stirrer, adding polyvinylidene fluoride with the mass 3 times of that of the modified microgel and polyvinylpyrrolidone with the mass 0.4 time of that of the modified microgel into the stirrer, and stirring and mixing the mixture to obtain film forming liquid;
(4) The film forming liquid obtained in the step (3) is coated on a glass plate by a scraper with the thickness of 200 mu m, and is immersed in a gel bath, the glass plate is taken out after standing for 2min at the temperature of 20 ℃, the film is uncovered, the water treatment nano material composite film blank is obtained, the water treatment nano material composite film blank is washed by deionized water for 8 times, and the water treatment nano material composite film is obtained after drying for 3h at the temperature of 60 ℃;
(5) Performing index analysis on the water treatment nano material composite film obtained in the step (4);
the step (1) is to mix the carbon nano tube and the mixed acid liquid according to the mass ratio of 1:40, mixing, stirring, reacting, filtering, drying to obtain an acidified carbon nano tube, and mixing dicyclohexylcarbodiimide and 4-dimethylaminopyridine according to a mass ratio of 11:1, adding N.N-dimethylformamide with the mass of dicyclohexylcarbodiimide being 80 times and acidified carbon nanotubes with the mass of dicyclohexylcarbodiimide being 0.2 times, stirring and dispersing to obtain a carbon nanotube dispersion liquid, and mixing the carbon nanotube dispersion liquid and polyacrylic acid according to the mass ratio of 60:1, mixing, stirring and reacting under nitrogen atmosphere, filtering, drying to obtain a pre-modified carbon nano tube, and mixing the pre-modified carbon nano tube with N.N-dimethylformamide according to the mass ratio of 1:50, mixing, adding diethylenetriamine with the mass 10 times of that of the pre-modified carbon nano tube, stirring for reaction, filtering, and drying to obtain the modified carbon nano tube;
the gel bath in the step (4) is deionized water.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103464004A (en) * 2013-06-21 2013-12-25 浙江海洋学院 High strength nanometer modified ultrafilter membrane and preparation method thereof
CN104201353A (en) * 2014-09-03 2014-12-10 深圳市贝特瑞纳米科技有限公司 Titanium-series oxide/carbon nano tube composite anode material and preparation method thereof
CN105749766A (en) * 2016-03-02 2016-07-13 同济大学 Preparation method of polyvinylidene fluoride/TiO2 nano-sol composite ultrafiltration membrane
CN110079179A (en) * 2019-05-30 2019-08-02 江苏美乔科技有限公司 Wear-resisting anti-aging water lustering oil of one kind and preparation method thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102294180B (en) * 2010-06-22 2013-06-19 浙江海洋学院 Preparation method of nano TiO2-modified PVDF (Polyvinylidene Fluoride) ultrafiltration membrane
US9827517B2 (en) * 2011-01-25 2017-11-28 President And Fellows Of Harvard College Electrochemical carbon nanotube filter and method
ES2395507B1 (en) * 2011-06-03 2013-12-19 Nanobiomatters Research & Development, S.L. NANOCOMPOSED MATERIALS BASED ON METAL OXIDES WITH MULTIFUNCTIONAL PROPERTIES
CA2892085C (en) * 2011-11-22 2022-07-26 Znano Llc Filter comprising porous plastic material coated with hydophilic coating
CN104492282B (en) * 2014-12-24 2016-09-07 福州大学 The TiO of Ionic Liquid Modified2nano particle/PVDF composite micro porous film and preparation method thereof
CN111690972A (en) * 2019-03-06 2020-09-22 苏州鱼得水电气科技有限公司 Processing technology of high-temperature-resistant ceramic oxide film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103464004A (en) * 2013-06-21 2013-12-25 浙江海洋学院 High strength nanometer modified ultrafilter membrane and preparation method thereof
CN104201353A (en) * 2014-09-03 2014-12-10 深圳市贝特瑞纳米科技有限公司 Titanium-series oxide/carbon nano tube composite anode material and preparation method thereof
CN105749766A (en) * 2016-03-02 2016-07-13 同济大学 Preparation method of polyvinylidene fluoride/TiO2 nano-sol composite ultrafiltration membrane
CN110079179A (en) * 2019-05-30 2019-08-02 江苏美乔科技有限公司 Wear-resisting anti-aging water lustering oil of one kind and preparation method thereof

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