CN101037553B - Preparation and application method of optically catalysed environment protection type coating - Google Patents
Preparation and application method of optically catalysed environment protection type coating Download PDFInfo
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- CN101037553B CN101037553B CN2007100656769A CN200710065676A CN101037553B CN 101037553 B CN101037553 B CN 101037553B CN 2007100656769 A CN2007100656769 A CN 2007100656769A CN 200710065676 A CN200710065676 A CN 200710065676A CN 101037553 B CN101037553 B CN 101037553B
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Abstract
The invention provides a preparation and application method for photocatalysis environmental protection type painting, which relates to construction painting, especially provides a preparation and application method for photocatalysis function painting, which includes steps: mixing titanium-containing organic, water, chelating agent and hydrolysis inhibitor to prepare nano anatase type titanium dioxide water sol; adding metal, oxide or impure titanium dioxide photocatalyst into the titanium dioxide water sol and stirring equably. Using method is coating inorganic isolated layer firstly and coating the photocatalysis painting after drying. Advantages of the invention are: the prepared painting and using technique can be widely used for inner and outer wall surface of building and is harmless to bottom ainting, photocatalysis efficiency is high, cost is low, bonding is firm, transparency is good, preparation is simple, and usage is easy.
Description
Technical field
The present invention relates to building coating, particularly have the coating preparation and the using method of photo-catalysis function.
Background technology
Atmospheric pollution comprises outdoor topsoil and indoor atmospheric pollution, especially harm that human health is brought such as the formaldehyde in the room air, benzene series thing is higher than outdoor far away, as formaldehyde and benzene series thing is the potential carcinogenic and strong carcinogen of generally acknowledging in the world, and with other volatile organic matter, cause respiratory system, blood system and nervous system disorders, and can also cause fetal anomaly, need need to be resolved hurrily.The atmospheric pollution source is wide, harm is big, and especially volatile organic gas is not only of a great variety, and difficulty of governance is big, does not still have convenient effective and practical improvement method.Because the titanium dioxide semiconductor photocatalyst is under the illumination of certain wavelength, can produce active oxygen and hydroxyl with strong oxidation, formaldehyde and volatile organic compounds by the absorption of active oxygen and hydroxyl after, the oxidized inorganicss such as carbonic acid gas, water, oxygen that are reduced into, do not produce secondary pollution, applied widely, thereby have development potentiality in the air pollution treatment field.When photocatalyst was used for air pollution treatment, a kind of effective practical approach was that it is prepared into coating, utilized inner, external wall coating and the big characteristics of air contact area, improved the degradation efficiency to obnoxious flavour.
In application number is 01115625.2 and 01115626.0 Chinese patent, a kind of titania nano-paint is disclosed, the solvent of being made up of titanium dioxide nano-particle, organosilicon binding agent, water and alcohol evenly makes, this coating can form firm nano titania Clear coating on the surface of base material, have organic oxidative decomposition capacity under the irradiation of light, coatingsurface has Superhydrophilic.In application number is 200410027589.0 Chinese patent, a kind of multifunction green environment protection nanometer titania coating is disclosed, form by titanium dioxide, superfine alumina silicate, nano titanium oxide dispersion, light calcium carbonate, water-ground limestone, wollastonite powder, zinc sulfide white, talcum powder, dispersion agent, wetting dispersing agent, thickening material, defoamer, film coalescence aid, flow agent, water, emulsion binder etc., can solve the problem that nano titanium oxide is easily reunited well in coating; In application number is 03136596.5 Chinese patent, a kind of smooth purification environmental-protection type coating and paint-on technique are disclosed, this coating is heat-treated by TiO 2 sol and oxidiferous titanium dioxide complex sol, and the adding tensio-active agent makes, be coated in conventional organic coating surface, form one deck light purification environmental-protection type coating.But there are the following problems respectively for above-mentioned technology: the one, and easily bonded dose of titanium dioxide, various auxiliary agent, filler or tensio-active agent parcel, not only absorptivity weakens, and can not effectively contact with pollutent, a little less than the photocatalysis Decomposition effect; The 2nd, coating after the Long contact time, also can decompose organic substrate if directly be coated on the organic coating substrate gradually.
In order to overcome the deficiencies in the prior art, before this we to have invented application number be 200710065655.7 " a kind of preparation method of nano-anatase mine-titanium oxide water sol ", this invention provides a kind of short-cut method for preparing nano-anatase mine-titanium oxide water sol at low temperatures, this colloidal sol degree of crystallinity height, the stability and the transparency are good, can regulate concentration by direct according to actual needs dilute with water, both direct film forming on various material substrate also can directly prepare photochemical catalysis aqueous, environmental protective coating.
Summary of the invention
The present invention is the titanium oxide water sol of 200710065655.7 invention preparation based on application number, provides a kind of efficient, low-cost, and the preparation and the using method of the environment-friendly type light catalyzed coating that can not exert an influence to substrate.
Above-mentioned purpose of the present invention realizes by following approach:
In the nano-anatase mine-titanium oxide water sol that by raw material is titaniferous organism, water, sequestrant and hydrolysis inhibitor preparation, add one of following hotchpotch, mix:
(1) accounts for precious metal silver, platinum, gold, the palladium of weight percent 0.001%-0.01%, or account for the titanium dioxide optical catalyst of the above-mentioned precious metal of doping of weight percent 1%-50%;
(2) account for transition metal vanadium, chromium, manganese, iron, cobalt, nickel, copper, the zinc of weight percent 0.1%-10%, or account for the titanium dioxide optical catalyst of the above-mentioned transition metal of doping of weight percent 1%-50%;
(3) account for rare earth metal scandium, yttrium, lanthanum, cerium, praseodymium, the neodymium of weight percent 0.01%-20%, or account for the titanium dioxide optical catalyst of the above-mentioned rare earth metal of doping of weight percent 1%-50%;
(4) account for doped with non-metals nitrogen, carbon, sulphur, the fluorine of weight percent 1%-50%, the titanium dioxide optical catalyst of boron;
(5) account for oxide compound silicon-dioxide, aluminum oxide, stannic oxide, ferric oxide, Tungsten oxide 99.999, zirconium white, zinc oxide, vanadium oxide, manganese oxide, nickel oxide, cupric oxide, Indium sesquioxide, cerium oxide, bismuth oxide, lanthanum trioxide, the Neodymium trioxide of weight percent 0.5%-15%, or account for the titanium dioxide optical catalyst of the above-mentioned oxide compound of doping of weight percent 1%-50%.
Described doped precious metal, transition metal, rare earth metal, the shared weight percent of titanium dioxide optical catalyst nonmetal or oxide compound further are 5%-20%.
The application method of optical catalysed environment protection type coating is:
When using optical catalysed environment protection type coating of the present invention, in the spraying of the surface of conventional coating or brushing one deck inorganic barrier, spray or brush this optical catalysed environment protection type coating in insulation surface again after the drying earlier.
The raw material that described inorganic barrier adopted is selected from one or more the combination in silicon dioxide gel or alumina sol or zinc oxide colloidal sol or zirconia sol or the tin oxide sol.
The present invention is doping metals, oxide compound or adulterated titanium dioxide optical catalyst in nano-anatase mine-titanium oxide water sol as required, the wavelength region that the content of adjusting doping or adulterated titanium dioxide can be regulated absorption spectrum, and be sprayed at the surface of conventional coating by sealing coat, raising is to the degradation efficiency of obnoxious flavour, and its effect is as follows:
1. photocatalysis efficiency height: photocatalyst is not wrapped up by other composition, fully is exposed to coatingsurface, and the photo-catalysis function of nano titanium oxide is efficiently utilized.
2. the bottom organic coating is not caused damage: because of having adopted inorganic barrier, photocatalysis can not produce Decomposition to the bottom organic coating.
3. cost is low, and in conjunction with firmly, the transparency is good: because sealing coat and photocatalysis coating are thin, and form by colloidal sol, particle is tiny, thereby can reduce material cost significantly, and sealing coat and photocatalysis coating are thin, transparent and combine firmly with substrate.
4. the preparation method is simple, be easy to realize producing in enormous quantities: the titanium dioxide in the colloidal sol of the present invention directly generates the high Detitanium-ore-type of crystallization degree at a lower temperature in preparation process, stopping property, high thermal resistance to equipment during preparation do not have particular requirement, sediment-free produces, and need not steps such as filtration, washing, crystallization, heat; Simultaneously, can directly adopt commercially available doped titanium dioxide photocatalyst commodity to mix in the prepared above-mentioned colloidal sol.
5. easy to operate, be easy to promote the use of: during use, earlier at the spraying of the surface of conventional coating or brushing one deck inorganic barrier, the colloidal sol that sprays or brush TiO 2 sol or contain hotchpotch on its surface again after the drying.
Embodiment
(1) metal or the oxide compound coating preparation of aqueous sol of directly mixing
Embodiment 1: add Silver Nitrate in the nano-anatase mine-titanium oxide water sol that by raw material is titaniferous organism, water, sequestrant and hydrolysis inhibitor preparation, and mix, to account for the per-cent of mixed sols weight be 0.001% to the content of silver ions in the Silver Nitrate that is added.
Embodiment 2: add platinum nitrate in the nano-anatase mine-titanium oxide water sol that by raw material is titaniferous organism, water, sequestrant and hydrolysis inhibitor preparation, and mix, to account for the per-cent of mixed sols weight be 0.01% to the content of platinum ion in the platinum nitrate that is added.
Embodiment 3: add cupric nitrate in the nano-anatase mine-titanium oxide water sol that by raw material is titaniferous organism, water, sequestrant and hydrolysis inhibitor preparation, and mix, to account for the per-cent of mixed sols weight be 0.5% to the content of cupric ion in the cupric nitrate that is added.
Embodiment 4: add iron nitrate in the nano-anatase mine-titanium oxide water sol that by raw material is titaniferous organism, water, sequestrant and hydrolysis inhibitor preparation, and mix, to account for the per-cent of mixed sols weight be 3% to the content of iron ion in the iron nitrate that is added.
Embodiment 5: add zinc nitrate in the nano-anatase mine-titanium oxide water sol that by raw material is titaniferous organism, water, sequestrant and hydrolysis inhibitor preparation, and mix, to account for the per-cent of mixed sols weight be 7% to the content of zine ion in the zinc nitrate that is added.
Embodiment 6: add Scium trinitrate in the nano-anatase mine-titanium oxide water sol that by raw material is titaniferous organism, water, sequestrant and hydrolysis inhibitor preparation, and mix, to account for the per-cent of mixed sols weight be 0.05% to scandium ionic content in the Scium trinitrate that is added.
Embodiment 7: add lanthanum nitrate in the nano-anatase mine-titanium oxide water sol that by raw material is titaniferous organism, water, sequestrant and hydrolysis inhibitor preparation, and mix, to account for the per-cent of mixed sols weight be 8% to the content of lanthanum ion in the lanthanum nitrate that is added.
Embodiment 8: add cerous nitrate in the nano-anatase mine-titanium oxide water sol that by raw material is titaniferous organism, water, sequestrant and hydrolysis inhibitor preparation, and mix, to account for the per-cent of mixed sols weight be 15% to the content of cerium ion in the cerous nitrate that is added.
Embodiment 9: add the silicon-dioxide aqueous sol in the nano-anatase mine-titanium oxide water sol that by raw material is titaniferous organism, water, sequestrant and hydrolysis inhibitor preparation, and mix, to account for the per-cent of mixed sols weight be 0.5% to the content of silicon-dioxide in the silicon dioxide gel that is added.
Embodiment 10: add the aluminum oxide aqueous sol in the nano-anatase mine-titanium oxide water sol that by raw material is titaniferous organism, water, sequestrant and hydrolysis inhibitor preparation, and mix, to account for the per-cent of mixed sols weight be 1% to the content of aluminum oxide in the alumina sol that is added.
Embodiment 11: add nano zine oxide in the nano-anatase mine-titanium oxide water sol that by raw material is titaniferous organism, water, sequestrant and hydrolysis inhibitor preparation, and mix, the per-cent that the content of the nano zine oxide that is added accounts for mixed sols weight is 15%.
(2) coating of the titanium dioxide doping aqueous sol of containing metal, nonmetal or oxide compound preparation
Embodiment 12: add the nanometer that accounts for weight percent 5% and mix the platinum titanium dioxide optical catalyst in the nano-anatase mine-titanium oxide water sol that by raw material is titaniferous organism, water, sequestrant and hydrolysis inhibitor preparation, mix.
Embodiment 13: add the nanometer that accounts for weight percent 10% and mix the zinc titanium dioxide optical catalyst in the nano-anatase mine-titanium oxide water sol that by raw material is titaniferous organism, water, sequestrant and hydrolysis inhibitor preparation, mix.
Embodiment 14: add the nanometer that accounts for weight percent 20% and mix the lanthanum titanium dioxide optical catalyst in the nano-anatase mine-titanium oxide water sol that by raw material is titaniferous organism, water, sequestrant and hydrolysis inhibitor preparation, mix.
Embodiment 15: add the titanium dioxide optical catalyst that the nanometer that accounts for weight percent 15% is mixed silicon-dioxide in the nano-anatase mine-titanium oxide water sol that by raw material is titaniferous organism, water, sequestrant and hydrolysis inhibitor preparation, mix.
Embodiment 16: add the nanometer nitrating titanium dioxide optical catalyst that accounts for weight percent 20% in the nano-anatase mine-titanium oxide water sol that by raw material is titaniferous organism, water, sequestrant and hydrolysis inhibitor preparation, mix.
(3) coating and the performance evaluation of coating of the present invention on the conventional interior wall coating
1. apply: at the commercially available silicon dioxide gel of exsiccant interior wall coating surface spraying one deck, the coating of preparation among brushing one deck embodiment 14 dries naturally after the seasoning earlier.
2. scraping experiment: the metope of photocatalysis coating is arranged with the dark cotton repeated friction of exerting oneself, and with equal test conditions under be not coated with the powder that comes off on the cloth of comparison as a result of photocatalysis coating metope, the result shows: the metope that scribbles photocatalysis coating has better erasibility.
3. degradation of formaldehyde experiment: at area is 300 * 400mm
2And two surface of plate glass behind cleaning-drying evenly brush the sharp interior wall coating of the commercially available refined scholar of one deck, and the coating of preparation among brushing one deck embodiment 14 after the seasoning dries naturally and is placed on 350 * 450 * 450mm
3Closed cabinet in, case is mid-, and power is arranged is the common fluorescent lamp of 6W, and the starting point concentration of formaldehyde is 0.34mg/l in the case, after 7 days, concentration of formaldehyde is reduced to 0.06mg/l through the common fluorescent lamp illumination of 6W, degradation rate is 82.3%.
(4) coating and the performance evaluation of coating of the present invention on the conventional exterior coating
1. apply: at the commercially available alumina sol of the orange-yellow exterior coating of exsiccant surface spraying one deck, the unadulterated Detitanium-ore-type aqueous sol of brushing one deck dries naturally after the seasoning earlier.
2. solar irradiation senile experiment: the orange-yellow metope that scribbles photocatalysis coating and the orange-yellow metope that is not coated with photocatalysis coating are under the equal test conditions of natural climate, through Kunming sun in summer illumination after 60 days, latter's color takes place slight thin out, shows that the exterior coating that scribbles behind the photocatalysis coating has better anti-ultraviolet function.
3. degradation of formaldehyde experiment: at area is 300 * 400mm
2And two surface of plate glass behind cleaning-drying evenly brush the sharp exterior coating of the commercially available refined scholar of one deck, and the unadulterated Detitanium-ore-type aqueous sol of brushing one deck after the seasoning dries naturally and is placed on 350 * 450 * 450mm
3Closed cabinet in, case is mid-, and power is arranged is the ultraviolet lamp of 6W, and the starting point concentration of formaldehyde is 0.57mg/l in the case, after 6 hours, concentration of formaldehyde is reduced to 0.04mg/l through the UV illumination of 6W, degradation rate is 93%.
The scope of protection of the invention is not subjected to the restriction of cited content in the above embodiment.
Claims (4)
1. the preparation method of optical catalysed environment protection type coating, comprise by titaniferous organism, water, sequestrant and hydrolysis inhibitor being the nano-anatase mine-titanium oxide water sol of feedstock production, it is characterized in that in this anatase mine-titanium oxide water sol, adding one of following hotchpotch, and mix:
(1) accounts for precious metal silver, platinum, gold, the palladium of weight percent 0.001%-0.01%, or account for the titanium dioxide optical catalyst of the above-mentioned precious metal of doping of weight percent 1%-50%;
(2) account for transition metal vanadium, chromium, manganese, iron, cobalt, nickel, copper, the zinc of weight percent 0.1%-10%, or account for the titanium dioxide optical catalyst of the above-mentioned transition metal of doping of weight percent 1%-50%;
(3) account for rare earth metal scandium, yttrium, lanthanum, cerium, praseodymium, the neodymium of weight percent 0.01%-20%, or account for the titanium dioxide optical catalyst of the above-mentioned rare earth metal of doping of weight percent 1%-50%;
(4) account for doped with non-metals nitrogen, carbon, sulphur, the fluorine of weight percent 1%-50%, the titanium dioxide optical catalyst of boron;
(5) account for oxide compound silicon-dioxide, aluminum oxide, stannic oxide, ferric oxide, Tungsten oxide 99.999, zirconium white, zinc oxide, vanadium oxide, manganese oxide, nickel oxide, cupric oxide, Indium sesquioxide, cerium oxide, bismuth oxide, lanthanum trioxide, the Neodymium trioxide of weight percent 0.5%-15%, or account for the titanium dioxide optical catalyst of the above-mentioned oxide compound of doping of weight percent 1%-50%.
2. by the described optical catalysed environment protection type coating preparation method of claim 1, it is characterized in that described doped precious metal, transition metal, rare earth metal, the shared weight percent of titanium dioxide optical catalyst nonmetal or oxide compound further are 5%-20%.
3. the application method of optical catalysed environment protection type coating, it is characterized in that in use with the prepared optical catalysed environment protection type coating of claim 1 method, in the spraying of the surface of conventional coating or brushing one deck inorganic barrier, spray or brush this optical catalysed environment protection type coating in insulation surface again after the drying earlier.
4. by the application method of the described optical catalysed environment protection type coating of claim 3, it is characterized in that raw material that inorganic barrier adopts is selected from silicon dioxide gel or alumina sol or zinc oxide colloidal sol or zirconia sol or the tin oxide sol one or more combination.
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