CN1110361C - Nanometer-level TiO2 photocatalyst carried by metal net and its preparation - Google Patents
Nanometer-level TiO2 photocatalyst carried by metal net and its preparation Download PDFInfo
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- CN1110361C CN1110361C CN98121036A CN98121036A CN1110361C CN 1110361 C CN1110361 C CN 1110361C CN 98121036 A CN98121036 A CN 98121036A CN 98121036 A CN98121036 A CN 98121036A CN 1110361 C CN1110361 C CN 1110361C
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Abstract
The present invention relates to a metal mesh solid borne nanometer TiO2 photocatalyst which is characterized in that the catalyst takes a metal mesh with the diameter of 0.05 to 2mm and 10 to 200 meshes as a basis framework, the metal mesh is selected and is one of a stainless steel mesh, a galvanized iron wire mesh, a copper mesh and an aluminum mesh, a layer of uniform mixtures of nanometer TiO2 and a fixing agent wraps the surface of the metal mesh, the fixing agent is cement or a macromolecule adhesive, the content (by weight percentage)of the TiO2 is from 5 to 50%, and the rest is the fixing agent. A layer of the nanometer TiO2 wraps the outer part of a coating layer of the mixtures. The present invention has the advantages of high activity, difficult loss of the catalyst, low manufacturing cost and easy industrialization realization.
Description
Technical field
The present invention relates to a kind of nano-TiO of carried by metal net
2Photochemical catalyst and preparation.
Background technology
The control of environmental pollution is the important issue of the photocatalysis technology that develops rapidly over nearly 5 years with administering.Nano-TiO
2Powder can be CO with the multiple organic matter exhaustive oxidation in the water as a kind of photochemical catalyst of efficient, nontoxic and long service life
2And H
2O, non-secondary pollution, nearly institute comes extremely people's concern.How people have improved TiO
2Many fruitful work have been done in active aspect.But, owing to mostly be confined to suspension system, though catalyst activity is high, easily run off, and separate with shipwreck, operating cost is also higher, is difficult to be able in practice large-scale application.
At present, both at home and abroad the immobilized work of catalyst is concentrated on the solids such as inwall of glass, pottery, polymeric membrane and various pipes on the one hand (as Japan Patent: JP10103585A), and many effective immobilization technologies are proposed accordingly, as sol-gal process, coupling method, magnetron metallikon or the like.But because formed solid or organic film compare with suspension system the blocking and absorb of light, the catalyst after immobilized can reduce greatly to the utilization rate of light.On the other hand, people select some porous granule solids such as active carbon, sand, silica, aluminium oxide, clay, kaolin, molecular sieve etc. (as Japan Patent: JP8810601), though this has improved to the utilization rate of light with to the suction-operated of substrate, catalyst is difficult to reclaim problems such as easy loss but still exist.
Summary of the invention
The object of the present invention is to provide a kind of nano-TiO of carried by metal net
2Photochemical catalyst, it not only has high activity, and catalyst is difficult for running off, and cheap for manufacturing cost, is easy to realization of industrialization.
The invention provides a kind of carried by metal net nano-TiO
2Photochemical catalyst is characterized in that this catalyst:
--with Φ 0.05～2mm, 10～200 purpose wire nettings are basic skeleton, and wire netting is selected from a kind of of stainless (steel) wire, galvanized wire mesh, copper mesh, aluminium net;
--be coated with the layer of even nano-TiO at wire netting
2With the mixture of fixative, fixative is cement or polymer binder, and its weight percentage is TiO
25～50%, the fixative surplus;
--mixture coating wraps up one deck nano-TiO outward again
2
The present invention can also be at described TiO
2With adding porous granule such as active carbon, sand, silica, aluminium oxide, clay, kaolin, molecular sieve in the fixative mixture, addition is 0.5～10% weight.
Outermost TiO among the present invention
2Can carry out modification with platinum, palladium, ruthenium, rhodium, strontium, ferric iron, the modifier addition is 0.1～1% weight.
Fixative is preferably portland cement, aluminate cement, phosphate cement among the present invention.
The present invention also provides above-mentioned carried by metal net nano-TiO
2The preparation method of photochemical catalyst is characterized in that preparation process complies with following step and carry out:
(1) with wire netting under air atmosphere 300～900 ℃, roasting 2～10 hours;
(2) with TiO
2Evenly mix the furnishing pulpous state with fixative water or water-ethanol solution, the surface of the wire netting after coating (1) and handling;
(3) with TiO
2Colloidal sol is coated with or is sprayed at the surface of the net after handle (2).
Can carry out Passivation Treatment with the concentrated sulfuric acid, red fuming nitric acid (RFNA) or chloroazotic acid before the wire netting roasting in the preparation process of the present invention.The most handy sulfonate surfactant of wire netting after the Passivation Treatment soaks modification, strengthens TiO in the binding mode
2With the mixture of cement and combining of wire netting.
Cement and TiO in the preparation process of the present invention
2The most handy 200～400 mesh sieves sieve before the mixing.
The invention provides a kind of is the immobilized TiO of adhesive that skeleton is made into cement and/or macromolecule with the wire netting material
2Constitute TiO
2The photochemical catalyst system.This photochemical catalyst system both can be similar to the such high degree of dispersion of solid granule in whole reaction system, was easy to realize separating of catalyst and reaction system like that can be similar to solid film, not only can satisfy nano-TiO well
2Immobilized requirement, repeatedly scattering and the diffuse reflection effect that takes place on network framework by the multilayer mesh because of incident optical energy again improves the utilization rate to light.
The material that the present invention uses is cheap and easy to get, and technological process in simple and practical, light-catalyzed reaction system satisfy light dissemination and hydromechanical requirement, is a kind of economic, practical, innovation and creation with wide prospects for commercial application and higher commercial value.
Below by embodiment in detail the present invention is described in detail.
Description of drawings
Accompanying drawing 1 is the carried by metal net nano-TiO
2The catalyst pattern.
Accompanying drawing 2 is the immobilized nano-TiO of cement
2Absorption spectrum (making reference) with cement.
Accompanying drawing 3 is the immobilized nano-TiO of cement
2Absorption spectrum (making reference) with MgO.
The specific embodiment
With cleaned stainless steel Φ 0.4mm, 20 orders make its surface passivation modification with the concentrated sulfuric acid, put into lauryl sodium sulfate and soaked 10 minutes, again wire netting is placed roaster, 900 ℃ of roastings cooling naturally in 2 hours in the following 500 ℃ of roastings of air atmosphere 3 hours; Commercially available portland cement sieves through 200 mesh standard sieves, with nano-TiO
2Powder mixes, TiO
2Amount be 20%; Be coated on the wire netting material surface of having handled after this mixture added the certain viscosity of entry furnishing, use the method for blowing to blow the hole that to stop up open; After cement hardens slightly, again at its surface sprinkling nano-TiO several times
2Colloidal sol waits to do the nano-TiO that promptly obtains carried by metal net after consolidating
2Photochemical catalyst is seen accompanying drawing 1.The photochemical catalyst material solid supported above-mentioned wire netting is rolled into multilayered cylindrical, is positioned over promptly to constitute nano-TiO in the photo catalysis reactor
2The photochemical catalyst system.
Make reference with the cement behind the setting and hardening, record the immobilized catalyst absorption spectrum of tested cement and see Fig. 2, make reference with MgO, what record is seen accompanying drawing 3 by the immobilized catalyst absorption spectrum of cement, visible nano-TiO
2UV Absorption below 400 nano wave lengths.
Use above-mentioned stainless (steel) wire catalyst Pyrogentisinic Acid catalytic degradation, the results are shown in Table 1.At no nano-TiO
2Photochemical catalyst and nano-TiO arranged
2Carry out the photocatalytic degradation phenol reactant under the condition of photochemical catalyst, the concentration of surveying phenol with spectroscopic methodology over time must table 2.As seen, at no nano-TiO
2Under the situation of photochemical catalyst, phenol does not carry out photocatalytic degradation reaction, generates light is had the strong polymer that absorbs and carry out poly-reaction, and the concentration that reaction proceeds to 270 minutes phenol does not still descend, and the color of observing reactant liquor deepens gradually.And nano-TiO is being arranged
2Under the condition of photochemical catalyst, though reaction begin still have polymer to generate, but significantly descend when the concentration of reaction phenol when proceeding to 60 minutes is existing, phenol is thoroughly degraded when proceeding to 150 minutes, the color of in experiment, observing reactant liquor by colourless to yellow again to colourless.The activity of such catalysts composition that is further specified this solid support method and provided by table 2 is a nano-TiO
2
The concentration of table 1 phenol over time
| Access times | Reaction time (min) | |||||
| 0 | 30 | 60 | 90 | 120 | 150 | |
| Use for the first time | 100％ | 70％ | 31％ | 19％ | 0％ | |
| Use for the second time | 100％ | 75％ | 40％ | 23％ | 11％ | 0％ |
| After repeatedly using | 100％ | 73％ | 38％ | 21％ | 13％ | 0％ |
The concentration of table 2 phenol over time
| Reaction system | Reaction time (min) | |||||||||
| 0 | 30 | 60 | 90 | 120 | 150 | 180 | 210 | 240 | 270 | |
| No TiO 2Catalyst | 100％ | Form high polymer | ||||||||
| TiO is arranged 2Catalyst | 100％ | 75％ | 40％ | 23％ | 11％ | 0％ | ||||
With cleaned stainless steel net Φ 0.4mm, 20 orders make its surface passivation modification with the concentrated sulfuric acid, put into lauryl sodium sulfate and soaked 10 minutes, again wire netting is placed roaster, 900 ℃ of roastings cooling naturally in 2 hours in the following 500 ℃ of roastings of air atmosphere 3 hours; Commercially available portland cement sieves through 200 mesh standard sieves, with nano-TiO
2Powder mixes, TiO
2Amount be 20%; Be coated on the wire netting material surface of having handled after this mixture added the certain viscosity of entry furnishing, use the method for blowing to blow the hole that to stop up open; After cement hardens slightly, again at its surface sprinkling nano-TiO of platiniferous 0.2% several times
2Colloidal sol waits to do the nano-TiO that promptly obtains carried by metal net after consolidating
2Photochemical catalyst is seen accompanying drawing 1.The photochemical catalyst material solid supported above-mentioned wire netting is rolled into multilayered cylindrical, is positioned over promptly to constitute nano-TiO in the photo catalysis reactor
2The photochemical catalyst system.
Embodiment 3
With cleaned stainless steel net Φ 0.4mm, 20 orders make its surface passivation modification with the concentrated sulfuric acid, put into lauryl sodium sulfate and soaked 10 minutes, again wire netting is placed roaster, 900 ℃ of roastings cooling naturally in 2 hours in the following 500 ℃ of roastings of air atmosphere 3 hours; Commercially available portland cement sieves through 200 mesh standard sieves, with nano-TiO
2Powder and 2% active carbon mix TiO
2Amount be 20%; Be coated on the wire netting material surface of having handled after this mixture added the certain viscosity of entry furnishing, use the method for blowing to blow the hole that to stop up open; After cement hardens slightly, again at its surface sprinkling nano-TiO of platiniferous 0.2% several times
2Colloidal sol waits to do the nano-TiO that promptly obtains carried by metal net after consolidating
2Photochemical catalyst is seen accompanying drawing 1.The photochemical catalyst material solid supported above-mentioned wire netting is rolled into multilayered cylindrical, is positioned over promptly to constitute nano-TiO in the photo catalysis reactor
2The photochemical catalyst system.
Example 2,3 gained catalyst and example 1 catalyst carry out the photocatalytic degradation reaction of phenol, the results are shown in Table 3.
The concentration of table 3 phenol over time
| The catalyst composition | Reaction time (min) | |||||
| 0 | 30 | 60 | 90 | 120 | 150 | |
| Cement, nano-TiO 2 | 100％ | 75％ | 40％ | 23％ | 11％ | 0％ |
| Cement, nano-TiO 2(platinum is carried on the surface) | 100％ | 40％ | 10％ | 0％ | ||
| Cement, nano-TiO 2(platinum is carried on the surface), active carbon | 100％ | 25％ | 0％ | |||
Claims (8)
1. carried by metal net nano-TiO
2Photochemical catalyst is characterized in that this catalyst:
--with Φ 0.05～2mm, 10～200 purpose wire nettings are basic skeleton, and wire netting is selected from a kind of of stainless (steel) wire, galvanized wire mesh, copper mesh, aluminium net;
--be coated with the layer of even nano-TiO at wire netting
2With the mixture of fixative, fixative is cement or polymer binder, and its weight percentage is TiO
25～50%, the fixative surplus;
--mixture coating wraps up one deck nano-TiO outward again
2
2. by the described carried by metal net nano-TiO of claim 1
2Photochemical catalyst is characterized in that: at described TiO
2With adding porous granule in the fixative mixture, described porous granule is active carbon, sand, silica, aluminium oxide, clay, kaolin or molecular sieve, and addition is 0.5～10% weight.
3. by the described carried by metal net nano-TiO of claim 1
2Photochemical catalyst is characterized in that: outermost TiO
2Carry out modification with platinum, palladium, ruthenium, rhodium, strontium, ferric iron, the modifier addition is 0.1～1% weight.
4. by the described carried by metal net nano-TiO of claim 1
2Photochemical catalyst is characterized in that: fixative is portland cement, aluminate cement, phosphate cement.
5. press the described carried by metal net nano-TiO of claim 1 for one kind
2The preparation method of photochemical catalyst is characterized in that preparation process complies with following step and carry out:
(1) with wire netting under air atmosphere 300～900 ℃, roasting 2～10 hours;
(2) with TiO
2Evenly mix the furnishing pulpous state with fixative water or water-ethanol solution, the surface of the wire netting after coating (1) and handling;
(3) with TiO
2Colloidal sol is coated with or is sprayed at the surface of the net after handle (2).
6. by the described carried by metal net nano-TiO of claim 5
2The preparation method of photochemical catalyst is characterized in that: carry out Passivation Treatment with the concentrated sulfuric acid, red fuming nitric acid (RFNA) or chloroazotic acid before the wire netting roasting.
7. by the described carried by metal net nano-TiO of claim 6
2The preparation method of photochemical catalyst is characterized in that: the wire netting after the Passivation Treatment soaks modification with sulfonate surfactant.
8. by the described carried by metal net nano-TiO of claim 5
2The preparation method of photochemical catalyst is characterized in that: cement and TiO
2Sieve with 200～400 mesh sieves before mixing.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98121036A CN1110361C (en) | 1998-12-04 | 1998-12-04 | Nanometer-level TiO2 photocatalyst carried by metal net and its preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98121036A CN1110361C (en) | 1998-12-04 | 1998-12-04 | Nanometer-level TiO2 photocatalyst carried by metal net and its preparation |
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| CN1256170A CN1256170A (en) | 2000-06-14 |
| CN1110361C true CN1110361C (en) | 2003-06-04 |
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| CN98121036A Expired - Fee Related CN1110361C (en) | 1998-12-04 | 1998-12-04 | Nanometer-level TiO2 photocatalyst carried by metal net and its preparation |
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Cited By (1)
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| CN1304115C (en) * | 2005-07-08 | 2007-03-14 | 清华大学 | Method for preparing photocatalyst with high catalytic reduction activity |
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| US5215820A (en) * | 1990-11-30 | 1993-06-01 | Mitsubishi Rayon Co., Ltd. | Metal-electroconductive polymer composite fine particles and method for preparing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5215820A (en) * | 1990-11-30 | 1993-06-01 | Mitsubishi Rayon Co., Ltd. | Metal-electroconductive polymer composite fine particles and method for preparing same |
| CN1186774A (en) * | 1998-01-14 | 1998-07-08 | 中国科学院固体物理研究所 | Large mass TiO2 mesohole solid and preparing method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304115C (en) * | 2005-07-08 | 2007-03-14 | 清华大学 | Method for preparing photocatalyst with high catalytic reduction activity |
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