CN100563814C - The nano-crystalline photocatalysis reactor of continuous mobile type purifying air and water - Google Patents
The nano-crystalline photocatalysis reactor of continuous mobile type purifying air and water Download PDFInfo
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- CN100563814C CN100563814C CNB2007100183229A CN200710018322A CN100563814C CN 100563814 C CN100563814 C CN 100563814C CN B2007100183229 A CNB2007100183229 A CN B2007100183229A CN 200710018322 A CN200710018322 A CN 200710018322A CN 100563814 C CN100563814 C CN 100563814C
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Abstract
The invention discloses the nano-crystalline photocatalysis reactor of a kind of continuous mobile type purifying air and water.Its key problem in technology is: catalyst fixedly phase (2) is porous silica glass loaded with nano TiO
2Photochemical catalyst, the light transmittance of porous silica glass in 200～800nm wave-length coverage are greater than 90%, and density is 0.5～0.9g/cm
3, voidage is 65～75%.The present invention is that carrier is with TiO with the porous silica glass
2Adulterate body is deposited on the porous silica glass inner surface as photochemical catalyst, utilize the double grading that the porous silica glass light transmission is good and specific area is big, light-catalysed ability and efficient have been increased, structures such as the plate film that same category of device uses traditionally, periosteum have been changed, overcome that traditional structure etc. exists photochemical catalyst and the reactant contact area is little, carrier is to shortcomings such as energy of light source loss late height, makes nano-crystalline photocatalysis reactor enter high efficiency and practicability stage.
Description
Technical field
The present invention relates to the nano-crystalline photocatalysis reactor of a kind of continuous mobile type purifying air and water and manufacturing and designing of indoor air cleaner and drink water purifying treating apparatus thereof, belong to Nano semiconductor membrane material photo catalysis reactor technical field.
Background technology
Because synthetics such as the washing agent that uses in adhesive, paint vehicle and the daily life used in the interior architecture ornament materials, furniture, finishing manufacturing process, cosmetics can be emitted a large amount of VOCs to indoor, comprise that formaldehyde, benzene series thing, chloride, ketone, hydro carbons etc. all are detrimental to health to some extent.Therefore, the Nano semiconductor photo catalysis reactor becomes the research focus, and it can be used for the air cleaning that family, hospital, dancing hall, meeting room, historical relic deposit places such as exhibition.Drinking Water in China adopts traditional chlorine and chlorine-containing compound to handle water mostly on the other hand, make water have secondary pollution, and further also residual chlorine in vegetables in the export processing process and the marine product, the outlet processed food is affected, it is unfavorable to the more important thing is health, handles so photo catalysis reactor also can be used for drinking water disinfection.
Photo catalysis reactor is that light-catalyzed reaction takes place and final the degraded removed the device of nuisance, reactant is contacted with the catalyst large tracts of land, and will conveniently use.In mobile phase photo catalysis reactor, existing way according to catalyst, roughly can be divided into rotating plasma precursor reactant device, fluidized-bed reactor and fixed bed reactors three classes, wherein the fixed bed reactors kind is more, and it is different and different with structure mainly to be the catalyst carrier material: as use light transmission on the material relatively poor woven wire class, difform ceramic-like etc. are arranged; That uses the better material of light transmission has optical fiber [Chinese patent ZL01113708.8], glass plate, capillary glass tube [Chinese patent application ZL 200610029643.4], glass fiber, a macromolecular material etc.; And for example carrier structure is different traditional sheet frame shape [Chinese patent ZL 02144673.3], graininess, cellular, dull and stereotyped membranaceous and periosteum shape structures such as [Chinese patent ZL 01265866.9].Above mentioned various photo catalysis reactor all has advantage and purpose of design separately, but has shortcomings such as, catalyst not high to the energy of light source utilization rate and reactant contact area are little.
Summary of the invention
The object of the invention provides the big continuous mobile type purifying air of a kind of energy of light source utilization rate height, catalyst and reactant contact area and the nano-crystalline photocatalysis reactor of water, to overcome the main deficiency of prior art.
The present invention adopts following technical scheme to realize its goal of the invention:
The nano-crystalline photocatalysis reactor of continuous mobile type purifying air and water, it comprises fixedly phase (2), glass bushing (3), ultraviolet source (4), the phase import (5) of flowing of catalyst in the reactor shell (1), cylindrical shell (1), flowing exports (6) and flange (7) mutually.Described catalyst fixedly phase (2) is porous silica glass loaded with nano TiO
2Photochemical catalyst, the light transmittance of porous silica glass in 200～800nm wave-length coverage are greater than 90%, and density is 0.5～0.9g/cm
3, voidage is 65～75%.
Described nano-TiO
2Photochemical catalyst is the nano-TiO of metal ion mixing (with the metal oxide form)
2Photochemical catalyst, the metal ion mixing amount is TiO by mass percentage
21～4% of amount, metal ion is selected from Cu
2+, Ag
+, Fe
3+, Co
2+, Ni
2+, Tb
3+, Eu
3+, its salt such as Cu (Ac)
2, AgNO
3, FeCl
3, CoCl
2, Ni (NO
3)
2, Tb (NO
3)
3, Eu (NO
3)
3Deng.
Described glass bushing (3) is a quartz glass sleeve, and porous silica glass loaded optic catalyst fixedly phase (2) is laid in around the quartz glass sleeve by even the installation, has guaranteed evenly transmission effectively of ultraviolet source (4).
The phase import (5) of flowing is positioned at reactor bottom, and flowing mutually, outlet (6) is positioned at the reactor upper side.Design is the even transmission in order to ensure stream material like this; The phase import is positioned at the reactor lower part side if flow, and material forms turbulent flow easily, forms inhomogeneous flowing, and residence time of material is inhomogeneous, and is unfavorable to degrading.
The manufacture method of the nano-crystalline photocatalysis reactor of continuous mobile type purifying air and water, its key is that porous silica glass takes following processing method: quartz glass is become half garden ring cylinder shape porous silica glass through high temperature process, treat to handle 5 minutes with 3～5% hydrofluoric acid solution after its cooling, wash to pH=7 with deionized water or distilled water, at last with absolute ethanol washing, dehydration and dry.
The porous silica glass that above-mentioned processing is obtained impregnated in the butyl titanate ethanolic solution coating 30 minutes, took out air dry, again in 450 ℃～500 ℃ calcinings down, cooled off naturally and promptly obtained the load of carrier inner surface nano-TiO is arranged
2The carrier of photocatalyst of film, or be called fixedly phase of photochemical catalyst, the nano-TiO of the carrier surface that obtains
2Particle size is 20-50nm.
In order to improve activity of such catalysts and to catch short fast to reactant, at TiO
2In the metal ion (with the metal oxide form) that mixed, specific practice is: according to the difference of doped metal ion, also added soluble metallic salt in the butyl titanate ethanolic solution, the metal ion mixing amount is TiO by mass percentage
21～4% of amount, metal ion is selected from Cu
2+, Ag
+, Fe
3+, Co
2+, Ni
2+, Tb
3+, Eu
3+, its salt such as Cu (Ac)
2, AgNO
3, FeCl
3, CoCl
2, Ni (NO
3)
2, Tb (NO
3)
3, Eu (NO
3)
3Deng.
Above-mentioned photo catalysis reactor series and parallel combination can be obtained the photocatalysis air purifying device of different size specifications.
Above-mentioned photo catalysis reactor series and parallel combination can be obtained the photocatalytic water treatment device of different size specifications.
Compare with background technology, the present invention has the following advantages:
1, the Photoreactor among the present invention is with porous silica glass (loaded with nano TiO
2Adulterate body) place that takes place as light reaction, new material new construction design, having high printing opacity (200～800nm wavelength) rate, large contact surface, long-pending (density is 0.5～0.9g/cm
3, voidage is 65～75%, catalyst nano TiO
2Specific area 108m
2/ g); Compare with traditional photo catalysis reactor, bigger illuminating area and response area is provided, obtained higher photocatalysis efficiency, the photochemical catalyst load is firm, long-acting, not efflorescence, do not run off.
2, the photo catalysis reactor among the present invention can degradation capability be strong, speed is fast to the organic volatile in the air system (particularly formaldehyde), and other organic matters of purification of can degrading simultaneously; To organic volatile non-selectivity almost, oxidation operation, decomposition finally can be degraded to CO
2And H
2O.
3, the photo catalysis reactor among the present invention can be used for drink water purifying and sterilization.
4, the nano-crystalline photocatalysis reactor of continuous mobile type purifying air among the present invention and water can not cause secondary pollution to environment.
5, the nano-crystalline photocatalysis reactor of continuous mobile type purifying air among the present invention and water can be according to different demands, connection in series-parallel combination arbitrarily, and applying flexible is convenient, and volume is little, and running operation is easy, and energy consumption is low.
Description of drawings
Fig. 1 is the nano-crystalline photocatalysis reactor structural representation of continuous mobile type purifying air of the present invention and water;
Fig. 2 is the schematic diagram that photo catalysis reactor of the present invention is used for air purifier;
Fig. 3 is the schematic diagram that photo catalysis reactor of the present invention is used for appliance for treating drinking water;
Fig. 4 is the TiO on the carrier in the photo catalysis reactor of the present invention
2The TEM figure and the electron diffraction pattern of membrane material;
Description of reference numerals:
The 1-reactor shell 5-phase import of flowing
The fixedly mobile outlet mutually of phase 6-of 2-catalyst
3-glass bushing 7-flange
The 4-ultraviolet lamp tube
The specific embodiment
Embodiment 1: the manufacturing of photo catalysis reactor
1, reactor parts design processing
According to reactor each several part composition requirement, design drawing and to process or buy each parts standby;
2, the processing of porous silica glass carrier
Adopt hydrogen and oxygen to be expelled to the shower nozzle burning from gas cylinder through pressure-reducing valve respectively,, be processed into half garden ring cylinder shape porous silica glass of certain size through technological process for blowing methods such as drop-down thin, the bending of high temperature, kneadings; Treat that its cooling back handled 5 minutes with 3～5% hydrofluoric acid solution, wash to pH=7 with deionized water or distilled water again, use absolute ethanol washing, dehydration at last, standby after dry;
3, to loaded optic catalyst on the carrier
Compound concentration is 20% butyl titanate ethanolic solution, adds a certain amount of slaine (Cu (Ac)
2, AgNO
3, FeCl
3, CoCl
2, Ni (NO
3)
2, Tb (NO
3)
3, Eu (NO
3)
3), doping is TiO
21～4% of amount, stirring 2h is stablized, uniform transparency liquid; With carrier dip coating 30 minutes under normal temperature condition, take out back air dry in air then,, can obtain the carrier inner surface and adhere to nano-TiO is arranged again in 500 ℃ of calcinings 10 minutes and in stove, naturally cool to room temperature down
2The photochemical catalyst of adulterate body film, nano-TiO
2Particle size is 20-50nm (Fig. 4), TiO
2Specific area 108m
2/ g uses in order to the assembly reaction device;
4, reactor is installed
Carry out each parts assembling as shown in Figure 1, bottommost is installed stainless steel netted (40～60 order) distributor in reactor earlier, refilling when establishing concentric quartz glass sleeve 3 combination loading load step by step has the porous silica glass of catalyst, upper flange and sealing ring are installed at last, and so far reactor is made installation.Ultraviolet lamp tube can be put into or be changed when reactor uses at any time, and is convenient, flexible.
Embodiment 2: the manufacturing of photocatalysis air purifying device and degradation of formaldehyde thereof
The reactor size size can be: high 933mm, external diameter 64mm, internal diameter 61mm, optical path R=17.8mm, the power of ultraviolet lamp tube are that the centre wavelength of 39W and luminescent spectrum is 258.7nm, the optical path R=17.8mm of porous silica glass carrier, height 30-50mm.
The porous silica glass loaded with nano TiO that blowing obtains
2Photochemical catalyst, the light transmittance of porous silica glass in 200～800nm wave-length coverage are greater than 90%, and density is 0.85g/cm
3, voidage is 68%.Nano-TiO
2Photochemical catalyst metal ion mixing amount is TiO
22% (mass percent) of amount, slaine is selected from Cu (Ac)
2Calcining heat and time be 500 ℃ following 10 minutes.
As shown in Figure 2, two photo catalysis reactor tandem compounds can be obtained photocatalysis air purifying device.Use photocatalysis air purifying device airborne formaldehyde is carried out catalytic degradation, at gas flow 15L/min, during concentration of formaldehyde 1.0ppm, degradation rate degrades to state scale value (0.08mg/m airborne formaldehyde up to 95% under the continuous-flow state
3) below.
Embodiment 3: the manufacturing of photocatalytic water treatment device and drinking water sterilization thereof
The reactor size size can be: high 933mm, external diameter 64mm, internal diameter 61mm, optical path R=17.8mm, the power of ultraviolet lamp tube are that the centre wavelength of 39W and luminescent spectrum is 258.7nm, the optical path R=17.8mm of porous silica glass carrier, height 30-50mm.
The porous silica glass loaded with nano TiO that blowing obtains
2Photochemical catalyst, the light transmittance of porous silica glass in 200～800nm wave-length coverage are greater than 90%, and density is 0.70g/cm
3, voidage is 72%.Nano-TiO
2Photochemical catalyst metal ion mixing amount is TiO
23% (mass percent) of amount, slaine is selected from AgNO
3Calcining heat and time be 450 ℃ following 30 minutes.
As shown in Figure 3,10 photo catalysis reactor series and parallel combinations can be obtained photocatalytic water treatment device.Using photocatalytic water treatment device can carry out catalytic degradation to the Escherichia coli in the drinking water, at drinking water flow 1M
3/ h, the sterilization rate under the e. coli concentration 30cfu/L continuous-flow state reaches 100%.
Embodiment 4: the methyl orange in the photocatalytic water treatment device degradation of dye water
The photocatalytic water treatment device of Application Example 3 carries out catalytic degradation to the methyl orange in the dyestuff, at flow 0.2M
3/ h, the colour killing rate under the concentration 5ppm continuous-flow state reaches 90%.
Claims (8)
1, the nano-crystalline photocatalysis reactor of continuous mobile type purifying air and water, it comprises fixedly phase (2), glass bushing (3), ultraviolet source (4), the phase import (5) of flowing of catalyst in reactor shell (1), the cylindrical shell (1), outlet (6) and the flange (7) mutually that flow, and it is characterized in that: catalyst fixedly phase (2) is porous silica glass loaded with nano TiO
2Photochemical catalyst, the light transmittance of porous silica glass in 200～800nm wave-length coverage are greater than 90%, and density is 0.5～0.9g/cm
3, voidage is 65～75%.
2, photo catalysis reactor according to claim 1 is characterized in that: nano-TiO
2Photochemical catalyst is the nano-TiO of metal ion mixing
2Photochemical catalyst, the metal ion mixing amount is TiO by mass percentage
21～4% of amount, metal ion is selected from Cu
2+, Ag
+, Fe
3+, Co
2+, Ni
2+, Tb
3+, Eu
3+
3, photo catalysis reactor according to claim 1 is characterized in that: the phase import (5) of flowing is positioned at reactor bottom, and flowing mutually, outlet (6) is positioned at the reactor upper side.
4, the manufacture method of the described photo catalysis reactor of claim 1, the processing method that it is characterized in that porous silica glass is as follows: quartz glass is become half garden ring cylinder shape porous silica glass through high temperature process, treat to handle 5 minutes with 3～5% hydrofluoric acid solution after its cooling, wash to pH=7 with deionized water or distilled water, at last with absolute ethanol washing, dehydration and dry.
5, the manufacture method of the described photo catalysis reactor of claim 4, it is characterized in that: the porous silica glass that obtains be impregnated in the butyl titanate ethanolic solution coating 30 minutes, take out air dry, in 450 ℃～500 ℃ calcinings down, cooling promptly obtains the load of carrier inner surface naturally nano-TiO again
2The catalyst of film is phase fixedly.
6, the manufacture method of photo catalysis reactor according to claim 5 is characterized in that: according to the difference of doped metal ion, also added soluble metallic salt in the butyl titanate ethanolic solution, the metal ion mixing amount is TiO by mass percentage
21～4% of amount, metal ion is selected from Cu
2+, Ag
+, Fe
3+, Co
2+, Ni
2+, Tb
3+, Eu
3+
7, the described photo catalysis reactor series and parallel combination of claim 1 can obtain the photocatalysis air purifying device of different size specifications.
8, the described photo catalysis reactor series and parallel combination of claim 1 can obtain the photocatalytic water treatment device of different size specifications.
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| CN103101991A (en) * | 2013-02-07 | 2013-05-15 | 广州市大禹环保科技有限公司 | Immersed type photoelectrocatalysis reaction apparatus |
| CN103263823B (en) * | 2013-05-17 | 2015-10-21 | 王培根 | Double ion air upgrading clarifier |
| CN103463971B (en) * | 2013-09-05 | 2015-08-05 | 天津大学 | Based on the photocatalysis air cleaning device of dispersion fiber |
| CN103523855A (en) * | 2013-10-15 | 2014-01-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Supported photocatalytic degradation method and supported photocatalytic real-time on-line degradation device |
| CN105217712B (en) * | 2015-09-09 | 2017-11-10 | 洛阳理工学院 | A kind of Supported On Granular Activated Carbon nitrogen modifies nano titanium oxide drinking water disinfection tank |
| CN105617859B (en) * | 2016-01-28 | 2017-12-08 | 陈廷翰 | A kind of small air purifier of resistant to pollution photocatalysis Decomposition toxic gas |
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| CN111790335A (en) * | 2019-04-08 | 2020-10-20 | 上海交通大学 | Ultraviolet photochemical reactor device based on continuous flow technology |
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| CN113578294A (en) * | 2021-06-02 | 2021-11-02 | 深圳市光擎光电有限公司 | Method for producing photocatalytic core material having high specific surface area and use thereof |
| CN113599959A (en) * | 2021-06-02 | 2021-11-05 | 深圳市光擎光电有限公司 | Sterilization apparatus and sterilization method |
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