CN1846851A - Supported nanometer crystalline titania photocatalyst and its prepn process - Google Patents
Supported nanometer crystalline titania photocatalyst and its prepn process Download PDFInfo
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- CN1846851A CN1846851A CN 200610013609 CN200610013609A CN1846851A CN 1846851 A CN1846851 A CN 1846851A CN 200610013609 CN200610013609 CN 200610013609 CN 200610013609 A CN200610013609 A CN 200610013609A CN 1846851 A CN1846851 A CN 1846851A
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Abstract
The present invention relates to titania catalyst, and is supported nanometer crystalline titania photocatalyst and its preparation process. The supported nanometer crystalline titania photocatalyst consists of alumina pellet carrier of specific weight 0.5-5.0 g/cu cm and grain size 0.5-2.0 mm and nanometer crystalline TiO2 coating. The preparation process includes the following steps: preparing carrier, preparing precursor solution; and supporting. The alumina pellet carrier of the present invention has different pore sizes, low cost and high strength, and is suitable for industrial application.
Description
Technical field
Technical scheme of the present invention relates to a kind of titanium deoxide catalyst, specifically supported nanometer crystalline titania photocatalyst and preparation method thereof.
Background technology
Begin from the end of the seventies in last century, existing relevant semiconductor light-catalyst is handled the research report of all kinds of sewage both at home and abroad, and its degraded object relates to phenols, dyestuff, hydro carbons, surfactant, organic pigment, halogenated aromatic compound, polycyclic aromatic hydrocarbon, the multiple organic compound of agrochemical and part inorganic compound.Wherein, nano-TiO
2Powder has chemical stability height, fast light burn into indissoluble, nontoxic characteristics, and because it has darker valence-band level, so some compounds that are difficult to degrade by chemistry or biological method can pass through TiO under the light radiation condition
2Photocatalytic degradation mineralising Cheng Shui and CO
2This shows nano-TiO
2The powder photocatalytic edman degradation Edman is a kind of very promising water treatment new technology, particularly aspect the organic pollution in removing water body the potentiality that can not be ignored is arranged.Yet this water technology but still rests on the experimental stage at present, apart from industrial applications big distance is arranged still, and its main cause is to fail to solve nano-TiO
2Powder is difficult to reclaim and reusable problem in handling the waste water process.
At present, the common method that addresses this problem is with TiO
2Nanometer powder is fixed on a certain carrier and is prepared into supported titanium
2Photochemical catalyst.The nanocrystal TiO of support type
2The liquid-solid separation of photochemical catalyst is more or less freely, can overcome TiO effectively
2Nanometer powder is difficult to reclaim and reusable shortcoming in handling the waste water process.Chinese scholars has all obtained some progress in this research field, and wherein used carrier has silica gel, natural minerals, woven wire, zeolite, glass plate, glass fibre.For example, the disclosed carrier of CN 03132906.3 " load type titania photocatalyst and preparation method " is a Bio-sil; The carrier that CN 99102734.5 " preparation method of load type titania photocatalyst " is reported is the concavo-convex rod of natural minerals; Said carrier is a woven wire skeleton shape among the CN 01131093.6 " preparation method of nm crystal TiO 2 photocatalyst carried by metallic wire screen skeleton "; Carrier disclosed in the CN 200510122523.4 " preparation method of porous expanded perlite material load nanometer crystalline titania photocatalyst " is a porous expanded perlite material.Yet the preparation method of above-mentioned these load type titania photocatalysts exists preparation cost high and complex process or the relatively poor shortcoming of intensity.
Summary of the invention
Technical problem to be solved by this invention is: new supported nanometer crystalline titania photocatalyst and preparation method thereof is provided.Its carrier is the alundum (Al bead, and method is to adopt sol-gel process directly to carry out nano-TiO on alundum (Al bead surface
2The load of film makes the firm TiO of load
2Photochemical catalyst, thus overcome preparation cost high and complex process or the relatively poor shortcoming of intensity.
The present invention solves this technical problem the technical scheme that is adopted: the said supported nanometer crystalline titania photocatalyst of the present invention is by alundum (Al bead carrier and nanocrystal TiO
2Clad is formed.
The proportion of said alundum (Al bead carrier is 0.5～5.0g/cm in the supported nanometer crystalline titania photocatalyst of the present invention
3, particle diameter is 0.5～2.0mm.
The preparation method of supported nanometer crystalline titania photocatalyst of the present invention may further comprise the steps:
(1) preparation of carrier
With alundum (Al bead content is that 5～15% hydrochloric acid solution soaked 2～10 hours, taking out the back cleans 3 times with distilled water, after air-dry, put into baking oven, under the condition of bubbling air,, promptly become the alundum (Al bead carrier that disposes after the oven dry in 50 ℃～200 ℃ following roastings 1～5 hour;
(2) preparation of precursor solution
With butyl titanate, or metatitanic acid n-propyl, or isopropyl titanate, or tetraethyl titanate is a presoma, the volume ratio of various compositions is in the precursor solution: butyl titanate, or metatitanic acid n-propyl, or isopropyl titanate, or tetraethyl titanate: ethanol: water: diethanol amine: acetic acid=1: 1～15: 1.5～6.5: 0.1～0.9: 0.01～0.05, the addition sequence of five kinds of materials is: at first add entry in ethanol, under stirring condition, add acetic acid and diethanol amine simultaneously as stabilizing agent, at last with the presoma butyl titanate, or metatitanic acid n-propyl, or isopropyl titanate, or tetraethyl titanate dropwise joins in the above-mentioned mixed solution, in confined conditions with solution left standstill 2～8 days, the precursor sol of stable transparent;
(3) immobilized
At first the precursor sol with the preparation of above-mentioned (2) step evenly spreads upon on the alundum (Al bead carrier that is made by above-mentioned (1) step, again its rapid soaking is also taken out in the precursor sol of above-mentioned (2) step preparation fast, get rid of unnecessary precursor sol by drying device then, with the alundum (Al bead carrier aeration-drying of the wet precursor sol of load after 1 hour, again this alundum (Al bead carrier is positioned in the baking oven, under 40 ℃～130 ℃ temperature, dried through 1～7 hour, speed with 1～3 ℃/second is warming up to 200～600 ℃ under air atmosphere at last, keep temperature 1～6 hour, and formed nanocrystal TiO
2Layer, layer thickness is 20～600nm, makes of the present invention by alundum (Al bead carrier and nanocrystal TiO thus
2The supported nanometer crystalline titania photocatalyst that clad is formed.
The invention has the beneficial effects as follows: compare with silica gel, zeolite, glass plate, glass fibre, the concavo-convex rod of natural minerals, woven wire framework material and so on carrier, because the used alundum (Al bead carrier of supported nanometer crystalline titania photocatalyst of the present invention has multiple aperture and advantages of cheap price is arranged self, so select the alundum (Al bead to be adapted to industrial applications as the load of titanium dioxide optical catalyst, this is an obvious improvement.Method loaded with nano crystal grain TiO on the alundum (Al bead of immersion is smeared in utilization of the present invention
2Clad through roasting, is made supported nanometer crystalline titania photocatalyst, and technology is simple, the raw material consumption is few, nano titanium oxide utilization rate height, preparation time are short, it is little to pollute, be fit to industrialized mass.Compare the used alundum (Al bead carrier of supported nanometer crystalline titania photocatalyst of the present invention with porous expanded perlite material support and have higher intensity, prolonged the time that catalyst uses, also more be adapted to industrial applications.
Supported nanometer crystalline titania photocatalyst of the present invention itself is a loose structure, adsorption capacity is better, catalytic degradation waste water and airborne various organic matter are applicable to and handle industry and sanitary wastewater and airborne poisonous and harmful and the biological organic matter that is difficult to degrade efficiently.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples, and the cited case does not influence protection scope of the present invention.
The XRD figure of Fig. 1 supported nanometer crystalline titania photocatalyst of the present invention.
Fig. 2 utilizes supported nanometer crystalline titania photocatalyst static treatment reactive brilliant bule degradation curve of the present invention.
Specific implementation method
Among Fig. 1, a: alundum (Al bead loaded with nano crystal grain TiO
2,: Al
2O
3, O: anatase TiO
2, b: alundum (Al bead.Fig. 1 shows alundum (Al bead loaded with nano crystal grain TiO
2The front and back of photochemical catalyst, the difference during it shows in XRD, top is divided into alundum (Al bead load TiO
2After XRD, obviously demonstrate TiO in the component of bottom
2Characteristic peak, the bottom is divided into the XRD of alundum (Al bead itself.
Fig. 2 represents supported nanometer crystalline titania photocatalyst of the present invention is put into the quartz container that the reactive brilliant bule solution that configures is housed, static degradation treatment is 5 hours under ultraviolet source irradiation, and the navy blue dye solution just decoloured fully after 1 hour and is colourless transparent solution.This degradation curve shows: organic carbon content value TOC reduces to 1.46mg/L by 18.46mg/L.The Chinese of ordinate unit among the figure " TOC " means the organic carbon content value entirely.
With commercially available proportion is 0.5g/cm
3Particle diameter is that the alundum (Al bead 1000g content of 0.5mm is that 5% hydrochloric acid solution soaked 10 hours, taking out the back cleans three times with distilled water, after air-dry, put into baking oven under the condition of bubbling air in 50 ℃ of following roastings 5 hours, promptly become the alundum (Al bead carrier that disposes after the oven dry.
With the butyl titanate is presoma, the volume ratio of each composition is in the precursor solution: butyl titanate: ethanol: water: diethanol amine: acetic acid=1: 1: 1.5: 0.1: 0.01, the addition sequence of five kinds of materials is: at first add entry 150ml in the 100ml ethanolic solution, under stirring condition, add acetic acid 1ml and diethanol amine 10ml simultaneously as stabilizing agent, at last butyl titanate 100ml is dropwise joined in the above-mentioned mixed solution, in confined conditions with solution left standstill 2 days, the stable transparent precursor sol.
The precursor sol of above-mentioned preparation is evenly spread upon on the above-mentioned alundum (Al bead carrier that makes, again this carrier rapid soaking is taken out in above-mentioned precursor sol and fast, get rid of unnecessary precursor sol by drying device, with the alundum (Al bead carrier aeration-drying of the wet precursor sol of load after 1 hour, again this alundum (Al bead carrier is positioned over baking oven, under 40 ℃ of temperature, dried through 7 hours, speed with 1 ℃/second is warming up to 200 ℃ under air atmosphere at last, keep temperature 6 hours, and formed nanocrystal TiO
2Layer, layer thickness is 20nm, promptly makes of the present invention by alundum (Al bead carrier and nanocrystal TiO
2The supported nanometer crystalline titania photocatalyst that the carrier clad is formed.
With commercially available proportion is 2.5g/cm
3Particle diameter is that the alundum (Al bead 1000g content of 1.0mm is that 10% hydrochloric acid solution soaked 5 hours, taking out the back cleans three times with distilled water, after air-dry, put into baking oven under the condition of bubbling air in 100 ℃ of following roastings 2.5 hours, promptly become the alundum (Al bead carrier that disposes after the oven dry.
With the tetraethyl titanate is presoma, the volume ratio of each composition is in the precursor solution: tetraethyl titanate: ethanol: water: diethanol amine: acetic acid=1: 8: 4: 0.4: 0.02, the addition sequence of five kinds of materials is: at first add entry 400ml in the 800ml ethanolic solution, under stirring condition, add acetic acid 2ml and diethanol amine 40ml simultaneously as stabilizing agent, at last tetraethyl titanate 100ml is dropwise joined in the above-mentioned mixed solution, in confined conditions with solution left standstill 5 days, the stable transparent precursor sol.
The precursor sol of above-mentioned preparation is evenly spread upon on the above-mentioned alundum (Al bead carrier that makes, again this carrier rapid soaking is taken out in above-mentioned precursor sol and fast, get rid of unnecessary precursor sol by drying device, with the alundum (Al bead carrier aeration-drying of the wet precursor sol of load after 1 hour, again this alundum (Al bead carrier is positioned over baking oven, under 85 ℃ of temperature, dried through 4 hours, speed with 2 ℃/second is warming up to 400 ℃ under air atmosphere at last, keep temperature 3 hours, and formed nanocrystal TiO
2Layer, layer thickness is 300nm, promptly makes of the present invention by alundum (Al bead carrier and nanocrystal TiO
2The supported nanometer crystalline titania photocatalyst that the carrier clad is formed.
With commercially available proportion is 5g/cm
3Particle diameter is that the alundum (Al bead 1000g content of 2.0mm is that 15% hydrochloric acid solution soaked 2 hours, taking out the back cleans three times with distilled water, after air-dry, put into baking oven under the condition of bubbling air in 200 ℃ of following roastings 1 hour, promptly become the alundum (Al bead carrier that disposes after the oven dry.
With the isopropyl titanate is presoma, the volume ratio of each composition is in the precursor solution: isopropyl titanate: ethanol: water: diethanol amine: acetic acid=1: 15: 6.5: 0.9: 0.05, the addition sequence of five kinds of materials is: at first add entry 650ml in the 1500ml ethanolic solution, under stirring condition, add acetic acid 5ml and diethanol amine 90ml simultaneously as stabilizing agent, at last isopropyl titanate 100ml is dropwise joined in the above-mentioned mixed solution, in confined conditions with solution left standstill 8 days, the stable transparent precursor sol.
The precursor sol of above-mentioned preparation is evenly spread upon on the above-mentioned alundum (Al bead carrier that makes, again this carrier rapid soaking is taken out in above-mentioned precursor sol and fast, get rid of unnecessary precursor sol by drying device, with the alundum (Al bead carrier aeration-drying of the wet precursor sol of load after 1 hour, again this alundum (Al bead carrier is positioned over baking oven, under 130 ℃ of temperature, dried through 1 hour, speed with 3 ℃/second is warming up to 600 ℃ under air atmosphere at last, keep temperature 1 hour, and formed nanocrystal TiO
2Layer, layer thickness is 600nm, promptly makes of the present invention by alundum (Al bead carrier and nanocrystal TiO
2The supported nanometer crystalline titania photocatalyst that the carrier clad is formed.
With commercially available proportion is 1.0g/cm
3Particle diameter is that the alundum (Al bead 1000g content of 0.8mm is that 5% hydrochloric acid solution soaked 5 hours, taking out the back cleans three times with distilled water, after air-dry, put into baking oven under the condition of bubbling air in 150 ℃ of following roastings 4 hours, promptly become the alundum (Al bead carrier that disposes after the oven dry.
With the butyl titanate is presoma, the volume ratio of each composition is in the precursor solution: butyl titanate: ethanol: water: diethanol amine: acetic acid=1: 4: 4: 0.6: 0.02, the addition sequence of five kinds of materials is: at first add entry 400ml in the 400ml ethanolic solution, under stirring condition, add acetic acid 2ml and diethanol amine 60ml simultaneously as stabilizing agent, at last butyl titanate 100ml is dropwise joined in the above-mentioned mixed solution, in confined conditions with solution left standstill 5 days, stable transparent colloidal sol.
The precursor sol of above-mentioned preparation is evenly spread upon on the above-mentioned alundum (Al bead carrier that makes, again this carrier rapid soaking is taken out in above-mentioned precursor sol and fast, get rid of unnecessary precursor sol by drying device, with the alundum (Al bead carrier aeration-drying of the wet precursor sol of load after 1 hour, again this alundum (Al bead carrier is positioned over baking oven, under 50 ℃ of temperature, dried through 4 hours, speed with 1 ℃/second is warming up to 350 ℃ under air atmosphere at last, keep temperature 5 hours, and formed nanocrystal TiO
2Layer, layer thickness is 400nm, promptly makes of the present invention by alundum (Al bead carrier and nanocrystal TiO
2The supported nanometer crystalline titania photocatalyst that the carrier clad is formed.
With commercially available proportion is 2.0g/cm
3Particle diameter is that the alundum (Al bead 2000g content of 1.5mm is that 10% hydrochloric acid solution soaked 6 hours, taking out the back cleans three times with distilled water, after air-dry, put into baking oven under the condition of bubbling air in 200 ℃ of following roastings 4 hours, promptly become the alundum (Al bead carrier that disposes after the oven dry.
With the metatitanic acid n-propyl is presoma, the volume ratio of each composition is in the precursor solution: metatitanic acid n-propyl: ethanol: water: diethanol amine: acetic acid=1: 5: 4: 0.5: 0.02, the addition sequence of five kinds of materials is: at first add entry 400ml in the 500ml ethanolic solution, under stirring condition, add acetic acid 2ml and diethanol amine 50ml simultaneously as stabilizing agent, at last metatitanic acid n-propyl 100ml is dropwise joined in the above-mentioned mixed solution, in confined conditions with solution left standstill 6 days, stable transparent colloidal sol.
The precursor sol of above-mentioned preparation is evenly spread upon on the above-mentioned alundum (Al bead carrier that makes, again this carrier rapid soaking is taken out in above-mentioned precursor sol and fast, get rid of unnecessary precursor sol by drying device, with the alundum (Al bead carrier aeration-drying of the wet precursor sol of load after 1 hour, again this alundum (Al bead carrier is positioned over baking oven, under 60 ℃ of temperature, dried through 3 hours, speed with 2 ℃/second is warming up to 500 ℃ under air atmosphere at last, keep temperature 4.5 hours, and formed nanocrystal TiO
2Layer, layer thickness is 500nm, promptly makes of the present invention by alundum (Al bead carrier and nanocrystal TiO
2The supported nanometer crystalline titania photocatalyst that the carrier clad is formed.
Get the alundum (Al bead 4.0g of the load nano-titanium dioxide of any one preparation among the embodiment 1～5, put into the quartz container that the 50ml reactive brilliant bule solution that configures is housed, this quartz container being placed light source is the rectangular box body photo catalysis reactor of the 100w ultraviolet lamp tube of 254nm again, light source is positioned over 3cm place, sealing quartz container below, static degraded is 5 hours under ultraviolet source irradiation, organic carbon content value TOC reduces to 1.46mg/L by 18.46mg/L, and the navy blue dye solution decoloured fully after one hour and is colourless transparent solution.The degradation curve of processing reactive brilliant bule as shown in Figure 2.
Claims (3)
1. supported nanometer crystalline titania photocatalyst is characterized in that: by alundum (Al bead carrier and nanocrystal TiO
2Clad is formed.
2. supported nanometer crystalline titania photocatalyst according to claim 1 is characterized in that: the proportion of said alundum (Al bead carrier is 0.5～5.0g/cm
3, particle diameter is 0.5～2.0mm.
3. the preparation method of the described supported nanometer crystalline titania photocatalyst of claim 1 is characterized in that: may further comprise the steps:
(1) preparation of carrier
With alundum (Al bead content is that 5～15% hydrochloric acid solution soaked 2～10 hours, taking out the back cleans 3 times with distilled water, after air-dry, put into baking oven, under the condition of bubbling air,, promptly become the alundum (Al bead carrier that disposes after the oven dry in 50 ℃～200 ℃ following roastings 1～5 hour;
(2) preparation of precursor solution
With butyl titanate, or metatitanic acid n-propyl, or isopropyl titanate, or tetraethyl titanate is a presoma, the volume ratio of various compositions is in the precursor solution: butyl titanate, or metatitanic acid n-propyl, or isopropyl titanate, or tetraethyl titanate: ethanol: water: diethanol amine: acetic acid=1: 1～15: 1.5～6.5: 0.1～0.9: 0.01～0.05, the addition sequence of five kinds of materials is: at first add entry in ethanol, under stirring condition, add acetic acid and diethanol amine simultaneously as stabilizing agent, at last with the presoma butyl titanate, or metatitanic acid n-propyl, or isopropyl titanate, or tetraethyl titanate dropwise joins in the above-mentioned mixed solution, in confined conditions with solution left standstill 2～8 days, the precursor sol of stable transparent;
(3) immobilized
At first the precursor sol with the preparation of above-mentioned (2) step evenly spreads upon on the alundum (Al bead carrier that is made by above-mentioned (1) step, again its rapid soaking is also taken out in the precursor sol of above-mentioned (2) step preparation fast, get rid of unnecessary precursor sol by drying device then, with the alundum (Al bead carrier aeration-drying of the wet precursor sol of load after 1 hour, again this alundum (Al bead carrier is positioned in the baking oven, under 40 ℃～130 ℃ temperature, dried through 1～7 hour, speed with 1～3 ℃/second is warming up to 200～600 ℃ under air atmosphere at last, keep temperature 1～6 hour, and formed nanocrystal TiO
2Layer, layer thickness is 20～600nm, makes of the present invention by alundum (Al bead carrier and nanocrystal TiO thus
2The supported nanometer crystalline titania photocatalyst that clad is formed.
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| CN103039524A (en) * | 2012-11-24 | 2013-04-17 | 四川农业大学 | Preparation method of antimicrobial agent for corn fungal diseases |
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| CN114907042A (en) * | 2022-05-26 | 2022-08-16 | 福建工程学院 | Photocatalytic steel slag floating concrete and preparation method thereof |
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Granted publication date: 20081224 |