CN1137787C - Nanometer optical catalyst mother solution and its preparing method and use - Google Patents
Nanometer optical catalyst mother solution and its preparing method and use Download PDFInfo
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- CN1137787C CN1137787C CNB01101802XA CN01101802A CN1137787C CN 1137787 C CN1137787 C CN 1137787C CN B01101802X A CNB01101802X A CN B01101802XA CN 01101802 A CN01101802 A CN 01101802A CN 1137787 C CN1137787 C CN 1137787C
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Abstract
The present invention belongs to the technical field of photocatalysis, particularly relates to nanometer photocatalyst mother liquor, and a preparing method and the applications thereof. Titanate, titanium tetrachloride, titanium white powder, photocatalyst powder or the mixture of any of the materials accounting for 1% to 30% of total weight is mixed with an emulsifying agent accounting for 5% to 20% of the total weight, a stiffening agent accounting for 4% to 12% of the total weight, acid accounting for 1% to 10% of the total weight and water account for 25% to 89% of the total weight, and the nanometer photocatalyst mother liquor is prepared after thorough reaction by grinding and ultrasonic wave or stirring. The nanometer photocatalyst mother liquor can be used for purifying air and waste water with high efficiency, and a stable photocatalyst layer can be formed by coating the mother liquor on a porous material at a temperature below 300 DEG C. The present invention has the advantages of low use amount of organic solvent, and low production cost of a photocatalytic material, and the present invention is favorable for environmental protection.
Description
The invention belongs to the photocatalysis technology field, nanometer optical catalyst mother solution that particularly on porous material, supports and its production and use.
Semiconductor TiO
2, WO
3, MoO
3Or Fe
2O
3Deng nano particle, can produce hole-duplet at energy during greater than the photon irradiation of its semiconductor energy gap, the synergy of hole-duplet not only has strong oxidative degradation ability to the pollutant in the environment, but also has sterilizing function.Utilize ultraviolet ray irradiation TiO
2, WO
3, MoO
3Or Fe
2O
3Deng nano particle, can be the harmful substance catalytic oxidation in the empty G﹠W harmless object, so these nano particles are the good functional material, particularly TiO of environment purification
2The good photocatalysis characteristic of nano particle has a wide range of applications aspect environment purification.Usually need be with TiO
2, WO
3, MoO
3Or Fe
2O
3Be supported on the base material Deng nano particle, as on the surface of following material such as textile, nonwoven, paper, glass, pottery, steel, aluminium, stone material, timber or plastics etc., making the photocatalyst layer that one deck contains titanium dioxide.But above-mentioned nano particle is difficult to stably be supported on substrate surface with the form of pressed powder, needs specific method could realize that it fixes.At present, form above-mentioned photocatalyst layer the method that directly supports above-mentioned nano particle at substrate surface is arranged, known have on substrate surfaces such as plastics, pottery, resin, utilize chemical deposition (CVD), plasma gas-phase deposit (PECVD), ion sputtering method, electron beam evaporation plating method etc., but these method apparatus expensive, yield rate is low, thereby the manufacturing cost height, be difficult to large-scale production.
Forming light urges the agent layer to also have other method; as Japanese patent laid-open 5-207147 number report; above-mentioned catalyst granules is blended in the bonding agent; methods such as utilization spraying are coated on substrate surface; heat-treat after perhaps utilizing dip coating to be coated with and form catalyst layer; but, because this kind method causes many photocatalyst granulars to be embedded in the bonding agent, so can't give full play to catalytic action.What and for example PCT/JP9402077 reported directly with TiO
2, WO
3, MoO
3Or Fe
2O
3Deng the nano particle particles supported such as oxide-based bond layer surface, but the technology for preparing this bond layer and catalyst-loaded particle is very complicated.
Form light and urge the agent layer to also have other method, as JP08,299,789 disclose the titanium organic metal salt have been dissolved in the organic solvent, are coated on substrate surface then, and solvent evaporates titanium organic metal salt is hydrolyzed into moisture TiO
2Layer, then, TiO is burnt till in baking
2Catalyst layer, but this method can only be applied to glass, pottery, the metal surface of heatproof.Known also has, and opens among the flat 1-288321 as the spy, and titanium colloidal sol is coated on glass, the pottery, need just have good catalytic activity at the temperature sintering more than 400 ℃.Chinese patent application number and for example: 99109393.3 reports, the titanium sol-gel paint that utilizes light to help sol-gel process to prepare can be supported in the various substrates at normal temperatures and have good photocatalytic activity, but this method needs ultraviolet lighting in the preparation process of colloidal coating, and solvent is that the organic solvent cost is higher.
One of purpose of the present invention is to provide a kind of being easy to stably to be supported on the substrate surface, is the nanometer optical catalyst mother solution of primary solvent with water, reduces the consumption of organic solvent, reduces production costs and the favorable environment protection.
Another object of the present invention is to provide a kind of method for preparing nanometer optical catalyst mother solution, and this mother liquor can be coated on various solid substrates surface under lower temperature, forms stable and has the photocatalyst layer of highlight catalytic active.
The present invention also aims to provide a kind of purposes of nanometer optical catalyst mother solution, it can overcome apparatus expensive used when being supported on nano particle on the base material, and yield rate is low, and complex process, defectives such as cost height.Utilize porous material to have the characteristics of very large specific area and air permeability and good, under the effect of emulsifying agent, thickener, provide a kind of high-efficiency photocatalysis material that utilizes the prepared one-tenth of nanometer optical catalyst mother solution, can purify air efficiently and waste water.
The composition of efficient nano optical catalyst mother solution of the present invention, by weight percentage: titanate esters, titanium tetrachloride, titanium dioxide, photocatalyst powder or any mixture 1-30% between them, emulsifying agent 5-20%, thickener 4-15%, acid 1-10%, water 25-89%.
The preferred group of high efficiency photocatalyst nanometer mother liquor of the present invention becomes: titanate esters, titanium tetrachloride, titanium dioxide, photocatalyst powder or any mixture 5-15% between them, emulsifying agent 10-20%, thickener 2-5%, sour 5-10%, water 50-70%.
The preparation method of efficient nano optical catalyst mother solution of the present invention is as follows, by weight percentage:
Titanate esters, titanium tetrachloride, titanium dioxide, photocatalyst powder or any mixture between them of gross weight 1-30% will be accounted for, with the emulsifying agent that accounts for gross weight 5-20%, account for the thickener of gross weight 4-12%, the water mixing that accounts for the acid of gross weight 1-10% and account for gross weight 25-89%, by grinding and ultrasonic echography or stirring, fully be prepared into nanometer optical catalyst mother solution after the reaction.
The purposes of efficient nano optical catalyst mother solution of the present invention is coated on the mother liquor of making on the solid substrate surface, particularly is supported on the porous material, dries being lower than under 300 ℃ the temperature, forms stable and has the photocatalyst layer of highlight catalytic active.
The efficient nano optical catalyst mother solution preferably at room temperature is supported on the porous material, is prepared into high-efficiency photocatalysis material, to purify air efficiently and waste water.The coating process for preparing above-mentioned porous photocatalytic material has methods such as dipping, dip-coating, spraying or spin coating.
Described titanate esters is a kind of or any mixture between them in butyl titanate, tetraethyl titanate, the isopropyl titanate.
Described photochemical catalyst is TiO
2, WO
3, MoO
3Or Fe
2O
3Deng a kind of in the nano particle or any mixture between them.
Described acid is a kind of or any mixture between them in sulfuric acid, nitric acid, hydrochloric acid or the phosphoric acid.
Described emulsifying agent is a kind of or any mixture between them in lecithin, sucrose fatty ester, sorbitan carboxylic esters, methyl glycol fatty acid ester, glyceride, lauryl amine, diethanol amine, oleic acid or the polyglycereol etc.
Described thickener is a kind of or any mixture between them in starch, gelatin, pectin, carboxymethyl cellulose, sodium carboxymethylcellulose, methylcellulose, bentonite, imvite, oxidic polyethylene or the polyethylene glycol etc.
Described porous material is porous ceramics, porous enamel, honeycombed cement, stephanoporate aluminum product or porous, expanded glass etc.
The nanometer optical catalyst mother solution that the present invention is prepared is supported on the solid substrate surface, on the porous material that particularly supports, as porous ceramics, porous enamel, honeycombed cement, stephanoporate aluminum product, materials such as porous, expanded glass, very large specific area is arranged, the photocatalysis efficiency of porous photocatalytic material is improved, the gas permeability of porous material is fit to be applied to the current system of sky G﹠W class very much, for example these materials are applied to building, road equipment, the vitalizing semiconductor nanometer oxide particle forms hole-duplet under the effect of sunlight, outdoor air is purified, perhaps be applied to house decorative material, perhaps be made into the net that purifies air, under the exciting of lighting source or uviol lamp, room air purified.
Advantage of the present invention is can (be lower than 300 ℃) at low temperatures by emulsifying agent, thickener, sour acting in conjunction to prepare the high efficiency photocatalysis scavenging material, and technology condition is simple relatively.It is the nanometer optical catalyst mother solution of preparation based on water that the present invention also has an advantage, reduces the consumption of organic solvent, reduces production costs and the favorable environment protection.
Below in conjunction with embodiment and accompanying drawing technical scheme of the present invention is further described.
Fig. 1. be supported on the TiO on the porous ceramics
2Catalysis material is to the degradation results of acetaldehyde.
Fig. 2. be supported on the degradation results of porous, expanded catalysis material on glass to acetaldehyde.
Fig. 3. be supported on catalysis material on the porous aluminium flake to the degradation results of dyestuff rhodamine B solution.
A. the initial concentration absorbance of rhodamine B solution
B. be the solution absorbency of illumination degrading after 90 minutes
Fig. 4. be supported on the degradation results of the catalysis material PARA FORMALDEHYDE PRILLS(91,95) on the honeycombed cement.
Embodiment 1
No. 1 nanometer optical catalyst mother solution is composed as follows, by weight percentage:
With butyl titanate 10%, water 75%, concentrated hydrochloric acid 1%, lecithin 5%, lauryl amine 5%, methylcellulose 4% joins in the reactor, by grinding and fully stirring 10 hours, places after 7 days, promptly is prepared into nanometer optical catalyst mother solution No. 1.No. 1 nanometer optical catalyst mother solution is sprayed on the porous ceramics, dried 1 hour down, promptly prepare the porous ceramics catalysis material at 200 ℃.
Present embodiment is the porous ceramics catalysis sample for preparing under 200 ℃ temperature.Titanate esters and water fully react the back and generate TiO
2Under emulsifying agent lecithin, lauryl amine emulsification, generate emulsion then, stable dispersion is in the aqueous solution, under the methylcellulose effect, increase its stability after being coated on substrate surface at substrate surface, substrate surface can be stably fixed at, and the ultraviolet light degradation acetaldehyde of ultraviolet source can be effectively utilized.
Get the sample of an embodiment 1, area is 10 * 10cm
2, putting it into volume is in the experiment box of 4L, and the initial concentration of wherein testing aldehydes gas in the box is 16ppm, and the black light lamp of built-in 20W is degraded to aldehydes gas.Detecting once every the 20 minutes concentration to aldehydes gas with gas-chromatography (SHIMADZUGC-17AG type), is 4L with volume, and concentration is 16ppm acetaldehyde, can be decomposed 80% in 60 minutes, the results are shown in Figure 1.
Embodiment 3
No. 2 nanometer optical catalyst mother solution is composed as follows, by weight percentage:
With titanium tetrachloride 10%, water 70%, phosphoric acid 2%, glyceride 4%, lauryl amine 3%, diethanol amine 3%, polyglycereol 4%, carboxymethyl cellulose 4% joins in the reactor, by grinding and fully stirring 24 hours, place after 7 days, promptly be prepared into nanometer optical catalyst mother solution No. 2.No. 2 nanometer optical catalyst mother solutions are sprayed on porous, expanded on glass,, promptly prepare porous, expanded glass photocatalytic material 150-200 ℃ of oven dry 1 hour down.
Present embodiment is used the cheap initiation material of titanium tetrachloride, is prepared into nanometer optical catalyst mother solution under the effect of emulsifying agent, and it is coated on the porous, expanded porous photocatalytic material of making on glass, can effectively utilize the ultraviolet light degradation acetaldehyde of ultraviolet source.
Get the porous, expanded glass photocatalytic material of an embodiment 3, area is 10 * 10cm
2, putting it into volume is in the experiment box of 4L, and the initial concentration of wherein testing aldehydes gas in the box is 16ppm, and the black light lamp of built-in 20W is degraded to aldehydes gas.Detecting once every the 20 minutes concentration to aldehydes gas with gas-chromatography (SHIMADZUGC-17AG type), is 4L with volume, and concentration is 16ppm acetaldehyde, can be decomposed 90% in 120 minutes, as shown in Figure 2.
Embodiment 5
No. 3 nanometer optical catalyst mother solution is composed as follows, by weight percentage:
With titanium dioxide 10%, ferric oxide powder 5%, water 60%, phosphatase 24 %, the concentrated sulfuric acid 4%, glyceride 4%, methyl glycol fatty acid ester 3%, diethanol amine 2%, macrogol 4%, carboxymethyl cellulose 4% joins in the reactor, by grinding and fully stirring 24 hours, place after 7 days, promptly be prepared into nanometer optical catalyst mother solution No. 3.No. 3 nanometer optical catalyst mother solutions are sprayed on the porous aluminium flake, dried 30 minutes down, promptly prepare porous aluminium flake catalysis material at 100 ℃.
Porous photocatalytic material not only carries out effective cleaning reaction to acetaldehyde class pernicious gas, and nuisance in the water purified, present embodiment 5 is an initiation material with cheap titanium dioxide, under the effect of acid and ester, be prepared into nanometer optical catalyst mother solution, can under 100 ℃ of low temperature, be fixed on the porous material, as be fixed on the porous aluminium flake, can effectively the rhodamine B dye scavenging in the water be fallen.
Get one of embodiment 5 porous aluminium flake catalysis material, area is 5 * 5cm
2,, use the 400W lamp and high pressure mercury, to 50mL 1 * 10 at distance lamp 15cm place
-5MolL
-1Rhodamine B solution degrade.The result shows that sample can degrade rhodamine B fully substantially about 30 minutes, (ultraviolet spectra is by Shimadzu uv-1601pc spectrophotometer), and the result is as shown in Figure 3.
Embodiment 7
No. 4 nanometer optical catalyst mother solution is composed as follows, by weight percentage:
With titanium tetrachloride 5%, titanium dioxide 5%, molybdenum trioxide 2%, bentonite 1%, water 70%, phosphoric acid 2%, glyceride 4%, gelatin 4%, polyethylene glycol 3%, carboxymethyl cellulose 4%, join in the reactor, by grinding and ultrasonic 24 hours ultrasound intensity 80W, place after 7 days, promptly be prepared into nanometer optical catalyst mother solution No. 4.No. 4 nanometer optical catalyst mother solutions are sprayed on the honeycombed cement, dried 1 hour down, promptly prepare the honeycombed cement catalysis material at 150-200 ℃.
The multiple oxide particle of present embodiment 7 is prepared into nanometer optical catalyst mother solution under the effect of emulsifying agent, acid, it is sprayed on the honeycombed cement, can effectively remove formaldehyde.It is sprayed on the honeycombed cement, can effectively removes formaldehyde.
Get the honeycombed cement catalysis material of an embodiment 7, area is 10 * 10cm
2The gas decomposition apparatus is with embodiment 2, initial concentration is degraded for the 16ppm formaldehyde gas, detect once every the concentration of 20 minutes PARA FORMALDEHYDE PRILLS(91,95) gas with gas-chromatography (SHIMADZUGC-17AG type), with volume is 4L, concentration is 16ppm formaldehyde, can be decomposed 80% in 120 minutes, the result as shown in Figure 4.
Claims (11)
1. nanometer optical catalyst mother solution, it is characterized in that: the composition of nanometer optical catalyst mother solution, be by weight percentage: titanate esters, titanium tetrachloride, photocatalyst powder or any mixture 1-30% between them, emulsifying agent 5-20%, thickener 4-15%, acid 1-10%, water 25-89%.
2. nanometer optical catalyst mother solution as claimed in claim 1 is characterized in that: described titanate esters is a kind of or any mixture between them in butyl titanate, tetraethyl titanate, the isopropyl titanate.
3. nanometer optical catalyst mother solution as claimed in claim 1 is characterized in that: described photochemical catalyst is TiO
2, WO
3, MoO
3Or Fe
2O
3A kind of or any mixture between them in the nano particle.
4. nanometer optical catalyst mother solution as claimed in claim 1 is characterized in that: described emulsifying agent is a kind of or any mixture between them in lecithin, sucrose fatty ester, sorbitan carboxylic esters, methyl glycol fatty acid ester, glyceride, lauryl amine, diethanol amine, oleic acid or the polyglycereol.
5. nanometer optical catalyst mother solution as claimed in claim 1 is characterized in that: described thickener is a kind of or any mixture between them in starch, gelatin, pectin, carboxymethyl cellulose, sodium carboxymethylcellulose, methylcellulose, bentonite, imvite, oxidic polyethylene or the polyethylene glycol.
6. preparation method as each described nanometer optical catalyst mother solution of claim 1-5, it is characterized in that: titanate esters, titanium tetrachloride, photochemical catalyst powder art or any mixture between them that will account for gross weight 1-30%, with the emulsifying agent that accounts for gross weight 5-20%, account for the thickener of gross weight 4-12%, the water mixing that accounts for the acid of gross weight 1-10% and account for gross weight 25-89%, by grinding and ultrasonic echography or stirring, fully be prepared into nanometer optical catalyst mother solution after the reaction.
7. the preparation method of nanometer optical catalyst mother solution as claimed in claim 6, it is characterized in that: described titanate esters is a kind of or any mixture between them in butyl titanate, tetraethyl titanate, the isopropyl titanate.
8. the preparation method of nanometer optical catalyst mother solution as claimed in claim 6, it is characterized in that: described photochemical catalyst is TiO
2, WO
3, MoO
3Or Fe
2O
3A kind of or any mixture between them in the nano particle.
9. the preparation method of nanometer optical catalyst mother solution as claimed in claim 6, it is characterized in that: described emulsifying agent is a kind of or any mixture between them in lecithin, sucrose fatty ester, sorbitan carboxylic esters, methyl glycol fatty acid ester, glyceride, lauryl amine, diethanol amine, oleic acid or the polyglycereol.
10. the preparation method of nanometer optical catalyst mother solution as claimed in claim 6, it is characterized in that: described thickener is a kind of or any mixture between them in starch, gelatin, pectin, carboxymethyl cellulose, sodium carboxymethylcellulose, methylcellulose, bentonite, imvite, oxidic polyethylene or the polyethylene glycol.
11. purposes as each described nanometer optical catalyst mother solution of claim 1-5, it is characterized in that: the mother liquor of making is coated on the porous material, dry being lower than under 300 ℃ the temperature, form stable and have the photocatalyst layer of highlight catalytic active.
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| CN101526497B (en) * | 2009-04-15 | 2012-02-15 | 攀钢集团钢铁钒钛股份有限公司 | Method for preparing sample solution for detecting titanium tetrachloride |
| CN104841420A (en) * | 2015-05-05 | 2015-08-19 | 广州迪森热能技术股份有限公司 | Denitration catalyst activity mother liquor preparation method and application of denitration catalyst activity mother liquor |
| CN109603551A (en) * | 2018-12-15 | 2019-04-12 | 佛山市铁人环保科技有限公司 | A kind of photocatalysis treatment purification method preventing automobile exhaust pollution |
| CN112356176A (en) * | 2020-11-05 | 2021-02-12 | 南京国豪环保材料科技有限公司 | Plywood with formaldehyde room-temperature catalytic decomposition function and preparation method thereof |
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