CN110871058B - Photocatalytic unit and photocatalytic method thereof - Google Patents
Photocatalytic unit and photocatalytic method thereof Download PDFInfo
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- CN110871058B CN110871058B CN201811003021.3A CN201811003021A CN110871058B CN 110871058 B CN110871058 B CN 110871058B CN 201811003021 A CN201811003021 A CN 201811003021A CN 110871058 B CN110871058 B CN 110871058B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/007—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8634—Ammonia
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B01J35/39—
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Abstract
The invention discloses a photocatalytic unit and a photocatalytic method thereof. The photocatalytic unit includes: a photocatalyst and a light source device. The photocatalyst comprises a foamed ceramic carrier and TiO distributed on the surface of the foamed ceramic carrier 2 The crystal grain, the foamed ceramic carrier includes foamed ceramic and composite oxide, the foamed ceramic is open-cell foam structure, the pore edge of the foamed ceramic contains three-dimensional through micron-level pore channel, and the composite oxide is distributed on the surface of the pore edge and in the pore channel. When the photocatalytic unit is used for purifying gas, the photocatalytic activity and stability are good.
Description
Technical Field
The invention relates to a photocatalytic unit and a photocatalytic method thereof, belonging to the field of photocatalysis.
Background
Semiconductor photocatalytic oxidation is a novel technology which can make organic matters decomposed into carbon dioxide and water through photocatalysis at normal temperature and normal pressure, and does not cause secondary pollution, thus causing high attention of researchers in various countries in the world. Researches show that various organic pollutants in water and air can be effectively degraded by utilizing a semiconductor photocatalysis method, such as halogenated hydrocarbon, nitroaromatic, phenol, organic pigment, pesticide, surfactant and the like; cyanide, nitrite, thiocyanate and the like can also be converted into non-toxic or low-toxic compounds; can also be applied to the fields of antibiosis, deodorization, air purification, self-cleaning materials and the like. The semiconductor photocatalysts which have been studied so far mainly include metal oxides, sulfides and the like, among which titanium dioxide (TiO) 2 ) Has the characteristics of good chemical stability, safety, no toxicity, low cost and the like, and is widely researched and applied in the direction of photocatalytic oxidation.
The titanium dioxide photocatalyst is generally used in the form of powder, but this causes a suspension system in a fluid, thereby causing technical problems of difficulty in separation and difficulty in recovery, and thus limiting practical use. The titanium dioxide is fixed on the carrier, so that the defect of the suspension phase titanium dioxide photocatalyst can be overcome. Therefore, finding a suitable carrier and an efficient loading method to fix the catalyst and improve the photocatalytic efficiency of the catalyst are key to realizing the industrialization of the titanium dioxide photocatalyst, and are hot spots in the research field of the photocatalytic technology in recent years.
At present, when a ceramic carrier is adopted as a carrier material, a titanium dioxide loading method is generally adopted as a titanium glue loading method or a method of adding titanium oxide crystal grains into a binder loading method, and then the titanium oxide crystal grains are sintered at high temperature to prepare the supported photocatalyst. The ceramic supported photocatalyst has the technical problems that: first, the use of non-catalytic materials such as binders can affect the amount of titanium dioxide on the surface during loading and sintering, thereby affecting catalytic activity; secondly, when the titanium dioxide is loaded on the ceramic carrier, high-temperature roasting is generally adopted to increase the firmness of the titanium dioxide loading, but the titanium dioxide is easy to be sintered and generates a crystal phase with non-photocatalytic activity, thereby influencing the catalytic activity, and the problem that the titanium dioxide is easy to lose even if the titanium dioxide is roasted at high temperature, thereby influencing the activity stability of the catalyst; thirdly, the ceramic carrier is also prone to have a problem of uneven distribution when carrying titanium dioxide, thereby further affecting the catalytic activity and stability thereof.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a photocatalytic unit and a photocatalytic method thereof. When the photocatalytic unit is used for purifying gas, the photocatalytic unit has good activity and stability.
A first aspect of the present invention provides a photocatalytic unit comprising:
the photocatalyst is a foamed ceramic carrier loaded with TiO 2 The photocatalyst comprises a foamed ceramic carrier and TiO distributed on the surface of the foamed ceramic carrier 2 Crystal grains, wherein the foamed ceramic carrier comprises foamed ceramic and composite oxide, and the foamed ceramicThe porcelain is of an open-cell foam structure, the pore edges of the foamed ceramics contain three-dimensional through micron-sized pore channels, and composite oxides are distributed on the surfaces of the pore edges and in the pore channels;
and a light source device having a light emitting portion facing the photocatalyst.
The photocatalyst adopts a photocatalyst plate, the ultraviolet light source device adopts an ultraviolet LED lamp panel, the ultraviolet LED lamp panels are arranged on one surface or two surfaces of the photocatalyst plate, and further, the ultraviolet LED lamp panels are symmetrically arranged on the two surfaces of the photocatalyst plate. The photocatalyst plate and the ultraviolet LED lamp panel are arranged in parallel. The distance between the photocatalyst plate and the ultraviolet LED lamp plate is 0-10 cm, further 0-5 cm, and preferably 0.5-3.5 cm. Further, the thickness of the photocatalyst plate may be 0.3 to 3.0cm.
In the ultraviolet light source device, an ultraviolet LED lamp panel comprises a substrate and a plurality of LED ultraviolet light-emitting particles arranged on the substrate, namely a Uv-LED point light source. The ultraviolet light emitted by the ultraviolet LED lamp has a wavelength of 280-390 nm, which may be a single wavelength or a mixture of wavelengths, preferably a single wavelength, such as 365nm.
In the ultraviolet light source device, the LED ultraviolet light-emitting particles on the ultraviolet LED lamp panel can be arranged in an array form, and the vent holes can be arranged between adjacent arrays or not.
The substrate can be in a fence type, namely LED ultraviolet light-emitting particles which can be arranged in an array mode are arranged on the fence strips, and vent holes are formed among the fence strips. The ultraviolet LED lamp plate can set up the LED lamp simultaneously, also can both sides set up the LED lamp.
The photocatalytic unit is provided with N photocatalyst boards, ultraviolet LED lamp panels are arranged on two sides of each photocatalyst board and are arranged in parallel, and N is an integer larger than or equal to 1. The ultraviolet LED lamp panels arranged between the two adjacent photocatalyst boards are back to back and arranged on the two ultraviolet LED lamp panels of the single-sided LED lamp, and one ultraviolet LED lamp panel of the double-sided LED lamp can be selected.
The photocatalytic unit further comprises a fixing frame used for fixing the photocatalyst plate and the ultraviolet LED lamp plate.
The foamed ceramic carrier of the invention loads TiO 2 In the photocatalyst, tiO distributed on the surface of the foamed ceramic carrier 2 Crystal grain of TiO 5-50 μm in particle size 2 The crystal grains account for 70% or more, preferably 80% or more, and more preferably TiO with a particle size of 15 to 45 μm 2 The crystal grains account for 70% or more, preferably 80% or more.
The foamed ceramic carrier of the invention loads TiO 2 In the photocatalyst, tiO is used as the reference based on the weight of the catalyst 2 The total content of (A) is 5% to 40%, preferably 8% to 35%.
The foamed ceramic carrier of the invention loads TiO 2 In the photocatalyst, the weight of the titanium dioxide contained in the composite oxide in the foamed ceramic carrier accounts for the weight of the TiO in the catalyst 2 5 to 50 percent of the total weight.
The foamed ceramic carrier of the invention loads TiO 2 In the photocatalyst, the TiO 2 Mainly anatase type.
The foamed ceramic carrier of the invention loads TiO 2 In the photocatalyst, at least a part of the composite oxide is embedded in and/or penetrates through the pores.
The foamed ceramic carrier of the invention loads TiO 2 In the photocatalyst, the composite oxide comprises alumina and titanium dioxide, and can be a homogeneously distributed composite oxide or a heterogeneously distributed composite oxide, and the content of the titanium dioxide on the surface of the carrier is preferably higher than the content of the titanium dioxide in the carrier. The composite oxide accounts for 10-50% of the weight of the foamed ceramic carrier, and the weight content of titanium oxide in the composite oxide is 10-90%.
The foamed ceramic carrier of the invention loads TiO 2 In the photocatalyst, the alumina in the composite oxide is preferably gamma-Al 2 O 3 Further, it is preferable to use a composite oxide obtained by low-temperature calcination at a calcination temperature of 400 to 700 ℃, preferably 450 to 700 ℃.
The foamed ceramic carrier of the invention loads TiO 2 In the photocatalyst, the foamed ceramic can be used in the conventional wayThe composition of the foamed ceramic of the photocatalyst carrier can comprise one or more of alumina, zirconia, silicon carbide and silicon oxide, and preferably comprises alumina, and the alumina is alpha-Al 2 O 3 。
The foamed ceramic carrier of the invention loads TiO 2 In the photocatalyst, the open-cell ratio of the foamed ceramic is 40-90%, preferably 60-80%, the diameter of a cell hole is 1-5 mm, and the pore density is 8-60 ppi, preferably 8-30 ppi.
The foamed ceramic carrier of the invention loads TiO 2 In the photocatalyst, the pore edges of the foamed ceramic are provided with three-dimensional through micron-sized pore channels. The pore volume of the foamed ceramic is 0.1-0.5 mL/g, the pore volume occupied by the pore diameter of less than 20 mu m is less than 20% of the total pore volume, the pore volume occupied by the pore diameter of 20-80 mu m is 50-95% of the total pore volume, and the pore volume occupied by the pore diameter of more than 80 mu m is less than 10% of the total pore volume. The pore volume and the pore distribution of the foamed ceramic are micropore parameters measured by a mercury intrusion method. The outer surface of the foamed ceramic is provided with micron-sized pore openings which are uniformly distributed, and the diameter of each pore opening can be 1-100 mu m.
The foamed ceramic carrier of the invention loads TiO 2 In the photocatalyst, the composite oxide can also contain modification aids such as silicon, zirconium, magnesium, calcium, manganese and the like, and the content of the modification aids in terms of oxide accounts for less than 15% of the weight of the foamed ceramic carrier.
The foamed ceramic carrier of the invention loads TiO 2 A method of preparing a photocatalyst, comprising:
(1) Preparing titanium sol;
(2) Immersing the foamed ceramic carrier into the titanium sol obtained in the step (1) for slurry hanging, removing excess slurry, drying,
(3) Repeating the dipping process 0-5 times, preferably 1-4 times;
(4) And (4) carrying out heat treatment on the material obtained in the step (3) to obtain the photocatalyst.
The preparation method of the foamed ceramic carrier in the step (2) comprises the following steps: and (3) soaking the foam ceramic into the composite oxide precursor slurry to prepare the foam ceramic carrier.
In the preparation method of the foamed ceramic carrier, the composite oxide precursor slurry comprises the following components: nano titanium dioxide powder, alumina dry glue powder, peptizing acid, kaolin and water, wherein the nano titanium dioxide powder comprises the following components in percentage by weight: the alumina dry glue powder is calculated by alumina: peptizing acid: kaolin: the weight ratio of water is 1-9: 10:1 to 5:0.1 to 0.7:3.0 to 10.0 percent, wherein the alumina dry glue powder is dry powder obtained by drying aluminum hydroxide precipitate and can be prepared by a conventional neutralization method, an alcoholysis method and the like. The peptization acid can be one or more of inorganic acids such as nitric acid, hydrochloric acid and the like. Polyethylene glycol is preferably added into the composite oxide precursor slurry, and the addition amount of the polyethylene glycol accounts for 1-3% of the weight of the composite oxide precursor slurry. The molecular weight of the polyethylene glycol is 200-4000. The particle size of the nano titanium dioxide powder is less than 100nm, preferably 10-100 nm.
In the preparation method of the foamed ceramic carrier, the method for impregnating the composite oxide precursor slurry by the foamed ceramic can adopt a vacuum impregnation method, and can adopt one or more times of impregnation, preferably multiple times of impregnation, when multiple times of impregnation are adopted, the composite oxide precursor slurry can be the same or different, and the content of the nano titanium dioxide in the slurry subjected to the subsequent impregnation is preferably higher than that in the slurry subjected to the prior impregnation. After each impregnation, the excess slurry is removed, the slurry in the large pore passage is removed by blowing, and then the drying treatment is carried out. And finally, drying for the first time and roasting to obtain the foamed ceramic carrier. Wherein the drying can be carried out at room temperature and then dried at 40-90 ℃ for 4-24 hours. The roasting can be performed in multiple stages by adopting a temperature programming mode, wherein the roasting is performed for 1 to 8 hours at a temperature of between 200 and 300 ℃, then is performed for 1 to 6 hours at a temperature of between 400 and 700 ℃, preferably is performed for 2 to 8 hours at a temperature of between 200 and 300 ℃, and is performed for 2 to 5 hours at a temperature of between 450 and 700 ℃.
In the preparation method of the foamed ceramic carrier, the composite oxide precursor slurry used for the last impregnation is preferably prepared by mixing the nano titanium dioxide and the polyethylene glycol, and then mixing the mixture with the alumina dry glue powder, peptizing acid and water, so that at least part of the polyethylene glycol enters the nano titanium dioxide, more surfaces of the nano titanium dioxide are exposed outside the carrier in the subsequent treatment process, an easily enriched area is formed, the post-loaded titanium dioxide is more easily distributed around the nano titanium dioxide, the dispersity and the dispersion amount of the titanium dioxide on the surface of the carrier are improved, the size of titanium dioxide crystal grains can be better controlled, the firmness of the titanium dioxide in the catalyst is improved, and the activity and the stability of the catalyst are further improved.
The foamed ceramic carrier of the invention loads TiO 2 In the preparation method of the photocatalyst, the titanium sol in the step (1) can be prepared by a conventional method, and preferably, the following method is adopted: the titanium oxide precursor is dissolved in an organic solvent and mixed uniformly to prepare a titanium sol. The titanium oxide precursor may be titanium (IV) acetylacetonate. Preferably, carboxymethyl cellulose is added in the mixing process, and the molar ratio of the addition amount of the carboxymethyl cellulose to the titanium atoms is 1-7: 100; wherein the organic solvent is lower alcohol, such as C1-C5 alcohol, preferably one or more of methanol, ethanol and propanol, and more preferably isopropanol. The molar concentration of titanium in the titanium sol is 0.5-4.0 mol/L.
The foamed ceramic carrier of the invention loads TiO 2 In the preparation method of the photocatalyst, the slurry coating and the excess slurry removal in the step (2) can be carried out by a conventional method, for example, the slurry coating is carried out by an immersion method, normal pressure immersion can be adopted, vacuum immersion can be adopted, and excess slurry removal is carried out by extrusion by a rolling method.
The foamed ceramic carrier of the invention loads TiO 2 In the preparation method of the photocatalyst, the drying in the step (2) is drying for 4 to 24 hours at a temperature of between 50 and 95 ℃.
The foamed ceramic carrier of the invention loads TiO 2 In the preparation method of the photocatalyst, the heat treatment conditions in the step (4) are as follows: the roasting is carried out in the presence of water vapor and/or inert gas in a segmented mode, namely, the roasting is carried out for 3 to 8 hours at the temperature of 200 to 300 ℃, then the roasting is carried out for 1 to 6 hours at the temperature of 400 to 750 ℃, preferably the roasting is carried out for 3 to 8 hours at the temperature of 200 to 300 ℃, and the roasting is carried out for 2 to 5 hours at the temperature of 450 to 700 ℃. The inert gas may be nitrogen.
Adopt the present inventionThe photocatalyst prepared by the method adopts an open-cell foam structure, three-dimensional through micron-sized pore channels are distributed in pore edges of the foam ceramic, composite oxides are distributed on the surfaces of the pore edges and in the pore channels of the foam ceramic, at least a part of the composite oxides are embedded in and/or pass through the pore channels, and the main crystal phase of the composite oxides is gamma-Al 2 O 3 On one hand, the connectivity of the pore passages of the open-pore foamed ceramic is fully utilized, on the other hand, the micron-sized pore passages in the pore edges are fully utilized, the composite oxide is embedded or penetrated in the direction of micropores, not only can the strength of the foamed ceramic be enhanced, and larger external specific surface area is provided, but also when titanium sol is subsequently utilized to load titanium dioxide, low-temperature roasting can be adopted, the growth and aggregation of titanium dioxide grains can be easily carried out on the basis of the composite oxide, the micron-sized grains with uniformly distributed and high-activity phases are formed, the base parts of the micron-sized grains are integrated with a foamed ceramic carrier, and TiO can be improved 2 The firmness of the photocatalyst improves the stability of the photocatalyst.
When the method of the invention is used for preparing the photocatalyst, the heat treatment is preferably segmented heat treatment by adopting water vapor and/or inert gas to promote proper TiO 2 Grain growth, and improvement of TiO 2 The dispersion degree of crystal grains on the surface of the carrier is improved, and the TiO is also improved 2 The pore structure on the carrier promotes the contact area of water or gas and the photocatalyst easily, and simultaneously, the water or gas can pass through the photocatalyst quickly, thereby improving the treatment efficiency.
The photocatalytic unit of the present invention can be applied to existing electric appliances, such as air purifiers, refrigerators, air conditioners, etc., can also be applied to pipelines having a gas flow, such as exhaust air, ventilation equipment, exhaust gas discharge equipment, ventilation equipment, etc., and can also be used for transportation means, such as automobiles, cruise ships, submarines, airplanes, etc.
In a second aspect of the present invention, a photocatalytic method is provided, wherein the photocatalytic unit provided in the first aspect is adopted, and a gas to be purified passes through the photocatalytic unit, and a photocatalytic reaction is performed under the action of ultraviolet light and a catalyst, so as to obtain a purified gas.
In the photocatalysis method of the invention, the air inlet direction of the gas to be purified can be adjusted according to the requirement, and the air can be vertically fed, obliquely fed and the like.
In the photocatalysis method of the invention, N photocatalysis units can be adopted, and the N photocatalysis units can be arranged in parallel or in series. The plurality of photocatalytic units can be arranged in a flat plate shape or in a V shape. The arrangement modes of the N photocatalytic units can be the same or different.
In the photocatalytic method of the present invention, the wavelength of the ultraviolet light emitted by the ultraviolet LED lamp is 280-390 nm, which may be a single wavelength or a mixed wavelength, and is preferably a single wavelength, such as 365nm.
In the photocatalysis method, the distance between the ultraviolet LED lamp panel and the photocatalyst plate is 0-10 cm. Further, it is 0 to 5cm, preferably 0.5 to 3.5cm. Further, the thickness of the photocatalyst plate can be 0.3-3.0 cm.
In the photocatalytic method of the present invention, the radiation intensity on the photocatalyst plate is 0.01 to 500mW/cm 2 Preferably 0.5 to 70mW/cm 2 。
In the photocatalysis method of the invention, the gas to be purified is the gas containing volatile organic pollutants and/or sulfur and nitrogen-containing gas, such as indoor air, industrial gas and the like.
The photocatalysis method of the invention can remove various Volatile Organic Compounds (VOC) such as toluene, xylene, benzene, formaldehyde, acetaldehyde and homologues thereof, and also can remove various gases containing sulfur and nitrogen such as sulfur dioxide, hydrogen sulfide, ammonia and the like, and also can play a role in sterilization. The photocatalysis method can be used for purifying indoor air, industrial polluted gas, haze pollutants and the like, has good photocatalysis degradation performance, and has good application prospect.
Compared with the prior art, the photocatalysis unit and the photocatalysis method have the following advantages:
1. in the photocatalytic unit, the ultraviolet LED lamp panels are respectively arranged on two surfaces of the photocatalyst plate in parallel, the photocatalyst plate has a porous structure, and the ultraviolet LED lamp panels are provided with the ventilation holes, so that the improvement of gas fluidity and catalysis efficiency is facilitated. The method of the invention adopts the photocatalysis unit, which not only has convenient installation, but also can achieve good gas purification effect.
2. The photocatalytic unit adopts a foamed ceramic carrier to load TiO 2 The photocatalyst has higher activity and stability.
For a unit amount of TiO 2 The smaller the crystallite size, the larger the specific surface area, the higher the catalytic activity, while the smaller the crystallite size, the less easy to support, and even if supported, the loss or coverage by inactive components is likely to occur, thereby affecting the activity and stability of the catalyst. The inventor finds that TiO through a large number of experiments 2 The crystal grain grows on the foam ceramic carrier in proper micron size and forms titanium dioxide with high active phase, which is favorable for decomposing organic matter under the catalysis of ultraviolet light and has better activity 2 The base of the crystal grain is integrated with the foamed ceramic carrier, and the TiO can be greatly improved by the structure 2 Fixed strength of grains, tiO 2 Crystal grains are not easy to lose, and TiO is also used 2 The crystal grains have smooth crystal faces and are not easily covered by inactive components, so that the stability of the catalyst is greatly improved.
3. The photocatalytic unit adopts a foamed ceramic carrier to load TiO 2 The photocatalyst adopts an open-cell foam structure, the surface of the pore edges of the foam ceramic and the inside of the pore channels are distributed with composite oxides, at least a part of the composite oxides are embedded into and/or penetrate through the pore channels, and the main crystal phase of the composite oxides is gamma-Al 2 O 3 Has higher specific surface area, higher mechanical strength, higher aperture ratio and good adsorption and desorption performance, and simultaneously TiO 2 The crystal grains are distributed on the surface of the carrier in proper micron size, so that the contact chance with organic matters in water or gas is increased, and the TiO crystal grains are dispersed on the surface of the carrier in proper micron size 2 Not easy to lose, and has higher photocatalytic reaction activity and stability.
Drawings
FIG. 1 shows a TiO supported foamed alumina-based carrier according to the present invention 2 An appearance view of the photocatalyst;
FIG. 2 is a 500-fold enlarged view of a foamed alumina-based carrier A of the present invention by a scanning electron microscope;
FIG. 3 is an enlarged cross-sectional view of a photocatalyst according to the present invention; wherein, 1-TiO 2 Crystalline, 2-photocatalyst;
FIG. 4 is an XRD pattern of catalyst A obtained in example 1;
fig. 5 is a schematic view of an ultraviolet LED lamp panel according to an embodiment of the present invention, wherein the lamp panel includes a 3-ultraviolet LED lamp panel, a 31-substrate, 32-LED ultraviolet light emitting particles, and 33-ventilation holes;
FIG. 6 is a schematic view of a photocatalytic unit according to an embodiment of the present invention; wherein 4-the light-catalyzed unit, 3-an ultraviolet LED lamp panel and 5-a fixed frame;
FIG. 7 is a schematic view of a device for testing the performance of a photocatalytic unit of the catalyst of the present invention; wherein, 4-photocatalysis unit, 6-wind channel.
Detailed Description
The technical solution of the present invention is described in detail below with reference to examples, which do not limit the scope of the present invention. In the present invention, wt% is a mass fraction.
In the present invention, tiO is used 2 The crystal form of the crystal is measured by an XRD method, the instrument is a Rigaku D/max-2500X-ray diffractometer, a Cu target (0.15406 nm) is adopted, graphite single crystal filtering is carried out, the operating tube voltage is 40kV, the tube current is 30mA, the scanning step length is 0.026 degrees, and the scanning range is 5-70 degrees.
In the present invention, tiO is on the surface of the catalyst 2 The size and distribution of crystal grains are measured by scanning electron microscope, observed by Hitachi X650 scanning electron microscope, operating voltage 15kV, nitrogen protection, and intermittent metal spraying.
In the catalyst of the present invention, tiO 2 The content of (B) is measured by a chemical method. In the support of the invention, tiO 2 The content of (b) is measured by a chemical method.
In the present invention, the open cell content of the organic foam and the foamed alumina-based support is determined according to ASTM D6226-2005, with the pore density expressed in ppi as the number of pores per inch of length.
As shown in fig. 5, the ultraviolet LED lamp panel 3 includes a substrate 31 and a plurality of ultraviolet LED light emitting particles 32 disposed on the substrate 31, and the substrate 31 is further provided with a vent 33. The shape of the lamp panel 3 may be square, and as an alternative embodiment, may also be square, circular, oval or other shapes. The shape of the ventilation hole 33 is rectangular. As an alternative embodiment, a square, circular, oval or other shape is also possible. It should be understood that, the shape of the ultraviolet LED lamp panel 3 and the ventilation holes 33 can be determined by those skilled in the art according to the needs, the use place, the ventilation requirements, and the like, and the present invention is not limited thereto. The ultraviolet LED luminescent particles 32 are arranged in an array on the substrate, with vents 33 disposed between adjacent arrays. The substrate 31 is in a fence type, that is, the fence is provided with LED ultraviolet light emitting particles arranged in an array manner, and the ventilation holes 33 are formed between the fence. The number of the ultraviolet LED luminescent particles 32 can be adjusted according to the illumination intensity required by the photocatalyst.
As shown in fig. 6, the photocatalytic unit 4 includes an ultraviolet LED lamp panel 3, a photocatalyst plate 5, and a fixing frame 6. Wherein, two ultraviolet LED lamp panels 3 are respectively arranged on two sides of the photocatalyst plate 5 in parallel, and the photocatalyst plate 5 and the ultraviolet LED lamp panels 3 are fixed by adopting a fixing frame 6 to form a photocatalytic unit 4.
The foam ceramics used in the examples of the present invention and the comparative examples were alpha-Al 2 O 3 The pore edges of the foamed ceramic are provided with three-dimensional through micron-sized pore channels, and the diameter of an orifice on the outer surface of the foamed ceramic is 1-100 mu m.
The preparation process of the titanium sol is as follows: adding titanium (IV) acetylacetonate solid powder and carboxymethyl cellulose into isopropanol, and uniformly mixing to obtain titanium sol with the molar concentration of titanium of 3mol/L, wherein the molar ratio of the addition amount of the carboxymethyl cellulose to titanium atoms is 3:100.
example 1
According to the nano titanium dioxide powder (the particle size is less than 100nm, the same is as below): alumina dry glue powder (in alumina): peptizing acid: kaolin: the weight ratio of water is 1.5:10:2.5:0.4:6.0, mixing to prepare composite oxide precursor slurry A1;
mixing nano titanium dioxide powder with polyethylene glycol 600, and then mixing with alumina dry glue powder, peptized acid and water according to the proportion of nano titanium dioxide powder: alumina dry glue powder (in alumina): peptizing acid: kaolin: the weight ratio of water is 3:10:2.5:0.3:6.5, mixing to prepare composite oxide precursor slurry A2, wherein the addition of the polyethylene glycol accounts for 2% of the weight of the composite oxide precursor slurry;
the length of the foamed ceramic is 15cm, the width of the foamed ceramic is 15cm, the thickness of the foamed ceramic is 1cm, the opening rate of the foamed ceramic is 70%, the diameter of a pore of the foamed ceramic is 1-5 mm, and the pore density of the foamed ceramic is 10ppi. The pore volume of the foamed ceramic is 0.31mL/g, the pore volume occupied by the pore diameter of less than 20 micrometers is 10% of the total pore volume, the pore volume occupied by the pore diameter of 20-80 micrometers is 80% of the total pore volume, and the pore volume occupied by the pore diameter of more than 80 micrometers is 10% of the total pore volume. The pore volume and the pore distribution of the foamed ceramic are micropore parameters measured by a mercury intrusion method. Vacuum impregnating the composite oxide precursor slurry A1 twice in the foamed ceramic, drying for 6 hours at 70 ℃ after impregnation, then vacuum impregnating the composite oxide precursor slurry A2, drying for 6 hours at 70 ℃, and roasting for two sections, namely roasting for 4 hours at 200 ℃ and roasting for 3 hours at 650 ℃ to obtain a foamed ceramic carrier A; wherein the composite oxide accounts for 30% of the weight of the foamed ceramic carrier;
soaking the foamed ceramic carrier A into titanium sol for vacuum impregnation and slurry hanging, removing excessive slurry, drying at 70 ℃ for 6 hours, repeating the impregnation twice, then roasting in the presence of water vapor and nitrogen in sections, namely roasting at 200 ℃ for 4 hours, and then roasting at 650 ℃ for 3 hours to obtain the foamed ceramic carrier supported TiO 2 And the photocatalyst A is a square plate. Wherein, in the catalyst A, tiO 2 The total content of (A) is 12%.
In the obtained catalyst A, tiO was measured by XRD 2 Mainly anatase, see fig. 3.
Foamed ceramic carrier loaded TiO 2 The graph of photocatalyst A magnified 500 times by optical microscope is shown in FIG. 1, and from FIG. 1, it can be seen that TiO is on the outer surface of the catalyst 2 Distributed in small grains.
Measuring the prepared TiO on the surface of the catalyst by adopting a scanning electron microscope 2 Crystal grains and obtaining TiO by a statistical method 2 Grain size, wherein a representative catalyst surface is selected, the statistical area is about 20000 μm 2 Statistical TiO 2 The total number of crystal grains exceeds 500. TiO with the particle size of 15-45 mu m on the surface of the catalyst A, wherein the particle size of TiO is 5-50 mu m and accounts for 90% 2 The grains account for about 84%.
Observing the cross section of the catalyst by a scanning electron microscope, tiO 2 The crystal grains 1 are partially embedded in the catalyst 2, the non-embedded parts are distributed on the outer surface of the catalyst 2, the schematic diagram is shown in figure 2, and the three-dimensional through micron-sized pore channels of the foam ceramic pore edges are embedded and penetrated with alumina and titanium oxide composite oxides through observation of the pore edge parts.
Example 2
Preparing nano titanium dioxide powder: alumina dry glue powder (in alumina): peptizing acid: kaolin: the weight ratio of water is 2.0:10:2.0:0.5:6.0, mixing to prepare composite oxide precursor slurry B1;
mixing nano titanium dioxide powder with polyethylene glycol 600, and then mixing with alumina dry glue powder, peptized acid and water according to the proportion of the nano titanium dioxide powder: alumina dry glue powder (in alumina): peptizing acid: kaolin: the weight ratio of water is 2.5:10:2.5:0.3:6.5, mixing to prepare composite oxide precursor slurry B2, wherein the addition of the polyethylene glycol accounts for 2% of the weight of the composite oxide precursor slurry;
taking square foamed ceramic, wherein the length is 15cm, the width is 15cm, the thickness is 1cm, the opening rate is 70%, the diameter of a pore is 1-5 mm, and the pore density is 20ppi. The pore volume of the foamed ceramic is 0.26mL/g, the pore volume occupied by the pore diameter of less than 20 micrometers is 8 percent of the total pore volume, the pore volume occupied by the pore diameter of 20-80 micrometers is 82 percent of the total pore volume, and the pore volume occupied by the pore diameter of more than 80 micrometers is 10 percent of the total pore volume. The pore volume and the pore distribution of the foamed ceramic are micropore parameters measured by a mercury intrusion method. Vacuum impregnating the composite oxide precursor slurry B1 twice in the foamed ceramic, drying for 6 hours at 70 ℃ after impregnation, then vacuum impregnating the composite oxide precursor slurry B2, drying for 6 hours at 70 ℃, roasting for two sections, namely roasting for 4 hours at 200 ℃, and roasting for 3 hours at 650 ℃ to obtain a foamed ceramic carrier B; wherein the composite oxide accounts for 30% of the weight of the foamed ceramic carrier;
soaking the foamed ceramic carrier B into the titanium sol for vacuum impregnation and slurry hanging, removing excessive slurry, drying for 6 hours at 70 ℃, repeatedly soaking twice, then carrying out sectional roasting in the presence of water vapor and nitrogen, namely roasting for 4 hours at 200 ℃, and then roasting for 3 hours at 650 ℃ to obtain the foamed ceramic carrier loaded TiO 2 And the photocatalyst B is a square plate. Wherein, in the catalyst B, tiO 2 The total content of (A) is 15%.
In the obtained catalyst B, tiO was measured by XRD 2 Mainly anatase.
Measuring the prepared TiO on the surface of the catalyst by adopting a scanning electron microscope 2 Crystal grains and obtaining TiO by adopting a statistical method 2 Grain size, wherein a representative catalyst surface is selected, the statistical area is about 20000 μm 2 Statistical TiO 2 The total number of crystal grains exceeds 500. TiO of 15 to 45 μm particle size on the surface of the catalyst B, which accounts for 88% of the particle size of 5 to 50 μm 2 The grain size is about 83%.
Observing the cross section of the catalyst by a scanning electron microscope, tiO 2 The crystal grains 1 are partially embedded in the catalyst 2, and the non-embedded part is distributed on the outer surface of the catalyst 2, and the schematic diagram is shown in figure 2; by observing the hole edge part, the alumina and titanium oxide composite oxide is embedded and penetrated in the three-dimensional through micron-sized pore canal of the foam ceramic hole edge
Example 3
According to the weight ratio of nano titanium dioxide powder: alumina dry glue powder (in alumina): peptizing acid: kaolin: the weight ratio of water is 1.0:10:2.0:0.5:6.0, and preparing composite oxide precursor slurry C1.
Mixing nano titanium dioxide powder with polyethylene glycol 600, and then mixing with alumina dry glue powder, peptized acid and water according to the proportion of nano titanium dioxide powder: alumina dry glue powder (in alumina): peptizing acid: kaolin: the weight ratio of water is 3.0:10:3.0:0.3:8.0 percent of the mixture is mixed to prepare composite oxide precursor slurry C2, wherein the addition amount of the polyethylene glycol accounts for 2.5 percent of the weight of the composite oxide precursor slurry;
the same procedure as in example 1 was repeated. Vacuum impregnating the composite oxide precursor slurry C1 twice in the foamed ceramic, drying for 6 hours at 70 ℃ after impregnation, then vacuum impregnating the composite oxide precursor slurry C2, drying for 6 hours at 70 ℃, roasting for two sections, namely roasting for 3 hours at 220 ℃, and roasting for 4 hours at 600 ℃ to obtain a foamed ceramic carrier C; wherein the composite oxide accounts for 25% of the weight of the foamed ceramic carrier;
soaking the foamed ceramic carrier C into titanium sol for vacuum impregnation and slurry hanging, removing excessive slurry, drying at 70 ℃ for 6 hours, repeating the impregnation twice, then carrying out sectional roasting in the presence of water vapor and nitrogen, namely roasting at 220 ℃ for 3 hours, and then roasting at 600 ℃ for 4 hours to obtain the foamed ceramic carrier supported TiO 2 And the photocatalyst C is a square plate. Wherein, in the catalyst C, tiO 2 The total content of (A) is 18%.
In the obtained catalyst C, tiO was measured by XRD 2 Mainly anatase.
Measuring the prepared TiO on the surface of the catalyst by adopting a scanning electron microscope 2 Crystal grains and obtaining TiO by adopting a statistical method 2 Grain size, wherein a representative catalyst surface is selected, the statistical area is about 20000 μm 2 Statistical TiO 2 The total number of crystal grains exceeds 500. TiO of 5 to 50 μm or 89% particle size and 15 to 45 μm particle size on the surface of the catalyst C 2 The grains account for about 84%.
Observing the cross section of the catalyst by a scanning electron microscope, tiO 2 The crystal grains 1 are partially embedded in the catalyst 2, and the non-embedded part is distributed on the outer surface of the catalyst 2, and the schematic diagram is shown in figure 2; by observing the hole edge part, the alumina and titanium oxide composite oxide is embedded and penetrated in the three-dimensional through micron-sized pore canal of the foam ceramic hole edge.
Comparative example 1
The ceramic foam support A of example 1 was replaced with the α -Al used in example 1 2 O 3 Foamed ceramic is used as the carrier DA. Soaking the carrier DA in titanium sol for vacuum impregnation and slurry hanging, removing excessive slurry, drying at 70 ℃ for 6 hours, repeating the impregnation twice, then roasting in the presence of water vapor and nitrogen in sections, namely roasting at 200 ℃ for 4 hours, and then roasting at 650 ℃ for 3 hours to obtain the foamed ceramic carrier supported TiO 2 And (3) a photocatalyst DA. Wherein, in the catalyst DA, tiO 2 Is 10% of total content, tiO on the outer surface 2 The crystal grains are nano-scale titanium oxide.
Example 4
This example is basically the same as example 1, except that: adding no polyethylene glycol 600 into the composite oxide precursor slurry A2 to obtain the foam ceramic carrier-supported TiO 2 And (3) a photocatalyst D. In the catalyst D, the mass content of titanium oxide was 12%.
In the obtained catalyst D, tiO was measured by XRD 2 Mainly anatase.
Measuring the prepared TiO on the surface of the catalyst by adopting a scanning electron microscope 2 Crystal grains and obtaining TiO by a statistical method 2 Grain size, wherein a representative catalyst surface is selected, the statistical area is about 20000 μm 2 Statistical TiO 2 The total number of crystal grains exceeds 500. TiO of particle size 15 to 45 μm on the surface of catalyst D, which accounts for 85% of the particle size of 5 to 50 μm 2 The grains account for about 81%.
Observing the cross section of the catalyst by a scanning electron microscope, tiO 2 The crystal grains are partially embedded into the catalyst, and the non-embedded parts are distributed on the outer surface of the catalyst, and the schematic diagram is shown in figure 2; by observing the hole edge part, the alumina and titanium oxide composite oxide is embedded and penetrated in the three-dimensional through micron-sized pore canal of the foam ceramic hole edge.
Example 5
This embodiment is basically the same as embodiment 1, except that: soaking the obtained carrier A into titanium sol for vacuum soaking and slurry hanging, removing excessive slurry, drying at 75 ℃ for 6 hours, and repeating the step for 1 time;then adopting single-stage roasting in the presence of water vapor and nitrogen, namely roasting at 650 ℃ for 5 hours to obtain the foam ceramic carrier supported TiO 2 And (3) a photocatalyst E. In the catalyst E, the mass content of titanium oxide was 12.0%.
In the obtained catalyst E, tiO was measured by XRD 2 Mainly anatase.
Measuring the prepared TiO on the surface of the catalyst by adopting a scanning electron microscope 2 Crystal grains and obtaining TiO by a statistical method 2 Grain size, wherein the statistical area is about 20000 μm 2 Statistical TiO 2 The total number of crystal grains exceeds 1000. The particle size on the surface of the catalyst E is measured to be 5 to 50 mu mTiO 2 TiO with grain size of 15-45 microns and grain size of 84% 2 The grains account for about 80%.
Observing the cross section of the catalyst by a scanning electron microscope, tiO 2 The crystal grains are partially embedded into the catalyst, and the non-embedded parts are distributed on the outer surface of the catalyst, and the schematic diagram is shown in figure 2; by observing the hole edge part, the alumina and titanium oxide composite oxide is embedded and penetrated in the three-dimensional through micron-sized pore channels of the foam ceramic hole edge.
Example 6
The test is to test the photocatalytic performance of the photocatalyst A, wherein the test conditions are as follows:
(1) Testing raw materials: air with toluene, xylene, benzene, ammonia, formaldehyde, acetaldehyde, sulfur dioxide, and hydrogen sulfide as contaminants was used as the test feedstock, respectively.
(2) And (3) testing equipment: as shown in FIG. 6, the photocatalyst A is taken out to be made into a photocatalytic unit, and then the photocatalytic unit is fixed in an air duct with a fan of a corresponding specification to form the testing equipment, as shown in FIG. 7. The parameters of the photocatalyst A and the LED lamp are set as follows:
the photocatalyst A is plate-shaped: the length is 15cm, the width is 15cm, and the thickness is 1cm;
the ultraviolet LED lamp panel comprises a substrate and 48 LED ultraviolet light-emitting particles on the substrate, the LED ultraviolet light-emitting particles are evenly distributed on the substrate in an array manner, 8 LED ultraviolet light-emitting particles are distributed on each array, 6 rows of the array are formed, and the appearance of the substrate is in a fence shape as shown in figure 5. Ultraviolet LED luminescent particles emit towards the photocatalyst AThe wavelength of light is 365nm ultraviolet light, the length of the substrate is 15cm, the width of the substrate is 15cm, two ultraviolet LED lamp panels are placed on two sides of the photocatalyst A plate in parallel, the distance is 2cm, and the intensity of single-side ultraviolet light on the photocatalyst A reaches 10 mW/cm 2 ；
The cross section of the air duct is square, and the photocatalyst unit is hermetically placed in the air duct;
(3) Test method and test conditions: preparing a sample experiment chamber and a blank experiment chamber;
place the test equipment at 1m 3 And sealing the sample experiment chamber, and filling pollutants into the experiment chamber. Starting the test equipment and the LED lamp, wherein the feeding speed is 0.5L/min, the test temperature is 26 ℃, the normal pressure is realized, the test time is 1 hour, and the results are shown in Table 1;
the blank experiment chamber and the sample experiment chamber are operated differently, only the test equipment is started, but the LED lamp is not started, and the result is shown in table 1;
(4) The detection of the pollutant acetaldehyde is carried out according to GB/T18883-2002, the detection method of the benzene and the benzene series is carried out according to GB/T11737-1989, and the detection method of the formaldehyde is carried out according to GB/T18204.26-2000;
(5) The results of the catalyst sterilization test using a staphylococcus albus-containing gas as a raw material are shown in table 3.
Table 1 results of contaminant detection using catalyst a prepared in example 1
Examples 7 to 10
The detection method for contaminants purified and the detection method for sterilization were the same as in example 6 except that the catalyst samples were replaced with the catalysts B to E prepared in examples 2 to 5, respectively, and the results are shown in tables 2 and 3.
Comparative example 2
The detection method for purified contaminants and the detection method for sterilization were the same as in example 6 except that the catalyst sample was replaced with the catalyst DA prepared in comparative example 1, and the results are shown in tables 2 and 3.
Table 2 results of contaminant detection in the purification of catalyst prepared in examples 2 to 5 and comparative example 1
TABLE 3 results of the sterilization test using the catalysts prepared in examples and comparative examples
| Catalyst numbering | Testing microorganisms | Treatment time, 0h | Treatment time, 1h | Removal Rate (%) |
| Catalyst A | Staphylococcus albus | 6.5×10 4 | 85 | 99.87 |
| Catalyst B | Staphylococcus albus | 6.5×10 4 | 97 | 99.85 |
| Catalyst C | Staphylococcus albus | 6.5×10 4 | 92 | 99.86 |
| Catalyst D | Staphylococcus albus | 6.5×10 4 | 101 | 99.84 |
| Catalyst E | Staphylococcus albus | 6.5×10 4 | 103 | 99.84 |
| Catalyst DA | Staphylococcus albus | 6.5×10 4 | 108 | 99.83 |
Example 11
This example is a catalyst stability test.
Putting the catalyst A into a container provided with ultrasonic waves, wherein the ultrasonic treatment conditions are as follows: the volume ratio of water to catalyst is 4:1, the ultrasonic frequency is 30kHz, the power is 20W/L according to the volume of the solution, the temperature is 30 ℃, the treatment frequency is 5 times, each treatment time is 30min, then the catalyst A is used for the photocatalytic performance test, the test method is the same as the example 6, and the result shows that the removal rate of pollutants in each test is reduced, the reduction rate is less than 1 percent, and the removal rate of staphylococcus albus is 99.01 percent.
Examples 12 and 13
The stability of catalysts B and C was tested as in example 11, resulting in a reduction in the removal of each tested contaminant of less than 1.5% and a reduction in the removal of Staphylococcus albus of less than 1.5%. Examples 14 and 15
The stability of catalysts D and E was tested as in example 11, resulting in a reduction in the removal of each contaminant tested, between 2% and 3%, and about 2% reduction in the removal of Staphylococcus albus.
Comparative example 3
The stability of catalyst DA was tested as in example 11, and as a result, the removal rate of each contaminant tested was reduced to a level of 10% or more, and the removal rate of Staphylococcus albus was 84%.
Example 16
In the same example 6, except that "two ultraviolet LED lamp panels in the test condition (2) were placed in parallel on both sides of the photocatalyst A plate at an interval of 2cm, and the intensity of single-sided ultraviolet light on the photocatalyst A reached 10 mW/cm 2 "; the method is characterized in that two ultraviolet LED lamp panels are arranged on two sides of a photocatalyst A plate in parallel at an interval of 5cm, and the single-side ultraviolet intensity on the photocatalyst A reaches 0.8mW/cm 2 ", the results are shown in Table 4.
Table 4 example 16 test results for decontamination of contaminants
Claims (26)
1. A photocatalytic unit, comprising:
the photocatalyst is a foamed ceramic carrier loaded with TiO 2 Photocatalyst, said foamed ceramic carrier supporting TiO 2 In the photocatalyst, tiO distributed on the outer surface of the catalyst 2 Crystal grain of TiO 5-50 micron size 2 The crystal grains account for more than 70 percent; the foamed ceramic carrier comprises foamed ceramic and composite oxide, the foamed ceramic is in an open-cell foam structure, the pore edges of the foamed ceramic contain three-dimensional through micron-sized pore channels, the surface of the pore edges and the interior of the pore channels are distributed with the composite oxide, and the composite oxide comprisesAlumina and titania; in the foamed ceramic carrier, at least one part of composite oxide is embedded into and/or penetrates through the pore; the content of titanium dioxide in the surface of the carrier is higher than the content of titanium dioxide inside the carrier;
an ultraviolet light source device having a light emitting portion facing a photocatalyst.
2. The photocatalytic unit of claim 1, wherein the photocatalyst is a photocatalyst plate, the ultraviolet light source device is an ultraviolet LED lamp panel, and the ultraviolet LED lamp panel is provided on one or both surfaces of the photocatalyst plate.
3. A photocatalytic unit according to claim 2, characterized in that the photocatalyst plate is arranged in parallel with the ultraviolet LED lamp panel.
4. A photocatalytic unit according to claim 3, characterized in that the distance between the photocatalyst board and the ultraviolet LED lamp panel is 0-10cm.
5. The photocatalytic unit of claim 4, wherein the distance between the photocatalyst board and the ultraviolet LED lamp panel is 0.5-3.5 cm.
6. A photocatalytic unit according to claim 2, characterized in that the thickness of the photocatalyst plate is 0.3 to 3.0cm.
7. The photocatalytic unit of claim 2, wherein the ultraviolet LED lamp panel comprises a substrate and a plurality of LED ultraviolet light emitting particles disposed on the substrate; LED ultraviolet light-emitting particles on the ultraviolet LED lamp panel are arranged in an array mode, and ventilation holes are arranged or not arranged between adjacent arrays.
8. A photocatalytic unit according to claim 7, characterized in that the substrate is of a barrier type, i.e. the barrier bars are provided with LED UV emitting particles arranged in an array, and vent holes are provided between the barrier bars.
9. The photocatalytic unit of claim 2, wherein N photocatalytic boards are disposed in the photocatalytic unit, and ultraviolet LED lamp panels are disposed on both sides of each photocatalytic board and are disposed in parallel, where N is an integer greater than or equal to 1.
10. The photocatalytic unit of claim 2, further comprising a fixing frame for fixing the photocatalyst plate and the uv LED lamp plate.
11. Photocatalytic unit according to claim 1, characterized in that the ceramic foam support carries TiO 2 In the photocatalyst, tiO distributed on the outer surface of the catalyst 2 Crystal grain of TiO 5-50 micron size 2 The crystal grains account for more than 80 percent.
12. Photocatalytic unit according to claim 11, characterized by TiO distributed on the outer surface of the catalyst 2 Crystal grain of TiO 15-45 μm in size 2 The crystal grains account for more than 70 percent.
13. Photocatalytic unit according to claim 11, characterized by TiO distributed on the outer surface of the catalyst 2 Crystal grain of TiO 15-45 μm in particle size 2 The crystal grains account for more than 80 percent.
14. A photocatalytic unit according to claim 1 or 11, characterized in that TiO is based on the weight of the photocatalyst 2 The total content of the component (A) is 5 to 40 percent, and the weight of titanium dioxide contained in the composite oxide in the foamed ceramic carrier accounts for the weight of TiO in the photocatalyst 2 5 to 50 percent of the total weight.
15. A photocatalytic unit according to claim 14, characterized in that TiO is based on the weight of the photocatalyst 2 The total content of (A) is 8-35%.
16. A photocatalytic unit according to claim 14, characterized in that the composite oxide in the ceramic foam support contains TiO 2 Mainly anatase type.
17. A photocatalytic unit as set forth in claim 1, wherein said composite oxide comprises 10-50% by weight of the ceramic foam support, and wherein said composite oxide comprises 10-90% by weight of titanium oxide; the alumina in the composite oxide is gamma-Al 2 O 3 。
18. A photocatalytic unit as set forth in claim 1 wherein said ceramic foam comprises alumina, said alumina being α -Al 2 O 3 。
19. The photocatalytic unit of claim 18, wherein the cell edges of the ceramic foam have micron-sized cell channels running through three-dimensionally; the pore volume of the foamed ceramic is 0.1-0.5 mL/g, the pore volume of the foamed ceramic with the pore diameter of less than 20 mu m accounts for less than 20% of the total pore volume, the pore volume of the foamed ceramic with the pore diameter of 20-80 mu m accounts for 50-95% of the total pore volume, and the pore volume of the foamed ceramic with the pore diameter of more than 80 mu m accounts for less than 10% of the total pore volume.
20. The photocatalytic unit according to claim 18, wherein the outer surface of the ceramic foam has micron-sized pore openings with a diameter of 1 to 100 μm, and the pore openings are uniformly distributed.
21. The photocatalytic unit according to claim 1, wherein the ceramic foam has an open cell content of 40 to 90%, a cell diameter of 1 to 5mm, and a pore density of 8 to 60 ppi.
22. The photocatalytic unit of claim 21, wherein the ceramic foam has an open cell content of 60 to 80% and a pore density of 8 to 30ppi.
23. A photocatalytic method characterized by: using the photocatalytic unit according to any one of claims 1 to 22; the photocatalyst adopts a photocatalyst plate, the ultraviolet light source device adopts an ultraviolet LED lamp plate, and gas to be purified passes through the photocatalytic unit and enters into photocatalytic reaction under the action of ultraviolet light and the photocatalyst to obtain purified gas.
24. The photocatalytic method as set forth in claim 23, wherein the wavelength of ultraviolet light emitted from the ultraviolet LED lamp is 280 to 390nm; the distance between the ultraviolet LED lamp panel and the photocatalyst plate is 0-10cm; the radiation intensity on the photocatalyst plate is 0.01 to 500mW/cm 2 。
25. The photocatalytic method according to claim 24, wherein the ultraviolet LED lamp emits ultraviolet light at a single wavelength; the distance between the ultraviolet LED lamp panel and the photocatalyst plate is 0-5 cm; the radiation intensity on the photocatalyst plate is 0.5 to 70mW/cm 2 。
26. The photocatalytic method according to claim 24, wherein the ultraviolet LED lamp emits ultraviolet light having a wavelength of 365nm; the distance between the ultraviolet LED lamp panel and the photocatalyst plate is 0.5-3.5 cm.
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| CN102744049A (en) * | 2012-07-06 | 2012-10-24 | 长安大学 | Process for preparing TiO2 (titanium dioxide) film on aluminum-oxide foamed ceramic |
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| JP3791901B2 (en) * | 2001-07-16 | 2006-06-28 | 株式会社ノリタケカンパニーリミテド | Photocatalyst holder and method for producing the same |
| JP6866596B2 (en) * | 2015-09-30 | 2021-04-28 | Toto株式会社 | Photocatalyst coating |
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| JPH1085608A (en) * | 1996-09-17 | 1998-04-07 | Toto Ltd | Photocatalytic hydrophilic member and its production |
| CN2598626Y (en) * | 2002-12-16 | 2004-01-14 | 天津大学 | Chemical laboratory waste gas absorption-photocatalytic degradation cleaning devie |
| CN102744049A (en) * | 2012-07-06 | 2012-10-24 | 长安大学 | Process for preparing TiO2 (titanium dioxide) film on aluminum-oxide foamed ceramic |
| CN102872892A (en) * | 2012-10-24 | 2013-01-16 | 浙江大学苏州工业技术研究院 | Foamed ceramic based photocatalytic component and preparation method thereof |
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