CN101757902A - Method for preparing composite photocatalyst containing activated carbon coating - Google Patents
Method for preparing composite photocatalyst containing activated carbon coating Download PDFInfo
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Abstract
The invention discloses a method for preparing composite photocatalyst containing activated carbon coating. In the method, activated carbon as coating is attached on foam material matrix, so that activated carbon coating material is formed, the activated carbon coating material is used as carrier to carry titanium dioxide, wherein the titanium dioxide as an active component is 1 percent to 10 percent by weight, the activated carbon coating is 4 percent to 15 percent by weight, and the balance is the foam material matrix. Since the method uses the activated carbon coating as photocatalyst carrier, the dispersibility of the titanium dioxide as an active component can be effectively enhanced, the defects of the traditional activated carbon material, including loose structure and low strength, are overcome, the transmission of light in a system is improved, the process of transferring pollutant to the catalyst surface is improved, and moreover, the service life of activated carbon can be greatly prolonged.
Description
Technical field
The present invention relates to a kind of with semiconductor titanium dioxide (TiO
2) be the preparation method of the photochemical catalyst of active component, this catalyst is specially adapted to the purified treatment to room air.
Background technology
In recent years, along with a large amount of uses of interior architecture ornament materials, family expenses chemical substance, room air pollution more and more is subject to people's attention.Investigation shows that the organic concentration of room air is higher than outdoor, even is higher than the industrial area.From room air, identify hundreds of kind organic substance at present, wherein had plenty of carcinogenic substance.Used coating, bonding agent, paint, glued board, flooring laminate, wallpaper etc. all can discharge VOC in room, the office in air, thereby cause indoor pollution.Result of study to indoor main gas pollutant formaldehyde, toluene etc. shows titanium dioxide (TiO
2) photocatalysis oxidation technique showing unique advantage aspect this class hardly degraded organic substance pollutant handling.But, traditional TiO
2Photocatalysis technology exists that power consumption is big, catalyst recovery is difficult and problem such as efficient is low, so limited its industrialized application.Therefore, efficient TiO
2The developmental research of photochemical catalyst has been one of domestic and international most active research field.
The load of catalyst is to solve the effective way that the suspended phase catalyst separation reclaims, and can overcome characteristics such as suspended phase poor catalyst stability and easy poisoning.Load TiO
2In the process, the structures shape of carrier light in system transmittance process and material Transfer to the mass transport process of catalyst surface, also just determined the design of photo catalysis reactor and the efficient of photocatalytic system.A large amount of active carbons of discovering can be enriched to catalyst surface with the target contaminant in the reaction system, at TiO
2The surface produces a substrate enrichment environment, thereby has improved degradation rate, and simultaneously, by diffusion, the organic matter that is adsorbed is to TiO
2Surface migration, TiO
2The organic matter of degrading activity carbon surface makes carrier realize in-situ regeneration again, and this synergy further improves the photocatalytic activity of composite catalyzing.Therefore, with TiO
2Be fixed on the active carbon, both can have improved the efficient of catalyst, can solve the problem that catalyst separation reclaims again.Publication number is that the Chinese patent application " a kind of preparation method of absorbent charcoal loading titanium dioxide photocatalyst " of CN101244383A is that 50～100 purpose active carbons are carrier loaded TiO with particle diameter
2The preparation photochemical catalyst is used for degradable organic pollutant.Because this invention is employed is active carbon after the commercial active carbon fragmentation, and particle diameter is too little, and preparation process causes TiO easily
2Particle aggregation, and separation and removal process relative complex separate after the use and also cause material unaccounted-for (MUF) easily.Publication number is CN
The Chinese patent application of 1695797A " preparation method of absorbent charcoal loading titanium dioxide photocatalyst " adopts chemical vapour deposition technique with TiO
2Loading on particle diameter is on 40～60 purpose absorbent charcoal carriers, is used for photocatalysis degradation organic contaminant.The activated carbon particle size that this invention is used is too little, is applied in the packed bed, has the big and light skewness of bed pressure drop; Be applied in the suspension bed, wearing and tearing and efflorescence are difficult to be applied to gas phase easily.Publication number is that the Chinese patent application " a kind of titanium dioxide/active carbon fiber photocatalyst and preparation method thereof and the application in air cleaning " of CN 1803291A is carrier loaded TiO with NACF
2Make loaded photocatalyst, because fiber is nonrigid material, easy deformation and fragmentation in system also cause the TiO of load easily
2Come off, this has all influenced it to a certain extent and has amplified application.
Ceramic material has mechanical strength height, anti-vibration, characteristics such as high temperature resistant, corrosion-resistant, pottery and active carbon is combined can make this composite have the overall merit of the two.Publication number is that the United States Patent (USP) " active carbon and preparation method thereof " of US 4082661 is that the moulding porous ceramics of 1000～70000 dusts is the carrier impregnation resin with pore-size distribution, is used for highly purified filtration art behind the carbonization-activation.It is too small that this invents aperture, the grand hole of employed moulding porous ceramics, the resin of dipping is littler through the aperture, grand hole that obtains behind the carbonization-activation in the hole, increased the absorption resistance of the inner active carbon of ceramic-absorbent charcoal body, hindered the mass transport process between the active carbon of fluid media (medium) and ceramic-absorbent charcoal body inside, make the active carbon of material internal be not fully utilized, be not suitable for carrier of photocatalyst.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiency of prior art, a kind of preparation method who contains the activated carbon coating composite photocatalyst is provided, it with the activated carbon coating material as carrier of photocatalyst, can effectively improve the dispersed of titanium dioxide active component and overcome existing absorbent charcoal material short texture, the shortcoming that intensity is low is improved transmission and the pollutant mass transport process that be delivered to catalyst surface of light in system.
For solving the problems of the technologies described above, a kind of preparation method who contains the activated carbon coating composite photocatalyst of the present invention be with active carbon as coating attached on the foamed material matrix, form the activated carbon coating material, and be carrier loaded titanium dioxide with this activated carbon coating material, wherein the percentage by weight of each component is: the titanium dioxide active component is 1～10%, activated carbon coating is 4～15%, and all the other are the foamed material matrix.
Above-mentioned a kind of preparation method who contains the activated carbon coating composite photocatalyst, when being carrier loaded titanium dioxide with described activated carbon coating material, adopt infusion process that TiO 2 sol is supported on described activated carbon coating material support, obtain through high-temperature calcination, preparation process is as follows:
1) the titanium alkoxide is dissolved in the alcohol under vigorous stirring, and adds a certain amount of inhibitor and surfactant, slowly drip the mixed liquor of water, alcohol, acid, continue to stir; The volume ratio of titanium alkoxide and inhibitor, alcohol, water is 6～8: 1: 16～25: 0.75～1.5, and the addition of surfactant is 1～3% of a TiO 2 sol gross weight, mixes, and obtains TiO even, stable transparent
2Colloidal sol;
2) described activated carbon coating material support is dipped in 2～4h in the TiO 2 sol, takes out and be placed on gel ageing 12～24h in the closed container, put into drying box dry 2～4h under 80～110 ℃ of temperature conditions again; Dried carrier is placed in the resistance furnace under oxygen-free environment, rises to 450～650 ℃, insulation 40～90min from room temperature; Cool to room temperature afterwards with the furnace.
Above-mentioned a kind of preparation method who contains the activated carbon coating composite photocatalyst, used described titanium alkoxide is a butyl titanate when preparing described TiO 2 sol; Described alcohol is one or more the mixture in ethanol, isopropyl alcohol, the n-butanol; Described acid is one or more the mixture in nitric acid, sulfuric acid, the hydrochloric acid; Described inhibitor is a kind of in acetylacetone,2,4-pentanedione, glacial acetic acid, the diethanol amine; Described surfactant is one or more the mixture in polyethylene glycol, polyvinyl alcohol, the NPE.
Above-mentioned a kind of preparation method who contains the activated carbon coating composite photocatalyst, prepared attached to the described activated carbon coating on the foamed material by thermosetting resin, adopt thermosetting resin that impregnation technology will contain solvent to be coated in the surfaces externally and internally of foamed material, described thermosetting resin is as carbon precursor process curing process, charring process, activating process and clean process, obtain attached to the activated carbon coating on the foamed ceramics, described activated carbon coating is 5～20% of a described activated carbon coating material gross mass, coating layer thickness is 0.1～1mm, and the surface area of activated carbon coating is 800～1400m
2/ g, preparation technology is as follows:
1) impregnation technology: with the foamed material matrix after ultrasonic cleaning, drying is 4～8 hours under 105 ± 5 ℃ of conditions, put into the container that has chuck and thermosetting resin is housed, in maceration extract, flooded 4～16 hours, flooding has the warm water circulation in the chuck of used container, the temperature of warm water is 20～70 ℃; Take out being impregnated with in the calm device of foamed material matrix of thermosetting resin, remove unnecessary thermosetting resin by air scavenging or centrifuge;
2) curing process: will be impregnated with the foamed material matrix of thermosetting resin, at room temperature place 6～12 hours after, put into baking oven and solidify, 70 ℃ are played temperature, per minute heats up 1～4 ℃, is incubated 1～5 hour under 150 ℃ of temperature;
3) charring process: will heat up in oxygen-free environment through the foamed material matrix that curing process is handled, 150 ℃ are played temperature, and per minute heats up 2～10 ℃, carry out charing and handled cool to room temperature in oxygen-free environment 30-120 minute under 600～1000 ℃ of temperature;
4) physically activated technology: will in oxygen-free environment, heat up through foam-raw material of wood-charcoal material that charring process is handled, 150 ℃ are played temperature, per minute heats up 2～10 ℃, under 600～1000 ℃ of temperature, with supersaturation water steam or carbon dioxide is activated media, activation processing 30～120 minutes, cool to room temperature in oxygen-free environment;
5) chemical activation technology: will in potassium hydroxide (KOH) or NaOH (NaOH) saturated solution, flood 4～24 hours through foam-raw material of wood-charcoal material that charring process is handled, in baking oven, dried 2～12 hours under 120 ℃ of temperature conditions, in oxygen-free environment, heat up then, 150 ℃ are played temperature, per minute heats up 2～10 ℃, under 600～1000 ℃ of temperature, handled 10～120 minutes cool to room temperature in oxygen-free environment;
6) cleaning: the activated carbon coating composite that will handle through activating process is 5～20% hydrochloric acid (HCl) solution pickling 4～12 hours with mass concentration, washes with water to neutrality again.
Above-mentioned a kind of preparation method who contains the activated carbon coating composite photocatalyst, described foamed material matrix adopts a kind of in foamed ceramics or the foam metal.
Above-mentioned a kind of preparation method who contains the activated carbon coating composite photocatalyst, described foamed material matrix is a foamed ceramics, and its porosity is 50～90%, and its main aperture is made of the 3 D pore canal of diameter by 1mm～10mm random distribution.
Above-mentioned a kind of preparation method who contains the activated carbon coating composite photocatalyst, described thermosetting resin is a kind of of phenolic resins, epoxy resin, unsaturated polyester (UP), acrylic resin.
Above-mentioned a kind of preparation method who contains the activated carbon coating composite photocatalyst, described thermosetting resin is a phenolic resins, comprise unmodified phenolic resins and phenol-formaldehyde resin modified, described phenol-formaldehyde resin modified is one or more the mixture in melamine phenol-formaldehyde resin modified, aniline phenol-formaldehyde resin modified, epoxy modified phenolic resin, cashew nut shell oil or modified by cardanol phenolic resins, polyvinyl alcohol modification phenolic resins, the asphalt modification phenolic resins.
Above-mentioned a kind of preparation method who contains the activated carbon coating composite photocatalyst, solvent for use is one or more the mixture in methyl alcohol, ethanol, butanols, toluene, dimethylbenzene, the gasoline in the described thermosetting resin that contains solvent.
Above-mentioned a kind of preparation method who contains the activated carbon coating composite photocatalyst, described oxygen-free environment is by inert gas, CO
2Or N
2In one or more mix the back and constitute.
The present invention compared with prior art, has following advantage and effect owing to adopted technique scheme:
1, active carbon higher specific surface area and abundant pore structure can improve TiO
2Dispersiveness on carrier, and and TiO
2Have good concerted catalysis effect, improved TiO
2Catalytic efficiency, thereby can reduce TiO significantly
2Use amount.In addition, the TiO that makes of the present invention
2Average grain diameter is in the nanoscale scope, and average particle size range is 10～50nm, the even size distribution of particle diameter.
2, the porosity of foamed ceramics is 50～90%, its main aperture is made of the 3 D pore canal of diameter by 1mm～10mm random distribution, the pore structure that reaches the active carbon on surface in its hole is made of macropore, mesopore and micropore, so just can fully satisfy the mass transfer requirement of material Transfer, effectively bring into play the function of absorbent charcoal material to catalyst surface.The 3 D stereo network skeleton that foamed ceramics is intrinsic, the mutual air hole structure that connects, duct direction in the activated carbon coating composite of preparation also is to distribute for three-dimensional random, can improve the mass transfer of the gentle liquid phase of transmission of light in the photochemical catalytic oxidation process, to reduce the time of photocatalysis oxidation reaction, improve the efficient of Treatment by Photocatalysis Oxidation.
3, the foamed ceramics skeleton has greatly improved the intensity of active carbon, has avoided wearing and tearing and the breakable shortcoming of active carbon as carrier, has prolonged active carbon service life significantly.
4, the activated carbon coating material can be made different shape, no size restrictions as required.
The specific embodiment
The preparation method that embodiment 1 contains the activated carbon coating composite photocatalyst comprises the steps:
1, the preparation of activated carbon coating material: be 75% porous foam ceramic plate ultrasonic cleaning 20min with porosity, after 110 ℃ of temperature conditions are dried 4 hours down, put into and have chuck and the container that solid content is 70% liquid phenolic resin (solvent is an ethanol) is housed, the porous foam ceramic plate was flooded in maceration extract 12 hours; Dipping is 35 ℃ with the temperature of recirculated water in the container chuck.The porous foam ceramic plate that is impregnated with phenolic resins is taken out in container, the unnecessary resin of centrifugal removal under the rotating speed of 1500r/min, after at room temperature placing 12 hours, put into baking oven and be cured processing, 70 ℃ are played temperature, heating rate with 3 ℃/min rises to 150 ℃ of temperature, is incubated 2 hours.With the ceramic-resin material that is cured in nitrogen environment 150 ℃ play temperature, rise to 850 ℃ with the heating rate of 8 ℃/min and carry out charing and handled 80 minutes, in nitrogen environment, be cooled to room temperature.With 150 ℃ the temperature in nitrogen environment of the ceramic-resin carbon composite after the charing processing, heating rate with 10 ℃/min rises to 900 ℃, feed the supersaturation water steam and carried out activation processing 60 minutes, the steam total amount is the twice of resin-based charcoal amount, is cooled to room temperature in nitrogen environment.With mass concentration is the material that 10% HCl solution pickling obtains, and is washed to neutrality, and it is 7.46% ceramic-absorbent charcoal composite that drying obtains active carbon content, and wherein the specific area of active carbon is 1350m
2/ g, iodine sorption value are 1682.19mg/g.
2, TiO
2The preparation of colloidal sol: in there-necked flask, add 150ml absolute ethyl alcohol and 9.5ml acetylacetone,2,4-pentanedione, under vigorous stirring, drip the 75ml butyl titanate.Drip and finish, continue to stir 30min, obtain the yellow solution of homogeneous transparent, be designated as A liquid; Take by weighing weight content and account for TiO
2The polyethylene glycol of colloidal sol gross weight 1.5% dissolves in the 9.9ml distilled water, measures 1ml HNO simultaneously
3, the 75ml absolute ethyl alcohol and stirring makes it to mix, and is designated as B liquid; With the speed of buret with 0.2ml/s the B drop is added in the A liquid under the vigorous stirring, regulation system pH value to 2.5 continues to stir 2h, obtains the faint yellow TiO of homogeneous transparent at last
2Colloidal sol, it is standby to leave standstill 24h.
3, TiO
2Colloidal sol is load on carrier: will be dipped in TiO through cleaning and dry finished product ceramic-absorbent charcoal coating composite material
22h in the colloidal sol slowly lifts taking-up then, is put in gel ageing 24h in the closed container, puts into drying box dry 2h under 80 ℃ of temperature conditions again; Dried carrier is placed in the chamber type electric resistance furnace under nitrogen environment, is warming up to 250 ℃ from room temperature, insulation 30min with the heating rate of 10 ℃/min; Be warming up to 500 ℃ with same heating rate again, insulation 60min; Cool to room temperature afterwards with the furnace.Above-mentioned dipping-calcination process is repeated 2 times, obtain TiO
2Load capacity is 3.16% composite photo-catalyst.
Utilize this catalyst Treatment by Photocatalysis Oxidation indoor formaldehyde gas, 25 ℃ of reaction temperatures, reaction time 120min, relative humidity is 70%, initial concentration of formaldehyde is 2mg/m
3Condition under, the formaldehyde clearance can reach 94.3%.
The preparation method that embodiment 2 contains the activated carbon coating composite photocatalyst comprises the steps:
1, the preparation of ceramic-absorbent charcoal coating composite material: be 55% porous foam ceramic plate ultrasonic cleaning 20min with porosity, put into the container that has chuck and excessive thermosetting phenolic resin is housed in 110 ℃ of oven dry after 4 hours, the porous foam ceramic plate was flooded in maceration extract 12 hours; Dipping is 45 ℃ with the temperature of recirculated water in the container chuck.The porous foam ceramic plate that is impregnated with phenolic resins is taken out in container, the unnecessary resin of centrifugal removal under the rotating speed of 1500r/min, at room temperature place 12 hours after, put into baking oven and be cured processing, 70 ℃ are played temperature, rise to 150 ℃ of temperature with the heating rate of 4 ℃/min, are incubated 2 hours.With the ceramic-resin material that is cured in nitrogen environment 150 ℃ play temperature, rise to 850 ℃ with the heating rate of 10 ℃/min and carry out charing and handled 80 minutes, in nitrogen environment, be cooled to room temperature.With 150 ℃ the temperature in nitrogen environment of the ceramic-resin carbon composite after the charing processing, heating rate with 10 ℃/min rises to 900 ℃, feed the supersaturation water steam and carried out activation processing 60 minutes, the steam total amount is the twice of resin-based charcoal amount, is cooled to room temperature in nitrogen environment.With mass concentration is the material that 10% HCl solution pickling obtains, and is washed to neutrality, and it is 4.56% ceramic-absorbent charcoal composite that drying obtains active carbon content, and wherein the specific area of active carbon is 1100m
2/ g, iodine sorption value are 1432.24mg/g.
2, TiO
2The preparation of colloidal sol: in there-necked flask, add 30ml absolute ethyl alcohol, 6ml HNO
3With the 9ml acetylacetone,2,4-pentanedione, under vigorous stirring, drip the 60ml butyl titanate, drip and finish, continue to stir the yellow solution that 30min obtains homogeneous transparent, be designated as A liquid; Take by weighing weight content and account for TiO
2The polyethylene glycol of colloidal sol gross weight 1% (molecular weight: 20000) dissolve in the 12ml distilled water, measure the 60ml pentamethylene simultaneously and add a certain amount of NPE emulsifying agent, with above two kinds of solution mixing and to wherein adding isopropyl alcohol till the microemulsion that obtains clear, be designated as B liquid; With the speed of buret with 0.2ml/s the B drop is added in the A liquid under the vigorous stirring, regulation system pH value to 1.5 continues to stir 2h, obtains the faint yellow TiO of homogeneous transparent at last
2Colloidal sol, it is standby to leave standstill 24h.
3, TiO2 colloidal sol load on carrier: will be dipped in 4h in the TiO2 colloidal sol through cleaning and dry finished product ceramic-absorbent charcoal coating composite material, slowly lift taking-up then, be put in gel ageing 12h in the closed container, put into drying box dry 2h under 90 ℃ of temperature conditions again; Dried carrier is placed in the chamber type electric resistance furnace under nitrogen environment, is warming up to 250 ℃ from room temperature, insulation 30min with the heating rate of 2 ℃/min; Be warming up to 550 ℃ with same heating rate again, insulation 60min; Cool to room temperature afterwards with the furnace.Above-mentioned dipping-calcination process is repeated 2 times, obtain the TiO2 load capacity and be 3.52% composite photo-catalyst.
Utilize this catalyst Treatment by Photocatalysis Oxidation indoor formaldehyde gas, 25 ℃ of reaction temperatures, reaction time 120min, relative humidity is 70%, initial concentration of formaldehyde is 1mg/m
3Condition under, the formaldehyde clearance can reach 88.7%.
The preparation method that embodiment 3 contains the activated carbon coating composite photocatalyst comprises the steps:
1, the preparation method of ceramic-absorbent charcoal coating composite material: be 90% porous foam ceramic pipe ultrasonic cleaning 20min with porosity, after 110 ℃ of temperature conditions are dried 4 hours down, put into the container that has chuck and excessive thermosetting phenolic resin is housed, the porous foam ceramic pipe was flooded in maceration extract 16 hours; Dipping is 35 ℃ with the temperature of recirculated water in the container chuck.The porous foam ceramic pipe that is impregnated with phenolic resins is taken out in container, the resin that air scavenging is unnecessary, at room temperature place 10 hours after, put into baking oven and be cured processing, 70 ℃ are played temperature, rise to 150 ℃ of temperature with the heating rate of 1 ℃/min, are incubated 2 hours.With the ceramic-resin material that is cured in ar gas environment 150 ℃ play temperature, rise to 800 ℃ with the heating rate of 4 ℃/min and carry out charing and handled 60 minutes, in ar gas environment, be cooled to room temperature.Repeated impregnations-curing-carbonization process, ceramic-resin base carbon composite after twice charing processing was flooded 24 hours in the KOH saturated solution, in baking oven, under 120 ℃ of temperature conditions, dried 8 hours, 150 ℃ are played temperature in ar gas environment, heating rate with 10 ℃/min rises to 800 ℃, carry out activation processing 20 minutes, and in ar gas environment, be cooled to room temperature.With mass concentration is the material that 10% HCl solution pickling obtains, and is washed to neutrality, and it is 14.5% ceramic-absorbent charcoal composite that drying obtains active carbon content, and wherein the specific area of active carbon is 850m
2/ g, iodine sorption value are 909.36mg/g.
2, TiO
2The preparation of colloidal sol and TiO
2Colloidal sol on carrier load with embodiment 1.
Utilize this catalyst Treatment by Photocatalysis Oxidation indoor formaldehyde gas, 30 ℃ of reaction temperatures, reaction time 120min, relative humidity is 50%, initial concentration of formaldehyde is 2mg/m
3Condition under, the formaldehyde clearance can reach 90.2%.
The preparation method that embodiment 4 contains the activated carbon coating composite photocatalyst comprises the steps:
1, the preparation method of ceramic-absorbent charcoal coating composite material is with embodiment 3.
2, TiO
2The preparation of colloidal sol and TiO
2Colloidal sol on carrier load with embodiment 2.
Utilize this catalyst Treatment by Photocatalysis Oxidation indoor formaldehyde gas, 30 ℃ of reaction temperatures, reaction time 120min, relative humidity is 50%, initial concentration of formaldehyde is 1mg/m
3Under condition, the formaldehyde clearance can reach 85.5%.
The preparation method that embodiment 5 contains the activated carbon coating composite photocatalyst comprises the steps:
1, the preparation method of ceramic-absorbent charcoal coating composite material is with embodiment 3.
2, TiO
2The preparation of colloidal sol: in there-necked flask, add 100ml absolute ethyl alcohol and 12ml acetylacetone,2,4-pentanedione, under vigorous stirring, drip the 75ml butyl titanate, drip and finish, continue to stir the yellow solution that 30min obtains homogeneous transparent, be designated as A liquid; Take by weighing weight content and account for TiO
2The polyethylene glycol of colloidal sol gross weight 2% (molecular weight: 20000) dissolve in the 12ml distilled water, measure 2ml HCl simultaneously, the 75ml absolute ethyl alcohol and stirring makes it to mix, and is designated as B liquid; With the speed of buret with 0.2ml/s the B drop is added in the A liquid under the vigorous stirring, regulation system pH value to 2.5 continues to stir 2h, obtains the faint yellow TiO of homogeneous transparent at last
2Colloidal sol, it is standby to leave standstill 24h.
3, TiO
2Colloidal sol is load on carrier: will be dipped in TiO through cleaning and dry finished product ceramic-absorbent charcoal coating composite material
22h in the colloidal sol slowly lifts taking-up then, is put in gel ageing 12h in the closed container, puts into drying box dry 4h under 80 ℃ of temperature conditions again; Dried carrier is placed in the chamber type electric resistance furnace under nitrogen environment, is warming up to 250 ℃ from room temperature, insulation 30min with the heating rate of 2 ℃/min; Be warming up to 550 ℃ with same heating rate again, insulation 120min; Cool to room temperature afterwards with the furnace.Above-mentioned dipping-calcination process is repeated 2 times, obtain TiO
2Load capacity is 4.31% composite photo-catalyst.
Utilize this catalyst Treatment by Photocatalysis Oxidation indoor formaldehyde gas, 25 ℃ of reaction temperatures, reaction time 120min, relative humidity is 70%, initial concentration of formaldehyde is 2mg/m
3Condition under, the formaldehyde clearance can reach 84.7%.
Claims (10)
1. preparation method who contains the activated carbon coating composite photocatalyst, it is characterized in that, this method be with active carbon as coating attached on the foamed material matrix, form the activated carbon coating material, and be carrier loaded titanium dioxide with this activated carbon coating material, wherein the percentage by weight of each component is: the titanium dioxide active component is 1～10%, and activated carbon coating is 4～15%, and all the other are the foamed material matrix.
2. a kind of preparation method who contains the activated carbon coating composite photocatalyst as claimed in claim 1, it is characterized in that, when being carrier loaded titanium dioxide with described activated carbon coating material, adopt infusion process that TiO 2 sol is supported on described activated carbon coating material support, obtain through high-temperature calcination, preparation process is as follows:
1) the titanium alkoxide is dissolved in the alcohol under vigorous stirring, and adds a certain amount of inhibitor and surfactant, slowly drip the mixed liquor of water, alcohol, acid, continue to stir; The volume ratio of titanium alkoxide and inhibitor, alcohol, water is 6～8: 1: 16～25: 0.75～1.5, and the addition of surfactant is 1～3% of a TiO 2 sol gross weight, mixes, and obtains TiO 2 sol even, stable transparent;
2) described activated carbon coating material support is dipped in 2～4h in the TiO 2 sol, takes out and be placed on gel ageing 12～24h in the closed container, put into drying box dry 2～4h under 80～110 ℃ of temperature conditions again; Dried carrier is placed in the resistance furnace under oxygen-free environment, rises to 450～650 ℃, insulation 40～90min from room temperature; Cool to room temperature afterwards with the furnace.
3. a kind of preparation method who contains the activated carbon coating composite photocatalyst as claimed in claim 2 is characterized in that described titanium alkoxide is a butyl titanate; Described alcohol is one or more the mixture in ethanol, isopropyl alcohol, the n-butanol; Described acid is one or more the mixture in nitric acid, sulfuric acid, the hydrochloric acid; Described inhibitor is a kind of in acetylacetone,2,4-pentanedione, glacial acetic acid, the diethanol amine; Described surfactant is one or more the mixture in polyethylene glycol, polyvinyl alcohol, the NPE.
4. a kind of preparation method who contains the activated carbon coating composite photocatalyst as claimed in claim 1, it is characterized in that, prepared attached to the described activated carbon coating on the foamed material by thermosetting resin, adopt thermosetting resin that impregnation technology will contain solvent to be coated in the surfaces externally and internally of foamed material, described thermosetting resin is as carbon precursor process curing process, charring process, activating process and clean process, obtain attached to the activated carbon coating on the foamed ceramics, described activated carbon coating is 5～20% of a described activated carbon coating material gross mass, coating layer thickness is 0.1～1mm, and the surface area of activated carbon coating is 800～1400m
2/ g, preparation technology is as follows:
1) impregnation technology: with the foamed material matrix after ultrasonic cleaning, drying is 4～8 hours under 105 ± 5 ℃ of conditions, put into the container that has chuck and thermosetting resin is housed, in maceration extract, flooded 4～16 hours, flooding has the warm water circulation in the chuck of used container, the temperature of warm water is 20～70 ℃; Take out being impregnated with in the calm device of foamed material matrix of thermosetting resin, remove unnecessary thermosetting resin by air scavenging or centrifuge;
2) curing process: will be impregnated with the foamed material matrix of thermosetting resin, at room temperature place 6～12 hours after, put into baking oven and solidify, 70 ℃ are played temperature, per minute heats up 1～4 ℃, is incubated 1～5 hour under 150 ℃ of temperature;
3) charring process: will heat up in oxygen-free environment through the foamed material matrix that curing process is handled, 150 ℃ are played temperature, and per minute heats up 2～10 ℃, carry out charing and handled cool to room temperature in oxygen-free environment 30-120 minute under 600～1000 ℃ of temperature;
4) physically activated technology: will in oxygen-free environment, heat up through foam-raw material of wood-charcoal material that charring process is handled, 150 ℃ are played temperature, per minute heats up 2～10 ℃, under 600～1000 ℃ of temperature, with supersaturation water steam or carbon dioxide is activated media, activation processing 30～120 minutes, cool to room temperature in oxygen-free environment;
5) chemical activation technology: will in potassium hydroxide or NaOH saturated solution, flood 4～24 hours through foam-raw material of wood-charcoal material that charring process is handled, in baking oven, dried 2～12 hours under 120 ℃ of temperature conditions, in oxygen-free environment, heat up then, 150 ℃ are played temperature, per minute heats up 2～10 ℃, under 600～1000 ℃ of temperature, handled 10～120 minutes cool to room temperature in oxygen-free environment;
6) cleaning: the activated carbon coating composite that will handle through activating process is 5～20% hydrochloric acid solution pickling 4～12 hours with mass concentration, washes with water to neutrality again.
5. a kind of preparation method who contains the activated carbon coating composite photocatalyst as claimed in claim 1 is characterized in that, described foamed material matrix adopts a kind of in foamed ceramics or the foam metal.
6. a kind of preparation method who contains the activated carbon coating composite photocatalyst as claimed in claim 5, it is characterized in that, described foamed material matrix is a foamed ceramics, and its porosity is 50～90%, and its main aperture is made of the 3 D pore canal of diameter by 1mm～10mm random distribution.
7. a kind of preparation method who contains the activated carbon coating composite photocatalyst as claimed in claim 4 is characterized in that, described thermosetting resin is a kind of of phenolic resins, epoxy resin, unsaturated polyester (UP), acrylic resin.
8. a kind of preparation method who contains the activated carbon coating composite photocatalyst as claimed in claim 7, it is characterized in that, described thermosetting resin is a phenolic resins, comprise unmodified phenolic resins and phenol-formaldehyde resin modified, described phenol-formaldehyde resin modified is one or more the mixture in melamine phenol-formaldehyde resin modified, aniline phenol-formaldehyde resin modified, epoxy modified phenolic resin, cashew nut shell oil or modified by cardanol phenolic resins, polyvinyl alcohol modification phenolic resins, the asphalt modification phenolic resins.
9. a kind of preparation method who contains the activated carbon coating composite photocatalyst as claimed in claim 4, it is characterized in that solvent for use is one or more the mixture in methyl alcohol, ethanol, butanols, toluene, dimethylbenzene, the gasoline in the described thermosetting resin that contains solvent.
10. a kind of preparation method who contains the activated carbon coating composite photocatalyst as claimed in claim 2 is characterized in that described oxygen-free environment is by inert gas, CO
2Or N
2In one or more mix the back and constitute.
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