CN1962036A - A highly effective photocatalytic reactor and method for manufacturing the same - Google Patents
A highly effective photocatalytic reactor and method for manufacturing the same Download PDFInfo
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- CN1962036A CN1962036A CN 200610048743 CN200610048743A CN1962036A CN 1962036 A CN1962036 A CN 1962036A CN 200610048743 CN200610048743 CN 200610048743 CN 200610048743 A CN200610048743 A CN 200610048743A CN 1962036 A CN1962036 A CN 1962036A
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Abstract
The invention relates to a high-effect optical catalyst reactor and relative production, wherein one end of long frame is air inlet, while another end is air outlet; the longitudinal axle of frame has ultraviolet tube fixed by transverse porous plate inside the frame; between the frame and ultraviolet tube there is glass fiber carrier optical catalyst filled; the air outlet or air inlet has fan. The inventive reactor has simple structure and continuous reaction. It first disperse the nanometer titania or doping nanometer titania into the organic or inorganic adhesive and surface activator solution; then emerges the glass fiber carrier into solution; the coated catalyst is dried and baked to remove the adhesive. The invention can avoid preparing titania gel. And the invention has high optical catalysis activity property.
Description
Technical field
The invention belongs to the Pollution Control equipment technical field, be specifically related to be used for handling the photo catalysis reactor and the manufacture method thereof of air volatile contaminant.
Background technology
Removing VOC (VOCs) at present from air generally is to adopt methods such as absorption, absorption, high temperature incineration and catalytic burning.These methods all have certain limitation, all can bring secondary pollution.Photocatalysis technology have can carry out at normal temperatures and pressures, energy consume low, to characteristics such as the degradation efficiency height of pollutant, the multiple pollutants of can degrading simultaneously, therefore this technology will be a kind of very promising environmental improvement means, be particularly suitable for handling VOC and foul gas in the air.
Volatile contaminant in the photoactivation technical finesse air need be equipped with the photo catalysis reactor of photochemical catalyst.Problems such as present existing photo catalysis reactor structure is different, and some patented technology schemes or like product adopt active carbon cloth, corrugated paper, aluminium sheet etc. to make the photochemical catalyst of catalyst carrier, exist light transmission poor, and sensitive surface is little, and purification efficiency is low.Loaded optic catalyst can keep the adsorption capacity of photochemical catalyst to reactant on glass fibre, effectively reduces the absorption of carrier to light, thereby greatly improves the photocatalysis effect.
Summary of the invention
The object of the present invention is to provide a kind of highly effective photocatalytic reactor and its manufacture method of handling volatile contaminant in the air, this reactor adopts the titanium dioxide optical catalyst of glass fiber loaded titanium dioxide optical catalyst or glass fiber loaded doping.
The structure of product of the present invention is: an end of an elongate housing is that air inlet, the other end are the gas outlet, housing longitudinal axis position is provided with a ultraviolet lamp tube, this ultraviolet lamp tube is fixed by the horizontal porous plate that is located in the housing, housing and ultraviolet lamp tube are asked the titanium dioxide optical catalyst of glass fiber loaded titanium dioxide optical catalyst of filling or glass fiber loaded doping, and the gas outlet end or the air inlet end of housing are provided with blower fan.Said blower fan preferably is located at the gas outlet end of housing.Porous plate in the housing is preferably two, is located at the housing two ends respectively.Inner walls preferably is provided with reflector layer, and reflector layer can be to be close to aluminium foil or the tinfoil paper that inner walls is lined with.Housing can be made by materials such as lucite, plastics, stainless steels.Distance between fluorescent tube and the inner walls can be 0.5-10 centimetre, and is comparatively suitable with 2-5 centimetre when adopting 20 watts uviol lamp.Increase the intensity of illumination of uviol lamp, then can suitably increase filling thickness.Packed density is with 0.1-0.5g/cm
3Be advisable.
Reactor of the present invention is mainly used in photocatalysis and eliminates sealing and semiclosed human living space (as room, toilet, meeting room, ward and public place of entertainment etc.), and VOC in workshop and the plant and foul gas.Reactor both can use separately, also can use by a plurality of serial or parallel connections.
The manufacture method of product of the present invention is: the glass fiber loaded titanium dioxide optical catalyst of product filling or the titanium dioxide optical catalyst of glass fiber loaded doping, preparation according to the following steps:
(1) nano titanium oxide or the nano titanium oxide behind doping metals are put into the organic solvent that contains organic or inorganic binding agent and surfactant, allow nano titanium oxide or mix after nano titanium oxide be uniformly dispersed, the weight ratio of the nano titanium oxide after organic solvent and nano titanium oxide or the doping is 20～30: 1, the weight ratio of the nano titanium oxide after binding agent and nano titanium oxide or the doping is 0.5～2: 1, the weight ratio of the nano titanium oxide after surfactant and nano titanium oxide or the doping is 0.01～0.05: 1, and the weight ratio that doping metals accounts for titanium dioxide is 0.1～2%.The doping metals of nano titanium oxide can be that noble metal, transition metal or noble metal are crossed any combination with transition metal.Organic solvent can be alcohols, ketone compounds such as methyl alcohol, ethanol, propyl alcohol, acetone etc., wherein preferred absolute ethyl alcohol.Binding agent can be polyethylene glycol, triethanolamine, polyvinyl alcohol, carboxymethyl cellulose, silica, ethyl orthosilicate, boehmite etc.Surfactant can be Tween-20, Tween-80, Arlacel-20, Arlacel-80 etc.Said allow nano titanium oxide or mix after the finely dispersed technological means of nano titanium oxide be prior art, wherein preferably adopt ultrasonic concussion 10～35 minutes.
(2) thorough oil removing is cleaned and oven dry after glass fiber impregnated in the mixed liquor that makes by above-mentioned steps (1).Preferably allow the weight ratio of glass fibre and mixed liquor be 0.5～1.2: 1.
(3) glass fibre after will fully flooding evenly takes out in 60 ℃～100 ℃ dryings, carries out roasting in 300 ℃～600 ℃ subsequently, obtains glass fiber loaded photochemical catalyst after cooling off naturally.
More than said titanium dioxide can be that average grain diameter is 1-80nm, crystal formation is 100% anatase or the anatase titanium dioxide that contains the 0-20% rutile.In the glass fiber loaded optic catalyst that makes by the inventive method, titanium dioxide or mix after titanium dioxide account for 0.1～20% of glass fiber loaded optic catalyst gross weight.
Beneficial effect of the present invention: product structure is simple, can react continuously, and have stronger anti-deactivation, the catalyst difficult drop-off that manufacture method is easy, glass fiber loaded, photocatalytic activity height.
Description of drawings
Fig. 1 is the structural representation of product embodiments.
Structural representation when Fig. 2 uses for the series connection of product embodiments photo catalysis reactor.
The specific embodiment
Product embodiments: see Fig. 1.One end of lucite round barrel shape housing 1 is the air inlet of band dust cover, and the other end is the gas outlet, and the gas outlet end is provided with blower fan 7.20 watts of ultraviolet lamp tubes 4 are fixed by being located in the housing two transverse circular porous plates 2 at two ends respectively.The inwall of being close to housing 1 is lined with the aluminium foil reflector layer.Be filled between ultraviolet lamp tube 4 and the housing 1 is the nano titanium dioxide photocatalyst 3 that glass fiber loaded reactive metal mixes.The filling thickness of catalyst 3, promptly the distance between fluorescent tube 4 and the reflector layer is 4 centimetres, packed density is 0.3/cm
35 is quartzy containment vessels of fluorescent tube 4 among the figure, the 6th, and outlet.
During installation; elder generation packs ultraviolet lamp tube 4 in the quartzy containment vessel 5; containment vessel 5 one ends put circular porous plate 2; put into housing 1; again catalyst 3 looselys are inserted; put another circular porous plate 2 after filling up again, allow uviol lamp be fixed in the housing 1, again the dust cover of air inlet and the blower fan 7 of gas outlet are loaded onto.The big I of gas flow rate detects with flowmeter at the gas outlet end, regulates the rotating speed of blower fan and controls.This photo catalysis reactor both can use separately, also can connect or/and in parallel the use.Can decide according to concrete processing object.Structural representation when Fig. 2 is three reactor series connection uses.
If catalyst 3 adopts glass fiber loaded 5% (0.75%Pt-TiO
2) photochemical catalyst, three identical reactor series connection, fill 120g catalyst (actual titanium dioxide 6g, metal platinum 0.045g), light source adopts the uviol lamp of 20 watts (dominant wavelength is 254nm), air mass flow is 1.2L/min, and relative humidity is 57%, and the experimental result of handling the typical air pollutant with this photo catalysis reactor is as shown in table 1.(24 hours) do not observe catalysqt deactivation in the course of reaction.
Table 1 photo catalysis reactor is handled the experimental result of air pollutants
[glass fiber loaded 5% (0.75%Pt-TiO
2)]
| Pollutant | Inlet gas concentration (mg/m 3) | The concentration of giving vent to anger (mg/m 3) | Clearance (%) |
| Benzene | 110 | 5.50 | 95.0 |
| Toluene | 105 | 3.57 | 96.6 |
| Dimethylbenzene | 101 | 3.23 | 96.8 |
| Pyridine | 120 | 4.44 | 96.3 |
| Acetate | 117 | 6.79 | 94.2 |
| Tri-methyl indole (scatol) | 80 | 1.28 | 98.4 |
| Ammonia | 124 | 3.60 | 97.1 |
If catalyst 3 adopts glass fiber loaded 5% (0.5%Ru-TiO
2) photochemical catalyst, all the other conditions are the same, the experimental result of handling the typical air pollutant with this photo catalysis reactor is as shown in table 2: (24 hours) do not observe catalysqt deactivation in the course of reaction.
Table 2 photo catalysis reactor is handled the experimental result of air pollutants
[glass fiber loaded 5% (0.5%Ru-TiO
2)]
| Pollutant | Inlet gas concentration (mg/m 3 | The concentration of giving vent to anger (mg/m 3 | Clearance (%) |
| Benzene | 114 | 6.50 | 94.3 |
| Pyridine | 110 | 6.38 | 94.2 |
| Acetate | 124 | 9.42 | 92.4 |
| Tri-methyl indole (scatol) | 84 | 3.02 | 96.4 |
| Ammonia | 114 | 5.59 | 95.1 |
Method embodiment 1: prepare glass fiber loaded 5%TiO
2Photochemical catalyst.
Earlier glass fibre is cleaned the back dry for standby with hydrochloric acid, NaOH, distilled water, acetone successively.5mL triethanolamine, 0.2mL Arlacel-80 are dissolved in the 75mL absolute ethyl alcohol, stir, add 5.0g nano titanium oxide (average grain diameter 25nm), ultrasonic dispersion 30min, the glass fibre primary that takes by weighing 100g cleaning back dry for standby joins in the ultrasonic scattered liquid that contains titanium dioxide, dipping, coating stir.With the glass fibre that flooded catalyst 100 ℃ of dryings 5 hours in baking oven, roasting in Muffle furnace afterwards: under the bubbling air condition, from room temperature, rise to 200 ℃ with 5 ℃/min, kept 2 hours, rise to 550 ℃ with 10 ℃/min again, kept 5 hours, obtain the photochemical catalyst of glass fiber loaded 5% titanium dioxide naturally after the cooling.
Method embodiment 2: prepare glass fiber loaded 5% (0.75%Pt-TiO
2) photochemical catalyst.
This example is the Pt of mix earlier 0.75% (weight ratio) in nano titanium oxide, the titanium dioxide of the Pt that will mix afterwards by 5% mass loading on glass fibre.With 20.0g TiO
2(average grain diameter 25nm) and 1.60ml contain the H that Pt is 94.9mg/ml
2PtCl
6Solution and 14.0g water mixing and stirring, ultrasonic dispersion 30min mixing, oven dry is ground into powder.With the 30mL/min hydrogen flow rate,, obtain containing 0.75%Pt-TiO at 350 ℃ of following hydrogen reduction 180min
2Catalyst.Subsequent step is undertaken by example 1 described program, and difference is that the catalyst 5.0g that gets doping 0.75%Pt replaces pure nano titanium oxide, is prepared into glass fiber loaded 5% (0.75%Pt-TiO
2) photochemical catalyst.
Method embodiment 3: prepare glass fiber loaded 5% (0.5%Ru-TiO
2) photochemical catalyst.
This example is 0.5% the Ru of mixing in nano titanium oxide earlier, the titanium dioxide of the Ru that will mix afterwards by 5% mass loading on glass fibre.With 20.0 gram TiO
2(average grain diameter 25nm) and 1.86mlRuCl
3Solution (Ru content is 54mg/ml) and 14.0 gram water mixing and stirring, ultrasonic dispersion 30min, oven dry, be ground into powder, with hydrogen reduction 180min under 350 ℃, obtain containing the catalyst of 0.5% metal Ru, with the 30mL/min hydrogen flow rate, at 350 ℃ of following hydrogen reduction 180min, obtain containing 0.5%Ru-TiO
2Catalyst.Subsequent step is undertaken by example 1 described program, and difference is that the catalyst 5.0g that gets doping 0.5%Ru replaces pure nano titanium oxide, is prepared into glass fiber loaded 5% (0.5%Ru-TiO
2) photochemical catalyst.
Method embodiment 4: prepare glass fiber loaded 5% (0.5%Ru-TiO
2) photochemical catalyst.
Catalyst component of this example load and content are identical with embodiment 3, and the reducing agent of employing is a hydrazine hydrate.With 20.0gTiO
2(average grain diameter 25nm) and 1.86mL RuCl
3Solution (Ru content is 54mg/ml) and 12.0mL water mixing and stirring, ultrasonic dispersion 30min, adding 2mL concentration is 20% hydrazine hydrate (transferring to pH=12.00 with NaOH in advance), stirs, oven dry is ground into powder.Subsequent step is undertaken by example 1 described program, and difference is that the catalyst 5.0g that gets doping 0.5%Ru replaces pure nano titanium oxide, is prepared into glass fiber loaded 5% (0.75%Pt-TiO
2) photochemical catalyst.
Method embodiment 5: being averaged particle diameter is 50nm, the anatase titanium dioxide that contains 15% rutile is put into the organic solvent-acetone that contains binding agent triethanolamine, surfactant Arlacel-80, ultrasonic concussion allowed titanium dioxide be uniformly dispersed in 2O minute, made mixed liquor.The weight ratio of acetone and titanium dioxide is 21: 1, and the weight ratio of triethanolamine and titanium dioxide is 1.8: 1, and the weight ratio of Arlacel-80 and titanium dioxide is 0.015: 1.Will be in the glass fiber impregnated mixed liquor that is making after thorough oil removing is cleaned and dried, the weight ratio of glass fibre and mixed liquor is 1: 1.The abundant dipping glass fibre after is evenly taken out in 80 ℃ of dryings, carry out roasting in 600 ℃ subsequently, obtain glass fiber loaded photochemical catalyst after cooling off naturally.
Method embodiment 6: being averaged particle diameter is 70nm, crystal formation is that the titanium dioxide of 100% anatase is put into the organic solvent absolute ethyl alcohol that contains binding agent carboxymethyl cellulose, surfactant Tween-80, ultrasonic concussion allowed titanium dioxide be uniformly dispersed in 35 minutes, made mixed liquor.The weight ratio of absolute ethyl alcohol and titanium dioxide is 30: 1, and the weight ratio of carboxymethyl cellulose and titanium dioxide is 0.7: 1, and the weight ratio of Tween-80 and titanium dioxide is 0.045: 1.Will through thorough oil removing clean and oven dry after glass fiber impregnated in the mixed liquor that makes by above-mentioned steps, the weight ratio of glass fibre and mixed liquor is 0.6: 1.The abundant dipping glass fibre after is evenly taken out in 60 ℃ of dryings, carry out roasting in 300 ℃ subsequently, obtain glass fiber loaded photochemical catalyst after cooling off naturally.
Method embodiment 7: the nano titanium oxide of getting mixed 0.2% cerium and 1% silver medal (weight ratio), average grain diameter and be 5nm is put into the propyl alcohol that contains ethyl orthosilicate and Tween-20, ultrasonic concussion 35 minutes, allow the nano titanium oxide after mixing be uniformly dispersed, make mixed liquor.The weight ratio of the nano titanium oxide after propyl alcohol and the doping is 25: 1, and the weight ratio of the nano titanium oxide after ethyl orthosilicate and the doping is 1.5: 1, and the weight ratio of the nano titanium oxide after Tween-20 and the doping is 0.03: 1.Glass fibre (its displaing micro picture is seen Fig. 1) is cleaned the back oven dry with hydrochloric acid, NaOH, distilled water, acetone successively, put into the above-mentioned mixed liquor that makes, the weight ratio of glass fibre and mixed liquor is 1.2: 1.The abundant dipping glass fibre after is evenly taken out in 70 ℃ of dryings, carry out roasting in 400 ℃ subsequently, obtain glass fiber loaded photochemical catalyst after cooling off naturally.
Above embodiment only is described further invention, and scope of the present invention is not subjected to the limitation of illustrated embodiment.
Claims (10)
1, a kind of highly effective photocatalytic reactor, it is characterized in that: an end of an elongate housing is that air inlet, the other end are the gas outlet, housing longitudinal axis position is provided with a ultraviolet lamp tube, this ultraviolet lamp tube is fixed by the horizontal porous plate that is located in the housing, the titanium dioxide optical catalyst that the glass fiber loaded reactive metal of filling mixes between housing and ultraviolet lamp tube, the gas outlet end or the air inlet end of housing are provided with blower fan.
2,, it is characterized in that blower fan is located at the gas outlet end of housing as the said reactor of claim 1.
3, as the said reactor of claim 1, it is characterized in that the porous plate in the housing is two, be located at the housing two ends respectively.
4, as the said reactor of claim 1, it is characterized in that: inner walls is provided with reflector layer, and reflector layer is to be close to aluminium foil or the tinfoil paper that inner walls is lined with.
5,, it is characterized in that the distance between fluorescent tube and the inner walls is 0.5-10 centimetre as the said reactor of claim 1.
6,, it is characterized in that housing is a cylindrical shape as the said reactor of claim 1.
7,, it is characterized in that the air inlet band dust cover of housing as the said reactor of claim 1.
8, as the manufacture method of the said reactor of claim 1, it is characterized in that: the glass fiber loaded titanium dioxide optical catalyst of reactor filling or the titanium dioxide optical catalyst of glass fiber loaded doping prepare according to the following steps:
(1) nano titanium oxide or the nano titanium oxide behind doping metals are put into the organic solvent that contains organic or inorganic binding agent and surfactant, allow nano titanium oxide or mix after nano titanium oxide be uniformly dispersed, the weight ratio of the nano titanium oxide after organic solvent and nano titanium oxide or the doping is 20～30: 1, the weight ratio of the nano titanium oxide after binding agent and nano titanium oxide or the doping is 0.5～2: 1, the weight ratio of the nano titanium oxide after surfactant and nano titanium oxide or the doping is 0.01～0.05: 1, and the weight ratio that doping metals accounts for titanium dioxide is 0.1～2%;
(2) thorough oil removing is cleaned and oven dry after glass fiber impregnated in the mixed liquor that makes by above-mentioned steps (1).Preferably allow the weight ratio of glass fibre and mixed liquor be 0.5～1.2: 1;
(3) glass fibre after will fully flooding evenly takes out in 60 ℃～100 ℃ dryings, carries out roasting in 300 ℃～600 ℃ subsequently, obtains glass fiber loaded photochemical catalyst after cooling off naturally.
9, as the said manufacture method of claim 8, the doping metals that it is characterized in that nano titanium oxide is that noble metal, transition metal or noble metal are crossed any combination with transition metal.
10,, it is characterized in that organic solvent is an absolute ethyl alcohol as the said manufacture method of claim 8.
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| CN102060349A (en) * | 2010-10-29 | 2011-05-18 | 山东大学 | Vertical continuous photocatalysis reaction device and application thereof |
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| CN111167306A (en) * | 2020-01-13 | 2020-05-19 | 福州大学 | Method for degrading inorganic malodorous pollutant ammonia gas by ultraviolet light illumination |
| CN111853714A (en) * | 2020-07-07 | 2020-10-30 | 北京科技大学 | Photocatalytic optical fiber lamp and manufacturing method thereof |
| CN112090273A (en) * | 2020-08-28 | 2020-12-18 | 中北大学 | Photocatalyst-loaded filler and its high-gravity NO removalxApparatus and process of |
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