CN108285174B - WO (WO)3-ZrO2Preparation method of photocatalytic sewage treatment membrane - Google Patents
WO (WO)3-ZrO2Preparation method of photocatalytic sewage treatment membrane Download PDFInfo
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- CN108285174B CN108285174B CN201810299467.9A CN201810299467A CN108285174B CN 108285174 B CN108285174 B CN 108285174B CN 201810299467 A CN201810299467 A CN 201810299467A CN 108285174 B CN108285174 B CN 108285174B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Environmental & Geological Engineering (AREA)
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Abstract
The invention relates to the field of sewage treatment, and particularly discloses a preparation method of a WO3-ZrO2 photocatalytic sewage treatment membrane, which comprises the following steps: adding ammonium fluorozirconate into an organic acid solution, heating in a water bath and stirring, adding sodium tungstate into the solution, stirring, adding ethylenediamine into the obtained solution, heating in the water bath and stirring to obtain zirconium dioxide gel; dissolving zirconium dioxide gel, cerium nitrate and an organic polymer in a propanol solution, uniformly mixing, evaporating the solution in an oven, adding a carbon nano tube, then carrying out hydrothermal treatment, coating the slurry obtained after the hydrothermal treatment and cooling on a base material, and drying at room temperature to obtain a film; the obtained film is taken down from the substrate and is subjected to heat treatment under vacuum, and the WO3-ZrO2 photocatalytic sewage treatment film is obtained. The WO3-ZrO2 photocatalytic sewage treatment film prepared by the method greatly improves the stability of the photocatalytic film and prolongs the service life of the photocatalytic sewage treatment film.
Description
Technical Field
The invention relates to the field of sewage treatment, and particularly discloses a preparation method of a WO3-ZrO2 photocatalytic sewage treatment membrane.
Background
The traditional sewage treatment method has the problems of high cost, low efficiency, secondary pollution and the like. Researches show that the photocatalytic semiconductor nano oxide can degrade various pollutants by using ultraviolet rays, can oxidize and decompose hydrocarbons, surfactants, organic dyes, nitrogen-containing organic matters, organophosphorus insecticides, wood preservatives and the like in water, and can be used for sewage treatment.
When the powder photocatalytic oxide is used for sewage treatment, the problems that the powder is difficult to recover, the light transmittance is influenced by the suspended powder and the like exist; therefore, in recent years, titanium dioxide films are frequently used for photocatalysis, but the problems of small contact area, low catalytic efficiency, short service life and the like exist.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a preparation method of a WO3-ZrO2 photocatalytic sewage treatment membrane.
In order to achieve the above purpose, the present invention adopts the following scheme.
A method for preparing a WO3-ZrO2 photocatalytic sewage treatment membrane, ammonium fluorozirconate is added into an organic acid solution, wherein the weight ratio of ammonium fluorozirconate: the molar ratio of the organic acid is 1: (0.5 to 10); heating the mixture in a water bath to 90 ℃ and stirring, reacting for 3 hours, and adding sodium tungstate into the solution, wherein the weight ratio of sodium tungstate: the molar ratio of ammonium fluorozirconate is 1:3, the solution is stirred and then ethylenediamine is added to the resulting solution, wherein the molar ratio of ammonium fluorozirconate: the molar ratio of ethylene diamine is 1: (1-15), heating to 85 ℃ in a water bath, stirring for 1 hour, and continuously keeping the temperature of 85 ℃ for reacting for 24 hours to obtain zirconium dioxide gel; dissolving zirconium dioxide gel, cerium nitrate and an organic polymer in a propanol solution, wherein the zirconium dioxide gel: cerium nitrate: the mass ratio of the organic polymer is 1: (0.03-0.2): (2-15); after uniform mixing, evaporating the solution in an oven for 50%, and adding carbon nanotubes, wherein the mass ratio of the carbon nanotubes to the zirconium dioxide gel is 1: (800-3000); then carrying out hydrothermal treatment at 150 ℃ for 3 hours, coating the slurry obtained after the hydrothermal treatment and cooling on a base material, and drying at room temperature to obtain a film; the obtained film is taken down from the substrate and is subjected to heat treatment under vacuum to obtain the WO3-ZrO2 photocatalytic sewage treatment film.
The method comprises the following steps of taking ammonium fluorozirconate as a raw material, adding an acid solution and an alkali solution respectively, and mixing to obtain gel with more uniform dispersion, wherein the film components obtained from the gel are more uniformly distributed, and the strength of the film is improved.
Further, the mass concentration of the organic acid solution is 5-30%.
Further, the organic acid is selected from one of citric acid and trichloroacetic acid.
Further, the organic polymer is selected from one of polymaleic anhydride, polyurethane and hydroxypropyl methyl cellulose.
In one aspect, the heat treatment method is as follows: treating at 200 deg.C for 1-2 hr, heating to 350 deg.C for 0.5 hr, and cooling to 160 deg.C for 3-5 hr.
In another aspect, the substrate is one of glass and metal.
By adopting the three-stage heat treatment process, impurities in the material can be effectively removed, defects caused by overlarge stress change of the film in the heat treatment process can be prevented, and the quality of the finished film is effectively improved.
The invention has the beneficial effects that: the WO3-ZrO2 photocatalytic sewage treatment film prepared by the method greatly improves the stability of the photocatalytic film and prolongs the service life of the photocatalytic film on the basis of adding tungsten trioxide to ensure that the photocatalytic activity of the film is higher.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example one
The preparation method of the WO3-ZrO2 photocatalytic sewage treatment membrane is characterized in that ammonium fluorozirconate is added into a citric acid solution with the mass concentration of 25%, wherein the mass ratio of the ammonium fluorozirconate: the molar ratio of citric acid is 1: 0.5; heating the mixture in a water bath to 90 ℃ and stirring, reacting for 3 hours, and adding sodium tungstate into the solution, wherein the weight ratio of sodium tungstate: the molar ratio of ammonium fluorozirconate is 1:3, the solution is stirred and then ethylenediamine is added to the resulting solution, wherein the molar ratio of ammonium fluorozirconate: the molar ratio of ethylene diamine is 1: 1, heating to 85 ℃ in a water bath, stirring for 1 hour, and continuously keeping the temperature of 85 ℃ for reacting for 24 hours to obtain zirconium dioxide gel; dissolving zirconium dioxide gel, cerium nitrate and polyurethane in a propanol solution, wherein the zirconium dioxide gel: cerium nitrate: the mass ratio of polyurethane is 1: 0.2: 2; after uniform mixing, evaporating the solution in an oven for 50%, and adding carbon nanotubes, wherein the mass ratio of the carbon nanotubes to the zirconium dioxide gel is 1: 3000A; then carrying out hydrothermal treatment at 150 ℃ for 3 hours, coating the slurry obtained after the hydrothermal treatment and cooling on a base material, and drying at room temperature to obtain a film; and taking the obtained film down from the substrate, putting the film into a muffle furnace, regulating the environment in the furnace to be vacuum, treating the film for 2 hours at 200 ℃, then heating the film to 350 ℃, carrying out heat treatment for 0.5 hour, and finally cooling the film to 160 ℃ for treatment for 3 hours to obtain the WO3-ZrO2 photocatalytic sewage treatment film.
Example two
The preparation method of the WO3-ZrO2 photocatalysis sewage treatment membrane is characterized in that ammonium fluorozirconate is added into a trichloroacetic acid solution with the mass concentration of 8%, wherein the mass ratio of the ammonium fluorozirconate: the molar ratio of trichloroacetic acid is 1: 10; heating the mixture in a water bath to 90 ℃ and stirring, reacting for 3 hours, and adding sodium tungstate into the solution, wherein the weight ratio of sodium tungstate: the molar ratio of ammonium fluorozirconate is 1:3, the solution is stirred and then ethylenediamine is added to the resulting solution, wherein the molar ratio of ammonium fluorozirconate: the molar ratio of ethylene diamine is 1: heating to 85 ℃ in water bath, stirring for 1 hour, and continuously keeping the temperature of 85 ℃ for reacting for 24 hours to obtain zirconium dioxide gel; dissolving zirconium dioxide gel, cerium nitrate and polymaleic anhydride in a propanol solution, wherein the zirconium dioxide gel: cerium nitrate: the mass ratio of the polymaleic anhydride is 1: 0.03: 15; after uniform mixing, evaporating the solution in an oven for 50%, and adding carbon nanotubes, wherein the mass ratio of the carbon nanotubes to the zirconium dioxide gel is 1: 800; then carrying out hydrothermal treatment at 150 ℃ for 3 hours, coating the slurry obtained after the hydrothermal treatment and cooling on a base material, and drying at room temperature to obtain a film; and taking the obtained film down from the substrate, putting the film into a muffle furnace, regulating the environment in the furnace to be vacuum, treating the film for 1 hour at 200 ℃, then heating the film to 350 ℃, carrying out heat treatment for 0.5 hour, and finally cooling the film to 160 ℃ for treatment for 5 hours to obtain the WO3-ZrO2 photocatalytic sewage treatment film.
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.
Claims (4)
1. WO (WO)3-ZrO2The preparation method of the photocatalytic sewage treatment membrane is characterized by comprising the following steps: adding ammonium fluorozirconate to the citric acid or trichloroacetic acid solution, wherein the ratio of ammonium fluorozirconate: the molar ratio of citric acid or trichloroacetic acid is 1:
(0.5-10) heating in water bath to 90 ℃ and stirring, reacting for 3 hours, and adding sodium tungstate into the solution, wherein the weight ratio of sodium tungstate: the molar ratio of ammonium fluorozirconate is 1:3, the solution is stirred and then ethylenediamine is added to the resulting solution, wherein the molar ratio of ammonium fluorozirconate: the molar ratio of ethylene diamine is 1: (1-15), heating to 85 ℃ in a water bath, stirring for 1 hour, and continuously keeping the temperature of 85 ℃ for reacting for 24 hours to obtain zirconium dioxide gel; dissolving zirconium dioxide gel, cerium nitrate, polymaleic anhydride or polyurethane or hydroxypropyl methyl cellulose in a propanol solution, wherein the zirconium dioxide gel: cerium nitrate: the mass ratio of the polymaleic anhydride or polyurethane or hydroxypropyl methyl cellulose is 1: (0.03-0.2): (2-15);
after uniform mixing, evaporating the solution in an oven for 50%, and adding carbon nanotubes, wherein the mass ratio of the carbon nanotubes to the zirconium dioxide gel is 1: (800-3000); then carrying out hydrothermal treatment at 150 ℃ for 3 hours, coating the slurry obtained after the hydrothermal treatment and cooling on a base material, and drying at room temperature to obtain a film; removing the obtained film from the substrate, and performing heat treatment under vacuum to obtain WO3-ZrO2A photocatalytic sewage treatment film.
2. WO according to claim 13-ZrO2The preparation method of the photocatalytic sewage treatment membrane is characterized by comprising the following steps: the mass concentration of the citric acid or trichloroacetic acid solution is 5-30%.
3. WO according to claim 13-ZrO2The preparation method of the photocatalytic sewage treatment membrane is characterized by comprising the following steps: the heat treatment mode is as follows: treating at 200 deg.C for 1-2 hr, heating to 350 deg.C for 0.5 hr, and cooling to 160 deg.C for 3-5 hr.
4. WO according to claim 13-ZrO2The preparation method of the photocatalytic sewage treatment membrane is characterized by comprising the following steps: the substrate is one of glass and metal.
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| CN110404589A (en) * | 2019-08-01 | 2019-11-05 | 上海环境卫生工程设计院有限公司 | A kind of photocatalysis film and its preparation method and application |
| CN112933999B (en) * | 2021-02-26 | 2022-03-22 | 南京大学环境规划设计研究院集团股份公司 | Preparation method of self-cleaning membrane material for capping of sewage station |
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| CN102180705B (en) * | 2011-02-28 | 2013-04-10 | 武汉大方机电有限公司 | Preparation method for titanium dioxide thin layer loaded on surface of inorganic ceramic matrix |
| CN103048363B (en) * | 2011-10-12 | 2015-01-14 | 中国科学院合肥物质科学研究院 | Metallic oxide material with mesoporous-macroporous composite structure as well as preparation method and application thereof |
| US20150001155A1 (en) * | 2013-06-26 | 2015-01-01 | Corning Incorporated | Methods and apparatus for synthesis of stabilized zero valent nanoparticles |
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