CN1222580C - Photocatalytic coating material having photocatalytic activity and adsorption property and method for preparating same - Google Patents
Photocatalytic coating material having photocatalytic activity and adsorption property and method for preparating same Download PDFInfo
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- CN1222580C CN1222580C CNB028107993A CN02810799A CN1222580C CN 1222580 C CN1222580 C CN 1222580C CN B028107993 A CNB028107993 A CN B028107993A CN 02810799 A CN02810799 A CN 02810799A CN 1222580 C CN1222580 C CN 1222580C
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Abstract
Disclosed is a photocatalytic coating sol composition and the method for preparing the same. The photocatalityc coating sol composition comprising 0.1% to 20% by weight of a photocatalyst, 0.1% to 10% by weight of an inorganic adsorbent, 1% to 20% by weight of an inorganic binder, 55% to 95% by weight of an organic solvent and if necessary 0.1% by weight to 10% by weight of a metal compound. Specifically, the present invention can remove harmful substances by coating photocatalytic coating sol composition prepared from photocatalyst, inorganic adsorbent, inorganic binder, metal compound and organic solvent on metal filter such as aluminum etc., and plastic filter such as polyethylene and polypropylene etc.used in environmental contaminants treatment system or air conditioning plant such as air-conditioner and air-cleaner, according to any one of and ordinary coating techniques such as spray method or dipping method etc. at room temperature.
Description
Technical field
The present invention relates to light catalyzed coating sol composition and preparation method thereof, more particularly, the present invention relates to the application of photoactivation coating sol composition coating environmental purification system, described coating method is, at room temperature, adopt for example coating technology commonly used such as spraying method or pickling process, by inorganic adhesive, stainless steel for example, as non-ferrous metals such as aluminium wire netting, non-woven, porcelain filter and as polyethylene plastic filters such as (PE) on, coating has the photocatalyst sol coating composition of high absorption property and highlight catalytic active.
Background technology
Before this, the traditional method of processing environment pollutent can be divided into two kinds.A kind of is physico-chemical process, comprises absorption, condensation, solvent wash and catalytic oxidation.Another kind is a bioremediation.Yet absorption method and condensation method can not thoroughly be handled pollutent effectively, so the application of these two kinds of methods is restricted.The solvent wash method is a kind of chemical deodorizing method, and this method is passed through in the chemical substance and pollutent, thereby for limited zone, the clearance rate of pollutent is very high.But, there are some shortcomings in aforesaid method, because need supplementary unit to spray chemical substance, so that this chemical substance and pollutent are reacted effectively in the zone that has huge source of pollution, in the enormous amount and the high place of concentration of pollutent, must adopt in a large amount of chemical substances and pollutent.In addition, in direct combustion method and catalytic oxidation, the material that causes polluting is removed through oxidation, and its elimination efficiency is very high, but can produce for example NO
xAnd SO
xDeng secondary pollutant, and the required cost of this method is higher.
Because the initial stage of the method for the biological treatment pollutent of employing microorganism drops into and running cost is low, thereby, this method has obtained widespread use in recent years, and for example the Europe and the developed industrial country of North America be in this method of active research, and this method has entered commercialization stage.In this method, the various microorganisms that can clear the pollution off are fixed on the carrier, and this helps clearing the pollution off efficiently.In addition, this method can also adopt the equipment of small dimension.Yet this method has problems technically, for example, pollutent must enter in the reactor that in fact carries out pollutant removal continuously as the nutriment of microorganism growth, the necessary routine cleaning of carrier, microorganism must obtain good control, and this method must operate continuously.
Recently, in order to address the above problem, people are more and more interested with the high-level oxidation technology of smell substance for adopting photocatalyst to clear the pollution off.For example, korean patent application No.1999-0052838 discloses a kind of strainer that uses photocatalyst; Wherein, on strainers such as non-woven, gac and zeolite, be coated with titanium dioxide (TiO
2), zinc oxide (ZnO) and silver photocatalysts such as (Ag).Korean patent application No.2000-0034908 discloses a kind of method that adopts the photocatalyst treatment volatile organic compounds.Korean Utility Model Application No.2000-0029990 discloses a kind of device that adopts the titanium oxide treating water.
Photocatalysis oxidation reaction refers to, when energy when the optical energy irradiation of band gap is on photocatalyst, produced hole and electronics, the hydroxy radical qiao that produces in this hole (
-OH) under the strong oxidation, be adsorbed on gas phase or liquid phase organism generation decomposition reaction on the described photocatalyst surface.
Also promptly, photocatalyst shows catalytic activity by absorbing luminous energy, and the oxidizing power that is produced makes the environmental pollutant oxygenolysis.The representative substances that can cause light-catalyzed reaction can be, for example TiO
2, ZnO
2, ZnO, SrTiO
3, CdS, GaP, InP, GaAs, BaTiO
3, KNbO
3, Fe
2O
3, Ta
2O
5, WO
3, SnO
2, Bi
2O
3, NiO, Cu
2O, SiO, SiO
2, MoS
2, InPb, RuO
2, CeO
2Deng, also can in above-mentioned photocatalyst, add for example metal and metal oxides thereof such as Pt, Rh, Ag, Cu, Sn, Ni, Fe during use.Wherein, that the most frequently used is titanium dioxide (TiO
2), because it is harmless, and have excellent photocatalysis activity and good fast light erosion, and with low cost.
But the titanium dioxide absorbing wavelength is reacted less than the energy of 388nm, produces electronics (conduction band) and hole (valence band).Therefore, except that Solar lamp, also can adopt glow lamp and mercury lamp to produce ultraviolet ray as light source.Electronics that is produced by above-mentioned reaction and hole are 10
-12Second is to 10
-9Carry out recombine between mutually in second.Yet if pollutent just has been adsorbed onto on the surface before electronics and hole recombine, electronics and hole just can make these pollutents decompose.
The reaction mechanism of this photocatalyst can be represented with following reaction formula 1-5.
[reaction formula 1]
[reaction formula 2]
[reaction formula 3]
[reaction formula 4]
[reaction formula 5]
In order to obtain and decomposing the photocatalytic activity material clear the pollution off by absorption, people have carried out deep research to the preparation method of the coating sol composition that contains photocatalyst (for example titanium dioxide).For example, PCT publication number WO96/029375 discloses a kind of antifog technology, and this technology can prevent to form mist or water droplet by for example applying photocatalyst layer on the transparent substrates such as mirror, camera lens and flat board on base material.This technology also is used to antifouling field in the practice, for example, with the strainer and the strainer of removing smell component (as the smog of cigarette) of titanium dioxide as the air purifier of photocatalyst, be used for water or antibacterial air filter airborne, that have antibacterial, also can be used for the antifouling of glass and ceramic tile.And the strainer that scribbles photocatalyst can be used for the photochemical catalysis system of decomposing volatile organic compound.Yet, because light-catalyzed reaction is a kind of surface reaction, so, the technology that needs exploitation can adsorb a large amount of organic pollutants or smell substance.
The liquid phase coating photocatalytic method of passing through the most commonly used is, is that initial substance prepares sol composition with the alkoxide of titanium, applies carrier (TOHKEMY No.5-253544) with said composition.Yet this method needs complicated step, for example, forms photocatalytic particle after the coating on carrier, forms the Detitanium-ore-type crystallization with high photocatalytic activity, and in 400 ℃ to 600 ℃ temperature range sintering so that make it attached on the carrier.These complicated steps make production cost high.
Secondly, the application of aforesaid method only limits to apply on the polymer materials of poor heat resistance such as for example plastics.In addition,, at high temperature handle subsequently, but still for example have problems such as energy consumption is big although also can on the ceramic tile of good heat resistance and pottery, carry out the photocatalytic coating.
In addition, do not adopt the gas-phase photocatalysis coating process of light catalyzed coating sol composition to comprise sputtering method or as the chemical Vapor deposition process of TOHKEMY No.60-44053.Yet these class methods also have problems, and for example, drop into height because of involving great expense of equipment causes the initial stage, and power consumption is big, and along with the increase of coating thickness can make the production cycle prolong.
In addition, if adopt sol-gel method to form titanium deoxid film on carrier, then need decomposing pollutant for a long time, because containing on the film of photocatalyst, the contact area of pollutent is limited.In order to utilize photocatalyst to remove pollutent in the environment effectively, need to increase the surface-area of photocatalyst or increase the intensity of light source.Specifically, the strainer as air-treating units such as air purifier and air-conditionings for being used for removing smell substance etc. needs about 10
-3Second treatment time, therefore need a kind of coating colloidal sol of exploitation with high adsorptive power and high photocatalytic activity.
Traditionally, in order under solution state, dissimilar particles to be uniformly dispersed each other, need carry out mechanically mixing (U.S. Patent No. 5 to dissimilar sol compositions, 591,380), perhaps will be dissolved in solvent simultaneously, so that preparation sol composition (U.S. Patent No. 4 as two kinds of alkoxides of initial substance, 176,089).Yet when mixing two kinds of sol compositions, the stability of sol composition reduces, and changes gel at short notice into.In coating process, the thickening of filming, meeting and carrier layering after the thermal treatment.And the shortcoming of this method is, when when dissolving initial substance simultaneously and disperse sol particle, and accurate red-tape operati condition.
The present inventor has carried out development research to the light catalyzed coating composition with high adsorptivity and high photocatalytic activity, and the result has finished the present invention on the basis of following discovery.
Summary of the invention
An object of the present invention is to provide light catalyzed coating sol composition and preparation method thereof, described light catalyzed coating sol composition can stop the leafing of the secondary pollutant that is produced by instantaneous light-catalyzed reaction, and has high photocatalytic activity.
Another object of the present invention provides a kind of method that can decompose and remove environmental pollutant and harmful microorganism etc., and this method for example adopts spraying method or pickling process to apply described light catalyzed coating sol composition on the strainer that is used for water treatment and air handling.
Therefore, one aspect of the present invention provides a kind of light catalyzed coating sol composition, described composition contains the photocatalyst of 0.1 weight % to 20 weight %, 0.1 weight % is to the inorganic adsorbent of 10 weight %, the organic solvent of 1 weight % to 20 weight % inorganic adhesives and 55 weight % to 95 weight %.
Another aspect of the present invention provides a kind of light catalyzed coating sol composition, described composition contains the photocatalyst of 0.1 weight % to 20 weight %, 0.1 weight % is to the inorganic adsorbent of 10 weight %, 1 weight % is to 20 weight % inorganic adhesives, the metallic compound of 55 weight % to the organic solvent of 95 weight % and 0.1 weight % to 10 weight %.
Another aspect of the present invention provides a kind of preparation method of described photocatalyst coating sol composition, described method comprises the steps: to mix the organic solvent of 1 weight % to 20 weight % inorganic adhesives and 55 weight % to 95 weight %, if necessary, also has strong acid or the highly basic of 0.1 weight % to 0.5 weight %; Under room temperature, 1000 to 1500rpm, stirred 10 to 30 minutes; In this mixture, add the inorganic adsorbent of 0.1 weight % to the photocatalyst powder of 20 weight % and 0.1 weight % to 10 weight %; In ultrasonic unit, handled 10 to 50 minutes then; If necessary, in this mixture, add the metallic compound of 0.1 weight % again to 10 weight %.
Described photocatalyst is selected from TiO
2, ZnO
2, ZnO, CaTiO, WO
3, SnO
2, MoO
3, Fe
2O
3, InP, GaAs, BaTiO
3, KNbO
3, Fe
2O
3Or Ta
2O
5, preferred TiO
2And/or ZnO, can use wherein a kind of separately, also can use wherein at least two kinds mixture.Undersized photocatalyst granular has higher photocatalytic activity.Therefore, the particulate mean diameter should be between 1 to 50nm, and preferred 1 arrives 10nm.
In addition, add the 0.01 weight % account for described photocatalyst gross weight oxide compound, can improve the speed of reaction of described photocatalyst to metal such as for example palladium, platinum, radium, tungsten, gold and silver and the copper of 5 weight % or metal.And, by described photocatalyst is mixed with hindered amine light stabilizer and triazole species UV light absorber, can suppress the damage of the caused light catalyzed coating film of light-catalyzed reaction, thereby improve the weather resistance of described photocatalyst.
Have no particular limits for inorganic adsorbent of the present invention, but preferably in light-catalyzed reaction, can adsorb the high absorbability inorganic materials of smell substance and objectionable impurities, more preferably for example contain silicate, talcum, the diatomite of magnesium or calcium or be coated with silver or the zeolite of cupric ion.
The inorganic adhesive that the present invention can adopt has for example different third oxygen compound, silane compound etc., the isopropoxide of preferred different third oxygen compound such as titanium.In addition, in order to control the hydrolysis rate of inorganic adhesive, can add small amount of acid or alkaline catalysts.
The used organic solvent of the present invention can be a lower alkyl alcohol, preferred dehydrated alcohol or Virahol etc.
In addition, have no particular limits for metallic compound of the present invention, but preferably can improve the material of anti-microbial effect and raw material color, the preferred mixture that adopts following a kind of material or multiple material to form: copper compound such as cupric acetylacetonate (copper (II)) and a hydrated copper acetate (copper (II)) etc., silver compound such as silver acetate etc., ferric oxide, zunsober, cadmium red, ochre, cadmium yellow, emerald, chromoxide green, Prussian blue, cobalt blue, manganese or carbon black, more preferably copper compound.
Set forth the preparation method of light catalyzed coating sol composition of the present invention below:
At first, mix the organic solvent of 1 weight % to 20 weight % inorganic adhesives and 55 weight % to 95 weight %, if necessary, also have strong acid or the highly basic of 0.1 weight % to 0.5 weight %, following step is under room temperature, 1000 to 1500rpm this mixture to be stirred 10 to 30 minutes.Then, in this mixture, add the photocatalyst powder of 0.1 weight % to 20 weight %.
In this mixture, add the inorganic adsorbent of 0.1 weight %, in ultrasonic unit, handled 10 to 50 minutes then, so that obtain coating sol composition of the present invention to 10 weight %.At this moment, on described inorganic adsorbent is attracted to and films, and for example objectionable impurities such as smell substance, elementary decomposed substance is decomposed by photocatalyst, elementary decomposable material is after photochemical catalysis, on secondary pollutant is attracted to and films, so the photolysis of photocatalyst makes objectionable impurities seldom can distribute and enters in the air.
In addition, if necessary, in order to strengthen the antibacterial of light catalyzed coating sol composition of the present invention, perhaps in order to strengthen the colour developing of filming through uviolizing, can use the metallic compound of 0.1 weight %, preferably use the metallic compound of 0.2 weight % to 5 weight % to 10 weight %.
Since photocatalyst coating sol composition of the present invention together with various oxide compounds can be distributed to equably film on, so method of the present invention is than the easier use of existing method and have more commercial value.And, in order to control the hydrolysis rate of inorganic adhesive, can add small amount of acid or alkaline catalysts.
Light catalyzed coating sol composition of the present invention can be coated on the required base material, dry then, described coating method has print process, spraying method, pickling process etc., preferred spraying method or pickling process.Wherein, the drying temperature when adopting spraying method and pickling process depends on solvent, and described drying temperature is generally 50 to 200 ℃, preferred 100 to 150 ℃.
Have no particular limits for described base material, but preferably can apply any material of the light catalyzed coating sol composition prepared according to the present invention.For example, the various carriers of effects such as described base material comprises need have antibiotic, deodorizing, pollution control perhaps are used for water treatment or prevent the strainer of air-polluting equipment, and metal, alloy, glass, curtain, wallpaper, packing, plastics and paper.
On base material, during the described light catalyzed coating sol composition of coating, must control the thickness of filming according to purposes.If the thickness of filming is greater than 0.1 μ m, then photocatalysis layer is securely attached on the base material, thereby can obtain the high coating structure of weather resistance.In addition, along with the increase of coating thickness, photocatalytic activity also increases.
On the other hand, if the thickness of filming greater than 5 μ m, then photocatalytic activity can not increase thereupon, because light source can not fully be delivered to the bottom of photocatalyst layer.Because the photocatalytic activity height of described thickness during less than 5 μ m is so preferably come selective light catalysis to film according to the transmission characteristic of light.
In addition, in order to improve the adsorptivity of pollutent, effectively with the gauge control of filming in the scope of 20 to 50 μ m.Therefore, can determine the thickness of photocatalyst layer in the scope of 5 to 50 μ m.
Light catalyzed coating sol composition of the present invention can be applied to the various carriers of effects such as need having antibiotic, deodorizing and pollution control, for example indoor article such as curtain, wallpaper; Daily necessities such as tent, umbrella, scarf etc.; Packaging vessel such as food product pack etc.; Agriculture field is as plastic sheeting for farm use of growing seedlings (raisingseedling sheet) etc.Can also adopt metal with photo-catalysis function and monometallic such as aluminium, iron, copper etc. to share as base material, and various alloy for example stainless steel, magnalium manganese alloy (pearl), brass, aluminium alloy, titanium alloy etc.
In addition, when according to the shape of used metal or quality and when on tinsel or plate, having applied common coating and coloured copperplate, can on this tinsel or plate, form by filming that light catalyzed coating sol composition of the present invention is formed.If filming of adhesive coating and photocatalyst has high transmittance and transparency, then can not destroy the tone of basic coating, thereby can improve its practicality.
The matrix structure of photocatalyst of the present invention might play a role simultaneously, for example it is coated to the window glass of automobile or various forms of transport, the window glass of buildings, in the time of on the strainer of refrigerator, refrigerator display case or environmental purification system, can utilize its function that objectionable impurities is decomposed, and can antibiotic and deodorizing, thereby have strengthened the anti-pollution function of glass surface.
Specifically, can adopt photocatalyst of the present invention to apply the plastic filter (for example polyethylene filter, polypropylene filter etc.) of environmental purification system, air conveying cleaner and air purifier.
Also can more fully understand other purposes of the present invention and advantage in conjunction with the accompanying drawings according to following detailed description.
Description of drawings
Fig. 1 has shown the photocatalytic activity figure of the wire netting that is coated with the light catalyzed coating sol composition, does not add inorganic adsorbent and metallic compound in the described light catalyzed coating sol composition.
Fig. 2 has shown the photocatalytic activity figure of the wire netting of the embodiment of the invention 6 that is coated with the light catalyzed coating sol composition.
Fig. 3 has shown the photocatalytic activity figure of the wire netting of the embodiment of the invention 7 that is coated with the light catalyzed coating sol composition.
The antibacterial experiment that Fig. 4 has shown wire netting is figure as a result, and described wire netting is coated with by the prepared light catalyzed coating sol composition of the present invention respectively and does not add inorganic adsorbent and the light catalyzed coating sol composition of metal ion.
The Decolorant Test that Fig. 5 has shown the polyethylene filter that is coated with light catalyzed coating sol composition of the present invention is figure as a result.
The activity test that Fig. 6 has shown the polyethylene filter that is coated with light catalyzed coating sol composition of the present invention is figure as a result.
Fig. 7 has shown the saturated activity test-results figure of the polyethylene filter that is coated with light catalyzed coating sol composition of the present invention.
Fig. 8 has shown the electron micrograph on the polyethylene filter surface that is coated with light catalyzed coating sol composition of the present invention.
Fig. 9 has shown the electron micrograph in the polyethylene filter cross section that is coated with light catalyzed coating sol composition of the present invention.
Embodiment
Describe the present invention below with reference to accompanying drawings and in conjunction with embodiment preferred.Following examples do not limit the scope of the invention.
With isopropoxide [Junsei Chemical Co., Ltd.], the dehydrated alcohol of 78.8 weight % and the mixed in hydrochloric acid of 0.2 weight % of the titanium of 5 weight %, under room temperature, 1200rpm, stirred 20 minutes.Then, the titania powder [Degussa P25, Germany] that in mixture, adds 10 weight %.
In the mixing solutions of gained, add the talcum [DUKSAN PURECHEMICAL Co., Ltd.] of 6 weight %, in ultrasonic equipment [BRANSON Ultrasonic Co., DHA-1000], handle more than 30 minutes then, obtain the coating sol composition.
Embodiment 2
With isopropoxide [Junsei Chemical Co., Ltd.], the dehydrated alcohol of 78.5 weight % and the mixed in hydrochloric acid of 0.2 weight % of the titanium of 5 weight %, under room temperature, 1200rpm, stirred 20 minutes.Then, the titania powder [Degussa P25, Germany] that in mixture, adds 10 weight %.
Talcum [the DUKSAN PURECHEMICAL Co. that in the mixing solutions of gained, adds 6 weight %, Ltd.], then at ultrasonic equipment [BRANSON Ultrasonic Co., DHA-1000] in handle more than 30 minutes, a hydrated copper acetate [the Junsei Chemical Co. that in gained solution, adds 0.3 weight % then, Ltd., Japan], obtain the coating sol composition.
Embodiment 3
Carry out the process identical with embodiment 1, difference is, is not the talcum that adopts 6 weight %, but adopts the diatomite [DUKSAN PURE CHEMICAL Co., Ltd.] of 5 weight %.
Embodiment 4
Carry out the process identical with embodiment 2, difference is, is not a hydrated copper acetate that adopts 0.3 weight %, but adopts the hydration silver acetate [Junsei Chem.Co., Ltd., Japan] of 0.3 weight %.
Embodiment 5
Mix the titanium dioxide [Degussa P25, Germany] of 3 weight %, the ethanol of 93 weight % and the hydrochloric acid of 0.2 weight %, under room temperature, 1200rpm, stirred 20 minutes then.
Magnesium Silicate q-agent [the Aldrich that in this mixing solutions, adds 3.8 weight %, the U.S.], then at ultrasonic equipment [BRANSON Ultrasonic Co., DHA-1000] in handle more than 30 minutes, cupric acetylacetonate [the Junsei Chemical Co. that in gained solution, adds 0.3 weight % then, Ltd., Japan], obtain the coating sol composition.
Embodiment 6
Use spraying method (diameter: 1.5 under the room temperature, pressure: 4kg) the coating sol composition that is made by embodiment 1 is coated to wire netting [Al salongs 4 * 8mm, 0.4T, Hyungjei MetalasCo., Korea S] on, then 120 to 150 ℃ of dryings, thereby obtain being coated with the wire netting of photocatalyst.
Embodiment 7
Carry out the step identical with embodiment 6, difference is there is not to adopt the coating sol composition that is made by embodiment 1, but adopts the coating sol composition that is made by embodiment 2.
Embodiment 8
Carry out the step identical with embodiment 6, difference is there is not to adopt the coating sol composition that is made by embodiment 1, but adopts the coating sol composition that is made by embodiment 3.
Embodiment 9
Carry out the step identical with embodiment 6, difference is there is not to adopt the coating sol composition that is made by embodiment 1, but adopts the coating sol composition that is made by embodiment 4.
Use spraying method (diameter: 1.5 under the room temperature, pressure: 4kg) the coating sol composition that is made by embodiment 5 is coated on the polyethylene filter [SW80M, Shinwu Co., Korea S], descend drying at 60 ℃ then, thereby obtain being coated with the polyethylene filter of photocatalyst.
Comparative example
With isopropoxide [Junsei Chemical Co., Ltd.], the dehydrated alcohol of 95 weight % and the mixed in hydrochloric acid of 0.2 weight % of the titanium of 5 weight %, under room temperature, 1200rpm, stirred 20 minutes.Then, the titania powder [Degussa P25, Germany] that in mixture, adds 10 weight %.Then gained solution was handled 30 minutes in ultrasonic equipment [BRANSON Ultrasonic Co., DHA-1000] or the longer time, thereby obtained the coating sol composition.
Subsequently, at room temperature use spraying method (diameter: 1.5, pressure: 4kg) gained coating sol composition is coated to wire netting [Al salongs 4 * 8mm, 0.4T, Hyungjei Metalas Co., Korea S] on, descend drying at 60 ℃ then, thereby obtain being coated with the wire netting of the photocatalyst that does not contain inorganic adsorbent and metallic compound.
Test
I) test of employing wire netting
The saturated activity test
To place in a plurality of batch reactors by the wire netting that is coated with photocatalyst that embodiment 6 to 9 and comparative example make respectively, by adding trieline (C
2HCl
3, TCE) measure rate of decomposition.The starting point concentration of trieline is about 2000ppm, and the volume of reactor is 125cm
3, with black lamp (wavelength 300nm to 368nm, maximum wavelength 400nm) [4W BLB, Sankyodenki, Japan] the irradiation wire netting, use Fourier transform infrared spectrometer (FTIR) [PerkinElmer, Spectrum one FT-IR spectrograph] to measure the rate of decomposition of trieline then.
Measurement result is shown in Fig. 1 to 3.
Fig. 1 has shown the activity of the wire netting that is coated with the light catalyzed coating sol composition that is made by comparative example, does not add inorganic adsorbent and metallic compound in the described light catalyzed coating sol composition.Fig. 2 has shown the photocatalytic activity figure of the wire netting that is coated with the light catalyzed coating sol composition that is made by the embodiment of the invention 6.Fig. 3 has shown the activity by the wire netting that is coated with the light catalyzed coating sol composition of the embodiment of the invention 7 preparations.
As shown in Figure 1, the result who is decomposed by photocatalyst is, trieline (10 to 20 minutes) in several minutes is decomposed, but detected the peak (C-Cl:856cm as the phosgene of intermediate when adopting trieline (TCE) for reactant
-1, C=O:1825cm
-1).
This shows that trieline can be decomposed fast by the light catalyzed coating sol composition, but deleterious phosgene may be dispersed in the air.
Therefore, if do not add inorganic adsorbent and metallic compound when preparation light catalyzed coating sol composition, then gained light catalyzed coating sol composition is not suitable for the optical catalyst filter of air-conditioning and air purifier.
By contrast, shown in Fig. 2 and 3, the activity of photocatalyst has reduced half, and after trieline decomposes, and compares with result by the wire netting gained of comparative example, does not detect the peak corresponding to the phosgene of secondary pollutant (by product).This shows because the inorganics of the high absorbability that secondary pollutant is added into is adsorbed, so be not dispersed in the air.
The germ resistance test
Prepare two culture dish that lid arranged (diameter: 100mm, height: the colon bacillus (Escherichia coli) of cultivation is housed, and 15mm) by two wire netting samples that are of a size of 3cm * 6cm of embodiments of the invention 8 preparations.Then, these two samples are put into two petri dishs that colon bacillus is housed respectively, shine one of them petri dish with black lamp [4W BLB, Sankyo Denki, Japan], and another petri dish is without UV-irradiation.The wavelength of described black lamp be 300nm to 368nm, maximum wavelength is 400nm, power is 4W, mounting distance is 5cm.In this experiment, the initial bacterium colony number of used colon bacillus is 70 of each petri dishs.
The results are shown in Figure 4.
As shown in Figure 4, after 6 hours, can find that the colon bacillus in the petri dish is killed fully with uviolizing.And under similarity condition in the undosed test, the bacterium colony number of colon bacillus does not reduce as can be seen.
Ii) adopt the test of polyethylene filter
Decolorant Test
In order to measure the adsorption activity of the polyethylene filter that is coated with the light catalyzed coating sol composition that makes by embodiment 10, to the culture dish that lid is arranged (diameter: 100mm, high: methylenum coeruleum (M.B.) [the methylenum coeruleum 2-3 hydrate that adds 25ml 0.8ppm 15mm), Junsei Chem, co.Ltd., Japan] aqueous solution, the polyethylene filter that is coated with photocatalyst that is made by embodiment 10 is immersed the culture dish that this has lid, then by using black lamp [4W BLB, Sankyo Denki, Japan] irradiation observes the bleaching level of the aqueous solution.The wavelength of described black lamp be 300nm to 368nm, maximum wavelength is 400nm, power is 4W, is installed in the place apart from petri dish 13cm.
The results are shown in Figure 5.As seen from Figure 5, the clearance rate of methylenum coeruleum (M.B.) aqueous solution is 84.4% after 30 minutes.
Deodorizing test
In order to be determined at the deodorizing rate under the gaseous state, it is the airtight SUS reactor central authorities of 125L that the polyethylene filter that is coated with photocatalyst that is made by embodiment 10 is placed capacity, injects smell substance Trimethylamine 99 (TMA) with the speed of 0.83m/s in reactor then.Inject Trimethylamine 99 (TMA) afterwards, measure clearance rate in time, the results are shown in Figure 6.
As shown in Figure 6, the clearance rate of Trimethylamine 99 is that the clearance rate of Trimethylamine 99 is 90.41% after 82.2%, 30 minute after 10 minutes.
The saturated activity test
It is in the airtight SUS reactor of 125L that the polyethylene filter that is coated with the light catalyzed coating sol composition that is made by embodiment 10 is placed capacity, and air-circulating fan is installed, and injects smell substance Trimethylamine 99 (TMA) then in this reactor.
By this air-circulating fan inner air is flowed with the speed of 0.83m/s, left standstill about 1 hour.Then, the concentration of Trimethylamine 99 (TMA) in the assaying reaction device.
Above-mentioned experiment is designated as circulation 1, finishes after the circulation 1, be coated with the polyethylene filter 1 hour of photocatalyst, repeat above-mentioned steps then with black lamp [4W BLB, SankyoDenki, Japan] irradiation.Above-mentioned the 2nd experiment is designated as circulation 2, repeats above-mentioned two circulations.
The result as shown in Figure 7.As seen from Figure 7, in 53 circulations, the removing effect of Trimethylamine 99 is 1002.7ppm, and the elimination efficiency of Trimethylamine 99 (TMA) is maintained at about 90%.
Antibacterial tests
With the antibacterial ability of vibration flask method mensuration polyethylene filter, the strainer that be coated with light catalyzed coating sol composition of described polyethylene filter for making by embodiment 10.
Vibration flask method herein can be carried out as follows:
At first, give sample (squares of 30 1cm * 1cm) and to after the known bacterium of (squares of 30 1cm * 1cm) inoculation in the same old way, inoculation liquid and a certain amount of neutralization solution are mixed, extract the bacterium of cultivating then, after measuring the bacterial count in this neutralization solution, calculate with respect to bacterium decrement in the same old way sample by following equation 1.
Adopt phosphate buffer solution (pH7.0 ± 0.2) as neutralization solution, adopt tween 80 (0.05%) as tensio-active agent, after under 35 ± 1 ℃, stirring and hatched 24 hours with 150 times/minute speed, the bacterial count of determination test bacterial solution.
[equation 1]
Bacterium decrement=[(after 24 hours behind the bacterial count of check sample-24 hour the bacterial count of coated sample)/bacterial count of check sample after 24 hours] * 100
Check sample wherein is the initial sample of uncoated, does not for example apply the polyethylene filter of light catalyzed coating sol composition.
Used known bacterial strain is streptococcus aureus (Straphylococcus aureus) ATCC 6538 and colon bacillus (Escherichia coli) ATCC 25992 in the above-mentioned vibration flask method.
The result is as shown in table 1 below.
By table 1 as seen, when adopted embodiment 7 and 10 be coated with the polyethylene filter of photocatalyst sol composition the time, the rate of increase of microorganism is very low, and the bacterial growth of check sample 30% to 40%.
Table 1
| Bacterial strain | Streptococcus aureus ATCC 6538 | Streptococcus aureus ATCC 6538 | Colon bacillus ATCC 25992 | Colon bacillus ATCC 25992 | |
| Sample | Blank | Embodiment 7 | | Embodiment | 10 |
| Postvaccinal moment | 1.8×10 5 | 1.8×10 5 | 1.7×10 5 | 1.7×10 5 | |
| Inoculate back 24 hours | 1.7×10 5 | ＜100 | 1.7×10 5 | ＜100 | |
| The decrement of bacterium (%) | - | 99.9 | - | 99.9 | |
| Rate of increase (%) | 33.9 | - | 37.1 | - |
Anti-microbial test
According to ASTM G-21 touchstone, test the anti-microbe ability of the polyethylene filter that is coated with the light catalyzed coating sol composition that makes by embodiment 10.
Used known bacterial strain is the short stalk of AN (Aspergillusniger) ATCC 9642, skin promise film mould (Penicillium pinophilium) ATCC 11797, Chaetomium globosum (Chaetomium globosum) ATCC 6205, green sticking broom mould (Gliocladiumvirens) ATCC 9645 and A Pululan mould (Aureobaidium Apullulans) ATCC15233 in the ASTM G-21 touchstone.
The gained result is 0 grade of ASTM G-21 touchstone.Wherein, 0 grade of not growth of the known bacterial strain of expression.
In addition, Fig. 8 and 9 has shown the surface of the polyethylene filter that is prepared by embodiment 10 and the electron micrograph in cross section respectively.
Confirm that by Fig. 8 and 9 surface that is coated with the light catalyzed coating sol composition is a porous, its coat-thickness is about 20 μ m.
Industrial applicibility
As mentioned above, the present invention has adopted inorganic adsorbent. The invention provides effective technology, this technology is applicable to environmental contaminants treatment system or air-conditioning equipments such as air-conditioning and air purifier.
Claims (8)
1. light catalyzed coating sol composition, described composition contains the photocatalyst of 0.1 weight % to 20 weight %, and this photocatalyst is selected from by TiO
2, ZnO
2, ZnO, CaTiO, WO
3, SnO
2, MoO
3, Fe
2O
3, InP, GaAs, BaTiO
3, KNbO
3, Fe
2O
3And Ta
2O
5The group of forming; 0.1 weight % is to the inorganic adsorbent of 10 weight %, this inorganic adsorbent is silicate, talcum, the diatomite of magnesium or calcium or is coated with silver and/or the zeolite of cupric ion; 1 weight % is to 20 weight % inorganic adhesives, and this inorganic adhesive is different third oxygen compound or silane compound; With the organic solvent of 55 weight % to 95 weight %, this organic solvent is dehydrated alcohol or Virahol.
2. light catalyzed coating sol composition as claimed in claim 1, described composition also contain the metallic compound of 0.1 weight % to 10 weight %.
3. light catalyzed coating sol composition as claimed in claim 2, wherein, described metallic compound is selected from the group of being made up of copper compound, silver compound, ferric oxide, zunsober, cadmium red, ochre, cadmium yellow, emerald, chromoxide green, Prussian blue, cobalt blue, manganese and carbon black.
4. light catalyzed coating sol composition as claimed in claim 1, wherein, the mean diameter of described photocatalyst granular is 5 to 50nm.
5. the preparation method of the described light catalyzed coating sol composition of claim 1 said method comprising the steps of:
Mix the organic solvent of 1 weight % to 20 weight % inorganic adhesives and 55 weight % to 95 weight %, under room temperature, 1000 to 1500rpm, this mixture was stirred 10 to 30 minutes then, wherein said inorganic adhesive is different third oxygen compound or silane compound, and described organic solvent is dehydrated alcohol or Virahol; With
In this mixture, add 0.1 weight % to the photocatalyst powder of 20 weight % and 0.1 weight % to the inorganic adsorbent of 10 weight %, in ultrasonic unit, handled 10 to 50 minutes then, wherein said photocatalyst is selected from by TiO
2, ZnO
2, ZnO, CaTiO, WO
3, SnO
2, MoO
3, Fe
2O
3, InP, GaAs, BaTiO
3, KNbO
3, Fe
2O
3And Ta
2O
5The group of forming, described inorganic adsorbent is silicate, talcum, the diatomite of magnesium or calcium or is coated with silver and/or the zeolite of cupric ion.
6. the preparation method of the described light catalyzed coating sol composition of claim 5 said method comprising the steps of:
Mix the organic solvent of 1 weight % to 20 weight % inorganic adhesives and 55 weight % to 95 weight %, and 0.1 weight % to strong acid or the highly basic of 0.5 weight %, under room temperature, 1000 to 1500rpm this mixture was stirred 10 to 30 minutes then, wherein said inorganic adhesive is different third oxygen compound or silane compound; Described organic solvent is dehydrated alcohol or Virahol; With
In this mixture, add the inorganic adsorbent of 0.1 weight % to the photocatalyst powder of 20 weight % and 0.1 weight % to 10 weight %, add the metallic compound of 0.1 weight % again to 10 weight %, handled 10 to 50 minutes in ultrasonic unit then, wherein said photocatalyst is selected from by TiO
2, ZnO
2, ZnO, CaTiO, WO
3, SnO
2, MoO
3, Fe
2O
3, InP, GaAs, BaTiO
3, KNbO
3, Fe
2O
3And Ta
2O
5The group of forming, described inorganic adsorbent is silicate, talcum, the diatomite of magnesium or calcium or is coated with silver and/or the zeolite of cupric ion.
7. base material, the preparation of described base material are to adopt print process, spraying method or pickling process coating as each described light catalyzed coating sol composition of claim 1 to 4, then drying.
8. base material as claimed in claim 7, wherein, described base material is aluminium strainer, polyethylene filter or polypropylene filter.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20010022270 | 2001-04-25 | ||
| KR0022270/2001 | 2001-04-25 |
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| Publication Number | Publication Date |
|---|---|
| CN1513040A CN1513040A (en) | 2004-07-14 |
| CN1222580C true CN1222580C (en) | 2005-10-12 |
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ID=19708680
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Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20050126428A1 (en) |
| KR (1) | KR100518956B1 (en) |
| CN (1) | CN1222580C (en) |
| WO (1) | WO2002085989A1 (en) |
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-
2002
- 2002-04-25 CN CNB028107993A patent/CN1222580C/en not_active Expired - Fee Related
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| KR100518956B1 (en) | 2005-10-05 |
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| WO2002085989A1 (en) | 2002-10-31 |
| CN1513040A (en) | 2004-07-14 |
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