CN1486785A - Prepn process of photocatalytic filtering net of foamed metal carrying nano Tio2 - Google Patents
Prepn process of photocatalytic filtering net of foamed metal carrying nano Tio2 Download PDFInfo
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- CN1486785A CN1486785A CNA031422071A CN03142207A CN1486785A CN 1486785 A CN1486785 A CN 1486785A CN A031422071 A CNA031422071 A CN A031422071A CN 03142207 A CN03142207 A CN 03142207A CN 1486785 A CN1486785 A CN 1486785A
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Abstract
The present invention belongs to the field of chemistry and chemical engineering. The loaded photocatalytic filtering net is prepared with foamed metal sheet as carrier and through preoxidation of the foamed metal sheet, soaking the preoxidized foramed metal sheet in sol with tetrabutyl titanate or titanium trichloride precursor, drying and sintering. Carried TiO2 as active component accounts for 3.0-9.8% of total photocatalytic filtering net weight. The foamed metal of the present invention has stable chemical performance and high air penetration; and the loaded photocatalytic filtering net has great carrying amout, great specific surface area, high combination performance and high photocatalytic activity. When cooperating with ultraviolet ligh source, the loaded photocatalytic filtering net may be used to eliminate organic pollutant effectively.
Description
Technical field
The present invention relates to a kind of preparation method of photocatalysis screen pack, particularly a kind of foam metal load TiO
2The preparation method of nano-photo catalytic screen pack.Belong to chemical field.
Background technology
Photocatalysis is a kind of emerging depollution of environment technology.Nano-TiO
2Photochemical catalyst oxidation or reduction effectively is adsorbed on its lip-deep pernicious gas molecule, and kill bacteria suppresses virus, and harmful organic substance, bacterium etc. can be converted into innocuous substances such as water and carbon dioxide, and without any secondary pollution.The photochemical catalyst of existing preparation is preparation TiO mostly
2Nano-powder is because TiO
2Photocatalysis need be with TiO
2Active component is fixed, and needs certain light action area and reaction time, therefore improves TiO
2Photocatalysis efficiency and the photocatalysis carrier that adopt to be fit to and carrying method be the key that solves photocatalysis technology.The seen host material that is used for load mainly is sheet glass, silica gel bead and ceramic honey comb etc. at present, utilizes the prepared photochemical catalyst of these carriers in use to have problems such as effective light-receiving area is little, vapour lock big, mechanical strength is not high, easy fragmentation.
Find by literature search, the Chinese invention patent application number is 01131093.6, name is called: the preparation method of nm crystal TiO 2 photocatalyst carried by metallic wire screen skeleton, this patent disclosure a kind of be the photochemical catalyst of carrier with the woven wire, at first be that presoma prepares transition zone colloidal sol with the tetrabutyl titanate, preparing with tetrabutyl titanate or titanium tetrachloride then is the active layer colloidal sol that presoma adds pore creating material again, transition zone colloidal sol is coated on the woven wire skeleton shape carrier of cleaning, utilize the method lift plated film that active layer colloidal sol directly has been coated on mesh-like skeleton carrier through cleaning or preplating on the mesh-like skeleton carrier of transition zone at last, drying, after the calcining, form TiO
2Film photocatalyst.Or directly use TiO
2Nano-powder is mixed with suspension, lifts preparation TiO on the woven wire framework material
2Powder attached type photochemical catalyst.Not only the woven wire response area is minimum for this method, and needs the preparation transition zone and add pore creating material etc., technology more complicated.
Summary of the invention
The object of the invention is to overcome the deficiency of above technical problem, and a kind of foam metal load TiO is provided
2The preparation method of nano-photo catalytic screen pack passes through to the design of photocatalysis screen pack and the improvement of support materials it, reaches the purpose that improves photocatalysis efficiency.The present invention is presoma with the titanium trichloride, can reduce organic discharging in the catalysis material preparation process; With the foam metal is that host material carries out load, and it is little to solve normal load material load area effectively, and vapour lock is big, problems such as bad mechanical strength.
The present invention is achieved by the following technical solutions, the present invention is that carrier carries out load with the foam metal sheet, at first before load photocatalytic activity component, the foam metal sheet is carried out pre-oxidation treatment, after the foam metal sheet after the pre-oxidation treatment floods in the colloidal sol that with butyl titanate or titanium trichloride is presoma, again drying, burn till and make support type photocatalysis screen pack, the TiO of institute's load
2The 3.0-9.8% of photocatalytic activity ingredients constitute photocatalysis screen pack gross weight.
Foam metal sheet carrier can be foam copper, nickel foam, foam iron and foamed aluminium, its good permeability, stable performance.In order to improve response area and photocatalytic activity component load capacity and the photocatalytic activity on carrier, before load photocatalytic activity component, metal foam sheet is carried out pre-oxidation treatment, its treatment temperature is 150-750 ℃, the processing time is 2-60min.Through having formed the intermediate layer between prepared photocatalytic activity component and the carrier after the pre-oxidation treatment, in conjunction with firm, load capacity is big, the photocatalytic activity height.
The present invention is the colloidal sol of presoma with butyl titanate or titanium trichloride, can make by following three kinds of methods, can select for use wherein a kind of during enforcement arbitrarily:
1, with the butyl titanate is presoma, the molar concentration of butyl titanate is 0.2～1mol/L in the precursor solution, wherein the molar percentage of each composition is: butyl titanate: diethanol amine=0.5～1: 1, ethyl orthosilicate: butyl titanate=0.01～0.05: 1, water: ethanol=0.5～1: 10.The preparation process of colloidal sol is: a certain amount of butyl titanate is added in the ethanolic solution, dropwise add diethanol amine while stirring, after fully stirring, dropwise add a certain amount of water and ethyl orthosilicate again, leave standstill its ageing of an angel with the sufficient solution of above-mentioned stirring is airtight, obtain transparent colloidal sol, display stand-by.
2, with the titanium trichloride be presoma, ammonia spirit is joined in the titanium oxide solution, generate black precipitate,, be placed under the room temperature dry after the washing sedimentation and filtration.Get above-mentioned black precipitate, add hydrogenperoxide steam generator, add distilled water in the course of reaction, and constantly stir, when reaction finished, solution was transparent brown-red solution, added the concentration that suitable water is adjusted colloidal sol again, final TiO
2The concentration of colloidal sol is 0.1～0.5mol/L, displays stand-by.
3, be presoma with the butyl titanate, the molar concentration of butyl titanate is 0.2～1mol/L in the precursor solution, and wherein the molar percentage of each composition is: butyl titanate: diethanol amine=0.5～1: 1, and water: ethanol=0.5～1: 10.The preparation process of colloidal sol is: a certain amount of butyl titanate is added in the ethanolic solution, dropwise add diethanol amine while stirring, after fully stirring, dropwise add a certain amount of water more while stirring, add 0.01～0.05g/ml powder TiO in above-mentioned colloidal sol
2, fully stirring, mixed sols solution is airtight to leave standstill its ageing of an angel, stand-by.
The present invention has substantive distinguishing features and marked improvement, the foam metal that the present invention is used, stable chemical performance, its good permeability; See through after the pre-oxidation treatment and load TiO
2, its load capacity is big, and specific area is big, and associativity is good, and the photocatalytic activity height by disposing suitable ultraviolet source, can be removed organic pollution effectively.
The specific embodiment
In conjunction with content of the present invention, provide following examples:
Embodiment 1:
1, be the preparation of the colloidal sol of presoma with the butyl titanate: be presoma with the butyl titanate, the molar concentration of butyl titanate is 0.2mol/L, the preparation process of colloidal sol is: the 6.81ml butyl titanate is added in the 90.91ml ethanolic solution, dropwise add diethanol amine 1.92ml while stirring, after fully stirring, dropwise add 0.36ml water and 0.1ml ethyl orthosilicate more while stirring, leave standstill its ageing of an angel with the sufficient solution of above-mentioned stirring is airtight, obtain transparent colloidal sol.
2, with foam metal nickel (surface density 420g/m
2Thickness 2.0mm) pre-oxidation treatment 60 minutes under 150 ℃ of temperature, cooling, then pretreated foam metal nickel is immersed in the above-mentioned colloidal sol 3 minutes, take out, to dry attached to the unnecessary colloidal sol in the foam metal hole with centrifugation, air dry was carried out the second time and is soaked after 30 minutes.550 ℃ of insulations 2 hours in heating furnace at last form on foam metal surface and to be mixed with SiO
2TiO
2Nano-photocatalyst, its load capacity are 4.8% (percentage by weight).With the degradation rate test shows to aldehydes gas, the degradation rate of this material reaches 82%.
Embodiment 2:
1, with the titanium trichloride is the preparation of the colloidal sol of presoma: with adding the ammoniacal liquor of 10ml in the 20ml titanium oxide solution, generate black precipitate,, be placed under the room temperature dry after the washing with sedimentation and filtration.Get above-mentioned black precipitate 1.25g, add the 20ml hydrogenperoxide steam generator, add 70ml distilled water in the course of reaction, and constantly stir, when reaction finished, solution was transparent brown-red solution, final TiO
2The concentration of colloidal sol is 0.15mol/L, displays stand-by.
2, with foam metal nickel (surface density 420g/m
2Thickness 2.0mm) pre-oxidation treatment 2 minutes under 750 ℃ of temperature, cooling, then pretreated foam metal nickel is immersed in the above-mentioned colloidal sol 3 minutes, take out, to dry attached to the unnecessary colloidal sol in the foam metal hole with centrifugation, air dry was carried out the second time and is soaked after 30 minutes.550 ℃ of insulations 1 hour in heating furnace at last form TiO on foam metal surface
2Nano-photocatalyst, its load capacity are 5.2% (percentage by weight).With the degradation rate test shows to aldehydes gas, the degradation rate of this material reaches 91%.
Embodiment 3:
1, be the preparation of the colloidal sol of presoma with the butyl titanate: be presoma with the butyl titanate, the molar concentration of butyl titanate is 1mol/L in the precursor solution, the preparation process of colloidal sol is: the 34.04ml butyl titanate is added in the 54.59ml ethanolic solution, dropwise add the 9.62ml diethanol amine while stirring, after fully stirring, dropwise add 1.75ml water more while stirring, in above-mentioned colloidal sol, add 2g powder TiO
2, fully stirring, mixed sols solution is airtight to leave standstill its ageing of an angel, stand-by.
2, the preparation of support type photocatalysis screen pack: with foam metal nickel (surface density 370g/m
2Thickness 1.5mm) pre-oxidation treatment 40 minutes under 250 ℃ of temperature, cooling, then pretreated foam metal is immersed in the above-mentioned colloidal sol 3 minutes, take out, to dry attached to the unnecessary colloidal sol in the foam metal hole with centrifugation, after the air dry 30 minutes, 550 ℃ are incubated 1.5 hours in heating furnace, form TiO at the foam metal nickel surface
2Film and TiO
2The photochemical catalyst that nano powder adheres to simultaneously, its load capacity are 3.0% (percentage by weight).With the degradation rate test shows to aldehydes gas, the degradation rate of this material reaches 81%.
Embodiment 4:
1, be the preparation of the colloidal sol of presoma with the butyl titanate: be presoma with the butyl titanate, the molar concentration of butyl titanate is 0.6mol/L in the precursor solution, the 20.42ml butyl titanate is added in the 72.74ml ethanolic solution, dropwise add diethanol amine 5.76ml while stirring, after fully stirring, dropwise add 1.08ml water and 0.35ml ethyl orthosilicate more while stirring, leave standstill its ageing of an angel with the sufficient solution of above-mentioned stirring is airtight, obtain transparent colloidal sol.
2, the preparation of support type photocatalysis screen pack: with foam metal nickel (surface density 370g/m
2, thickness 1.5mm) and pre-oxidation treatment 30 minutes under 350 ℃ of temperature, cooling, then pretreated foam metal copper is immersed in the above-mentioned colloidal sol 3 minutes, takes out, will dry attached to the unnecessary colloidal sol in the foam metal hole with centrifugation, after the air dry 30 minutes, carry out the second time and soak.550 ℃ of insulations 1 hour in heating furnace at last form on foam metal surface and to be mixed with SiO
2TiO
2Nano-photocatalyst, its load capacity are 7.8% (percentage by weight).With the degradation rate test shows to aldehydes gas, the degradation rate of this material reaches 91%.
Embodiment 5:
1, with the titanium trichloride is the preparation of the colloidal sol of presoma: 45ml ammoniacal liquor is joined in the 20ml titanium oxide solution, generate black precipitate, Chen Dian is filtered, be placed under the room temperature dry after the washing.Get above-mentioned black precipitate 4.2g, add the 60ml hydrogenperoxide steam generator, add 50ml distilled water in the course of reaction, and constantly stir, when reaction finished, solution was transparent brown-red solution, final TiO
2The concentration of colloidal sol is 0.5mol/L, displays stand-by.
2, the preparation of support type photocatalysis screen pack: with foam metal nickel (surface density 370g/m
2Thickness 1.1mm) pre-oxidation treatment 20 minutes under 450 ℃ of temperature, cooling, then pretreated foam metal is immersed in the above-mentioned colloidal sol 3 minutes, take out, will dry attached to the unnecessary colloidal sol in the foam metal hole with centrifugation, air dry is after 30 minutes, carry out the second time and soak, repeat to dry and dry run.At last in heating furnace 550 ℃ the insulation 1 hour, its load capacity is 7.8% (percentage by weight).With the degradation rate test shows to aldehydes gas, the degradation rate of this material reaches 90%.
Embodiment 6:
1, be the preparation of the colloidal sol of presoma with the butyl titanate: be presoma with the butyl titanate, the molar concentration of butyl titanate is 0.8mol/L in the precursor solution, the preparation process of colloidal sol is: the 27.23ml butyl titanate is added in the ethanolic solution, dropwise add the 7.67ml diethanol amine while stirring, after fully stirring, dropwise add 1.44ml water more while stirring, in above-mentioned colloidal sol, add the p25 TiO of 5g
2Powder fully stirs, and mixed sols solution is airtight to leave standstill its ageing of an angel, stand-by.
2, the preparation of support type photocatalysis screen pack: with foam metal nickel (surface density 420g/m
2Thickness 2.0mm) pre-oxidation treatment 10 minutes under 500 ℃ of temperature, cooling, then pretreated foam metal is immersed in the above-mentioned colloidal sol 3 minutes, take out, will dry attached to the unnecessary colloidal sol in the foam metal hole with centrifugation, air dry is after 30 minutes, carry out the second time and soak, repeat to dry and dry run.550 ℃ are incubated 1 hour in heating furnace, form TiO on the foam metal surface
2Film and TiO
2The photochemical catalyst that nano powder adheres to simultaneously, its load capacity are 9.8% (percentage by weight).With the degradation rate test shows to aldehydes gas, the degradation rate of this material reaches 92%.
Claims (4)
1, a kind of foam metal load TiO
2The preparation method of nano-photo catalytic screen pack, it is characterized in that, with the foam metal sheet is that carrier carries out load, at first before load photocatalytic activity component, the foam metal sheet is carried out pre-oxidation treatment, after the foam metal sheet after the pre-oxidation treatment floods in the colloidal sol that with butyl titanate or titanium trichloride is presoma, again drying, burn till and support type photocatalysis screen pack, the TiO of institute's load
2The 3.0-9.8% of photocatalytic activity ingredients constitute photocatalysis screen pack gross weight.
2, foam metal load TiO according to claim 1
2The nano-photo catalytic screen pack is characterized in that, described foam metal sheet carrier is a kind of in foam copper, nickel foam, foam iron and the foamed aluminium.
3, foam metal load TiO according to claim 1
2The preparation method of nano-photo catalytic screen pack is characterized in that, before load photocatalytic activity component metal foam sheet is carried out pre-oxidation treatment, and its treatment temperature is 150-750 ℃, and the processing time is 2-60min.
4, foam metal load TiO according to claim 1
2The preparation method of nano-photo catalytic screen pack is characterized in that, described is the colloidal sol of presoma with butyl titanate or titanium trichloride, makes by following three kinds of methods, and is optional wherein a kind of during enforcement:
(1), with the butyl titanate is presoma, the molar concentration of butyl titanate is 0.2～1mol/L in the precursor solution, wherein the molar percentage of each composition is: butyl titanate: diethanol amine=0.5～1: 1, ethyl orthosilicate: butyl titanate=0.01～0.05: 1, water: ethanol=0.5～1: 10, the preparation process of colloidal sol is: butyl titanate is added in the ethanolic solution, dropwise add diethanol amine while stirring, after fully stirring, dropwise add entry and ethyl orthosilicate again, leave standstill its ageing of an angel with the sufficient solution of above-mentioned stirring is airtight, obtain transparent colloidal sol, display stand-by;
(2), be presoma with the titanium trichloride, ammonia spirit is added in an amount of titanium oxide solution, generate black precipitate, with sedimentation and filtration, be placed on drying under the room temperature after the washing, get above-mentioned black precipitate, add hydrogenperoxide steam generator, add distilled water in the course of reaction, and constantly stir, when reaction finished, solution was transparent brown-red solution, add entry again and adjust the concentration of colloidal sol, final TiO
2The concentration of colloidal sol is 0.1～0.5mol/L, displays stand-by;
(3), with the butyl titanate be presoma, the molar concentration of butyl titanate is 0.2～1mol/L in the precursor solution, wherein the molar percentage of each composition is: butyl titanate: diethanol amine=0.5～1: 1, water: ethanol=0.5～1: 10, the preparation process of colloidal sol is: butyl titanate is added in the ethanolic solution, dropwise add diethanol amine while stirring, after fully stirring, dropwise add entry more while stirring, in above-mentioned colloidal sol, add 0.01～0.05g/ml powder TiO
2, fully stirring, mixed sols solution is airtight to leave standstill its ageing of an angel, stand-by.
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| CN1321739C (en) * | 2005-06-09 | 2007-06-20 | 上海交通大学 | Production of TiO2 naometer light catalyzing net from foam metal carrier |
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