CN102744049A - Process for preparing TiO2 (titanium dioxide) film on aluminum-oxide foamed ceramic - Google Patents
Process for preparing TiO2 (titanium dioxide) film on aluminum-oxide foamed ceramic Download PDFInfo
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- CN102744049A CN102744049A CN2012102338884A CN201210233888A CN102744049A CN 102744049 A CN102744049 A CN 102744049A CN 2012102338884 A CN2012102338884 A CN 2012102338884A CN 201210233888 A CN201210233888 A CN 201210233888A CN 102744049 A CN102744049 A CN 102744049A
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Abstract
The invention discloses a process for preparing a TiO2 (titanium dioxide) film on aluminum-oxide foamed ceramic. The process adopts a concrete implementation scheme that coating aluminum oxide slurry is coated on a foam rib by dipping and extruding, then foam is burned up, and finally, the aluminum-oxide foamed ceramic with high porosity is obtained in a high-temperature sintering manner; Ti collosol is uniformly coated on a pore wall of an aluminum-oxide foamed ceramic carrier by negative-pressure infiltration; and the TiO2 film which is uniformly and continuously distributed on the pore wall of the aluminum-oxide foamed ceramic is prepared by drying and thermal treatment. According to materials disclosed by the invention, the porous aluminum-oxide foamed ceramic serves as a base body; meanwhile, the base body has good resistance to acid and alkali corrosion due to the stable chemical properties of the Al2O3 (aluminum oxide) ceramic; in addition, the carrier material has good high-temperature resistance and oxidation resistance by virtue of a high-melting point of the Al2O3 ceramic. These properties of the materials well meet the requirements on properties of catalysts and the carrier which are used for purifying industrial wastewater, domestic sewage and toxic waste gas in extremely serious corrosive environments.
Description
Technical field
The invention belongs to the ceramic coating technical field, relate to a kind of TiO that on pottery, prepares
2The technology of film, especially a kind of TiO that is evenly distributed, has photocatalytic and nanometer grade thickness that on aluminium oxide foam ceramic matrix, prepares
2The preparation technology of film.
Background technology
Along with the continuous propelling of China's industrialization and urbanization, more and more darker to the influence of environment.The pollution problem of environment is also outstanding all the more, becomes the stumbling-block of restriction China rapid economic development gradually.The raising of people's living standard simultaneously also requires to have a good life living environment.For this reason, the purified treatment to industrial wastewater, sanitary sewage, poisonous fume has become problem demanding prompt solution.Because materials such as industrial wastewater, sanitary sewage mostly are in a kind of exceedingly odious corrosive atmosphere.In order to make the catalyst harmful substance of can under this operating mode, degrading long-term effectively, this just requires the carrier of catalyst to have good stable property and corrosion resistance.
TiO in industry
2Be otherwise known as " titanium white powder " TiO
2Have nontoxicly, chemical property is stable, acid-fast alkali-proof, excellent properties such as nonirritant.For nano-TiO
2Particle because its particle diameter is little, has absorption and scattering process to ultraviolet light, also has excellent photocatalysis activity, colour effect etc. simultaneously.Above characteristic makes TiO
2Can be used as catalysis material, solar cell material (photoelectric material), ultraviolet light screener, paint vehicle additive, sensor material and catalyst carrier etc.TiO
2Photocatalysis be mainly reflected in following direction: 1, the processing of organic polluting water.Present research report, TiO
2Organic pollutions such as semiconductor can degradating organic dye, organic-fuel, organophosphor, organic chloride, phenol.2, the degraded of inorganic pollution.Present discovers TiO under the illumination condition
2Can be with Cr
2O
7 2+Be reduced to Cr
3+, also can be with CN
-Be oxidized to OCN
-3, air cleaning.Adopt photocatalysis oxidation technique can at room temperature utilize airborne steam and oxygen to remove airborne pollutant, like pernicious gases such as nitrogen oxide, sulfide, formaldehyde.TiO
2Photocatalysis performance fails to reach large-area use, and its reason mainly contains following three aspects: 1, quantum efficiency is low.Simple TiO
2The height of recombination rate again that the light induced electron-hole of photochemical catalyst is right, photocatalysis performance is outstanding.There is document to point out, TiO
2Quantum efficiency is the highest to be no more than 20%, and lower photo-quantum efficiency is restriction photocatalysis practicability and industrialized main cause.2, spectral response range is narrow.Pure TiO
2Can only utilize the ultraviolet light part of solar radiation frequency spectrum scope about 4%.3, fixing condition is harsh.Because the powder catalyst is difficult to reclaim in making process, causes the waste of catalyst easily, increases cost for wastewater treatment, influences light-catalysed practical application, so need be with TiO
2Photochemical catalyst is fixed.
Adopt Al
2O
3Foamed ceramics is as TiO
2The carrier material of photochemical catalyst, its advantage mainly contains the following aspects: 1, foam ceramic material is a loose structure, can improve TiO significantly
2The effective area of catalyst.Al
2O
3The porosity of pottery can be controlled through regulating technological parameter exactly.Utilize sol-gel process with TiO
2On surface and the inner hole wall of photocatalyst coated and pottery, when the solution that is degraded or gas pass the foam ceramic material of high porosity, can improve the material total amount of catalyst surface absorption in large quantities, thereby improve light-catalysed efficient.Simultaneously, loose structure also can play the effect of solids in filtered water and the gas.2, Al
2O
3Pottery has stable chemical property, has certain corrosion resistance.Al
2O
3Pottery can passivation in strongly acidic solution, shows good anti-strong acid erosion character.In weakly alkaline solution, Al
2O
3Slow with alkali reaction, can think to have certain caustic corrosion resistance performance.In addition, Al
2O
3Pottery also can keep good stable property in organic solution.3, Al
2O
3The pottery fusing point is high, at adjustment TiO
2Kept fabulous high-temperature stability and non-oxidizability in the heat treatment process of crystal structure.Pure Al
2O
3The fusing point of pottery is 2010 ~ 2050 ℃, far above Detitanium-ore-type TiO
2Temperature (500 ~ 700 ℃) to the rutile inversion of phases.In addition, dystectic matrix helps TiO
2At high temperature bring into play photocatalysis, such as in the ironmaking processes to purification of waste gas etc.4, Al
2O
3Ceramic density is low, intensity hardness high, makes material easy to use and reliable.5, Al
2O
3Raw material is wide, price is low, for a large amount of production provides reliable guarantee.
The hole dimension of foamed ceramics depends primarily on the hole dimension of organic foam body, the factors such as coating thickness of slurry.The porosity of foamed ceramics can reach 80%-90%, has great advantage with filtration and the adsorption cleaning done impurity.Loose structure has greatly improved the surface area of material, makes to be filtered with the material that purifies fully to contact with filtering material, has improved the efficient that purifies effectively.In addition, Al
2O
3Foam ceramic material has that fusing point height, density are low, acid-alkali-corrosive-resisting, resistance to high temperature oxidation, characteristics such as chemical stability is good, elastic modelling quantity is high, hardness height.These characteristics make aluminium oxide foam pottery have more advantage as the carrier of catalyst than present achievement in research.Like the patent 200910023997.1 application in 2009 such as Yu Sen, a kind of solution-gel method prepares TiO
2The method of film.They utilize butyl titanate to prepare layer of even TiO on glass and silicon chip
2Film.The composite of this method preparation is because matrix is fine and close block, and effective usable floor area of catalyst is very limited.In order to improve the effective area of catalyst, Liu Zhengbing etc. have invented patent 200440094705.6, a kind of area load nano-TiO
2Metal screen.This composite utilizes net metal, has improved the surface area of catalyst effectively.But metallic matrix is all more less better than corrosion resistance, the high-temperature stability of pottery.For the operating mode of the conditions such as anhydrous, poisonous fume of severe corrosive, the life-span of metallic matrix is also not as ceramic matrix.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, provide a kind of and on aluminium oxide foam pottery, prepare TiO
2The technology of film, this technology are the photocatalysis TiO that on the hole wall of aluminium oxide foam pottery, covers one deck nano thickness
2Film.Can be good at solving the immobilization problem of catalyst under light-catalysed efficiency and the extreme harsh conditions like this.
The objective of the invention is to realize through following technical scheme:
Thisly on aluminium oxide foam pottery, prepare TiO
2The technology of film may further comprise the steps:
(1) preparation aluminium oxide foam ceramic matrix;
(2) preparation of Ti colloidal sol:
The precursor solute TiCl that will contain Ti
4Slowly be added drop-wise to the wide-mouth bottle that places cold bath to fill anhydrous ethanol solvent, make TiCl
4Concentration be controlled at 0.6 ~ 1.5mol/L, and then add deionized water and process colloidal sol, TiCl
4With the volume ratio of the deionized water that adds be 20,10,5,2 or 1; Stirring makes and mixes through cylinder, obtains Ti colloidal sol;
(3) aluminium oxide foam ceramic matrix is put into Ti colloidal sol and carry out repeatedly the negative pressure infiltration; Take out the aluminium oxide foam ceramic matrix that is adsorbed with Ti colloidal sol then, after heat treatment can on the hole wall of aluminium oxide foam ceramic matrix, make continuous Detitanium-ore-type or rutile TiO
2Film.
In the above step (1), the preparation of said aluminium oxide foam ceramic matrix is according to following steps:
1) preparation alumina slurry:
A) configuration is alumina powder jointed: according to mass ratio with 75% aluminium oxide, 10% silica, 7% kaolin, 3% bentonite and 5% talcum mix obtain alumina powder jointed;
B) configuration solution A: according to alumina powder jointed mass percent meter, get 2% ammonium polyacrylate, it is added in the deionized water; Sonic oscillation is handled 10-20min, with ammoniacal liquor the solution pH value is adjusted to 11 again, adds 2% Ludox again; Last sonic oscillation is even, obtains solution A;
C) configuration solution B: according to alumina powder jointed mass percent meter, get 0.5% carboxymethyl cellulose, obtain solution B with mixing in its adding deionized water;
D) with in the alumina powder jointed adding solution A, stir, and then add solution B and stir, obtain alumina slurry to lumps; The mass ratio 3:7 of total consumption of said deionized water and alumina powder jointed total consumption;
2) polyurethane foam preliminary treatment: with mass ratio is that 15% the NaOH aqueous solution carries out water bath processing to polyurethane foam, and temperature is 60 ℃, and the time is 2 ~ 6h; After the drying, carry out activation processing with the 5%PVA aqueous solution again, the time is 24h;
3) pretreated polyurethane foam is immersed in the alumina slurry, extruding makes evenly to be coated with inside and outside the foam and is covered with aluminium oxide repeatedly; The foam that will soak full slurry then takes out, and with the dull and stereotyped crushed foam redundant sizing agent of draining, only keeps the alumina slurry that applies on the foam muscle; Through low temperature drying, discharge foam and sintering then and obtain aluminium oxide foam ceramic matrix.
Above-mentioned steps 3) in, low temperature drying technology adopts 1 ℃/min to be warmed up to 40 ℃, and insulation 1h is raised to 80 ℃ with 1 ℃/min again, and insulation 1h is raised to 120 ℃ with 0.5 ℃/min again, insulation 2h.
Above-mentioned steps 3) in, said release foam and the concrete technology of sintering are: heating rate is 2 ℃/min between 0 ~ 200 ℃, and heating rate is 1 ℃/min between 200 ℃ ~ 600 ℃, is warmed up to 1550 ℃ of insulation 3h with 5 ℃/min again, and stove is chilled to room temperature.
In the above-mentioned steps (3), the number of times of the said infiltration of negative pressure repeatedly is 5 times, and the infiltration time is 20min at every turn.
In the above-mentioned steps (3), to the concrete technology of heat treatment of the aluminium oxide foam ceramic matrix that is adsorbed with Ti colloidal sol be: the speed with 2 ℃/min in the air heat-treatment furnace is heated to 60 ℃ from room temperature, insulation 10min; Speed with 2 ℃/min is heated to 70 ℃ again, insulation 10min; And then be raised to the heat treatment temperature in 550 ~ 1200 ℃ of scopes, insulation 60min with the speed of 2 ℃/min; Cool to room temperature at last with the furnace.
The present invention has following beneficial effect:
The present invention prepares TiO on aluminium oxide foam pottery
2The technology of film has significantly improved the effective area of catalyst carrier owing to adopted the Woelm Alumina foamed ceramics; Al
2O
3The pottery stable chemical property makes matrix have the performance of good acid-alkali-corrosive-resisting; Al
2O
3The high-melting-point of pottery makes composite have good heat-resistance and antioxygenic property, thereby photochemical catalyst can use under high-temperature.
Description of drawings
Fig. 1 is an aluminium oxide foam ceramic matrix macro morphology of the present invention;
Fig. 2 is the aluminium oxide foam pottery macro morphology that had soaked Ti colloidal sol of the present invention;
Fig. 3 is the aluminium oxide foam ceramic surface microscopic appearance that had soaked Ti colloidal sol of the present invention.
The specific embodiment
Below in conjunction with embodiment the present invention is done and to describe in further detail:
Embodiment 1
The preparation concrete operations of alumina slurry are following:
Select for use deionized water as dispersant; And with the deionized water separated into two parts that is added; Add the dispersant ammonium polyacrylate of 2wt% in a part of therein deionized water; Sonic oscillation is handled 10min, in another part deionized water, adds the carboxymethyl cellulose of 0.5wt% simultaneously and it is uniformly dispersed; With ammoniacal liquor the pH value of the polyacrylic acid ammonium salt solution that mixes is transferred to the Ludox that the back adds 2wt% about 11 again, behind the sonic oscillation 10min ceramic powder adding that mixes is wherein stirred to lumps.At last again carboxymethyl cellulose aqueous solution is poured into wherein to stir and obtain the ceramic size that solid content is 70wt%.Then ceramic size is poured in the airtight round vase, be placed on the homemade rotary mixer, roll and stirred 24 hours, pour out and place beaker.The polyurethane foam that to pass through the processing of the 15%NaOH aqueous solution and 5%PVA activated in water solution immerses in the alumina slurry, and extruding makes slurry be coated in fully on the muscle of foam repeatedly.The foam that will soak full slurry then takes out, and with the dull and stereotyped crushed foam redundant sizing agent of draining, only keeps the alumina slurry that applies on the foam muscle.Be warmed up to 40 ℃ through 1 ℃/min, insulation 1h is raised to 80 ℃ with 1 ℃/min again, and insulation 1h is raised to 120 ℃ with 0.5 ℃/min again, is incubated 2 hours and makes the foam of coating alumina fully dry.And then adopt that heating rate is 2 ℃/min between 0 ~ 200 ℃; Heating rate is 1 ℃/min between 200 ℃ ~ 600 ℃, is warmed up to 1550 ℃ of insulation 3h with 5 ℃/min again, and stove is chilled to room temperature; Can obtain the porosity and be 85 ~ 90% porous foam ceramic, as shown in Figure 1.
The proportioning of plated film colloidal sol is as shown in table 1.The cumulative volume of solution is 170ml, and TiCl4 is 5 than the ratio perseverance of water in every group of solution.During preparation colloidal sol, with TiCl
4Slowly (10/min) be added drop-wise to the wide-mouth bottle that places cold bath to fill absolute ethyl alcohol, and then add deionized water and process colloidal sol.Cylinders stirring through 72 hours mixes colloidal sol.With cleaned and Al that weigh
2O
3Ceramic matrix is put into every group of solution, takes out behind five negative pressure infiltration 20min.The ceramic matrix that is adsorbed with colloidal sol speed with 2 ℃/min in the air heat-treatment furnace is heated to 60 ℃ from room temperature, protects
The proportioning of table 1 coated solution
| The solution numbering | [Ti] molar concentration, mol/L | TiCl 4Amount, ml | The amount of ethanol, ml | The amount of water, ml |
| 1 | 0.6 | 12 | 155.6 | 2.4 |
| 2 | 0.9 | 17 | 149.6 | 3.4 |
| 3 | 1.2 | 23 | 142.4 | 4.6 |
| 4 | 1.5 | 29 | 135.2 | 5.8 |
Embodiment 2
(1) preparation aluminium oxide foam ceramic matrix;
1) preparation alumina slurry:
A) configuration is alumina powder jointed: according to mass ratio with 75% aluminium oxide, 10% silica, 7% kaolin, 3% bentonite and 5% talcum mix obtain alumina powder jointed;
B) configuration solution A: according to alumina powder jointed mass percent meter, get 2% ammonium polyacrylate, it is added in the deionized water; Sonic oscillation is handled 10-20min, with ammoniacal liquor the solution pH value is being adjusted to 11, adds 2% Ludox again; Sonic oscillation is even again, obtains solution A;
C) configuration solution B: according to alumina powder jointed mass percent meter, get 0.5% carboxymethyl cellulose, obtain solution B with mixing in its adding deionized water;
D) with in the alumina powder jointed adding solution A, stir, and then add solution B, obtain alumina slurry to lumps; The mass ratio 3:7 of total consumption of said deionized water and alumina powder jointed total consumption;
2) polyurethane foam preliminary treatment: with mass ratio is that 15% the NaOH aqueous solution carries out water bath processing to polyurethane foam, and temperature is 60 ℃, and the time is 2-6h; After the drying, carry out activation processing with the 5%PVA aqueous solution again, the time is 24h;
3) pretreated polyurethane foam is immersed in the alumina slurry, extruding makes evenly to be coated with inside and outside the foam and is covered with aluminium oxide repeatedly; The foam that will soak full slurry then takes out, and with the dull and stereotyped crushed foam redundant sizing agent of draining, only keeps the alumina slurry that applies on the foam muscle; Through low temperature drying, discharge foam and sintering then and obtain aluminium oxide foam ceramic matrix.Low temperature drying technology adopts 1 ℃/min to be warmed up to 40 ℃, and insulation 1h is raised to 80 ℃ with 1 ℃/min again, and insulation 1h is raised to 120 ℃ with 0.5 ℃/min again, insulation 2h.Said release foam and sintering are specially: adopt that heating rate is 2 ℃/min between 0 ~ 200 ℃, heating rate is 1 ℃/min between 200 ℃ ~ 600 ℃, is warmed up to 1550 ℃ of insulation 3h with 5 ℃/min again, and stove is chilled to room temperature.
(2) preparation of Ti colloidal sol:
The precursor solute TiCl that will contain Ti
4Slowly be added drop-wise to the wide-mouth bottle that places cold bath to fill anhydrous ethanol solvent, make TiCl
4Concentration be controlled at 0.6 ~ 1.5mol/L, and then add deionized water and process colloidal sol, TiCl
4With the volume ratio of the deionized water that adds be 20,10,5,2 or 1; Stirring makes and mixes through cylinder, obtains Ti colloidal sol;
(3) aluminium oxide foam ceramic matrix is put into Ti colloidal sol and carry out repeatedly negative pressure infiltration 5 times, the infiltration time is 20min at every turn.Take out the aluminium oxide foam ceramic matrix be adsorbed with Ti colloidal sol then, the heat treatment of the aluminium oxide foam ceramic matrix that is adsorbed with Ti colloidal sol is specially: the speed with 2 ℃/min in the air heat-treatment furnace is heated to 60 ℃ from room temperature, insulation 10min; Speed with 2 ℃/min is heated to 70 ℃ again, insulation 10min; And then be raised to the heat treatment temperature in 550 ~ 1200 ℃ of scopes, insulation 60min with the speed of 2 ℃/min; Cool to room temperature at last with the furnace.Promptly on the hole wall of aluminium oxide foam ceramic matrix, make continuous Detitanium-ore-type or rutile TiO
2Film, concrete pattern is shown in Fig. 2 and 3.
Claims (6)
1. one kind prepares TiO on aluminium oxide foam pottery
2The technology of film is characterized in that, may further comprise the steps:
(1) preparation aluminium oxide foam ceramic matrix;
(2) preparation of Ti colloidal sol:
The precursor solute TiCl that will contain Ti
4Slowly be added drop-wise to the wide-mouth bottle that places cold bath to fill anhydrous ethanol solvent, make TiCl
4Concentration be controlled at 0.6 ~ 1.5mol/L, and then add deionized water and process colloidal sol, TiCl
4With the volume ratio of the deionized water that adds be 20,10,5,2 or 1; Stir through cylinder, obtain Ti colloidal sol;
(3) aluminium oxide foam ceramic matrix is put into Ti colloidal sol and carry out repeatedly the negative pressure infiltration; Take out the aluminium oxide foam ceramic matrix that is adsorbed with Ti colloidal sol then, after heat treatment promptly on the hole wall of aluminium oxide foam ceramic matrix, make continuous Detitanium-ore-type or rutile TiO
2Film.
2. according to claim 1ly on aluminium oxide foam pottery, prepare TiO
2The technology of film is characterized in that, in the said step (1), the preparation of said aluminium oxide foam ceramic matrix is according to following steps:
1) preparation alumina slurry:
A) configuration is alumina powder jointed: according to mass ratio with 75% aluminium oxide, 10% silica, 7% kaolin, 3% bentonite and 5% talcum mix obtain alumina powder jointed;
B) configuration solution A: according to alumina powder jointed mass percent meter, get 2% ammonium polyacrylate, it is added in the deionized water; Sonic oscillation is handled 10-20min, with ammoniacal liquor the solution pH value is adjusted to 11 then, adds 2% Ludox again; Last sonic oscillation is even, obtains solution A;
C) configuration solution B: according to alumina powder jointed mass percent meter, get 0.5% carboxymethyl cellulose, obtain solution B with mixing in its adding deionized water;
D) with in the alumina powder jointed adding solution A, stir to lumps, and then add solution B, stirring obtains alumina slurry; The mass ratio 3:7 of total consumption of said deionized water and alumina powder jointed total consumption;
2) polyurethane foam preliminary treatment: with mass ratio is that 15% the NaOH aqueous solution carries out water bath processing to polyurethane foam, and temperature is 60 ℃, and the time is 2-6h; After the drying, carry out activation processing with the 5%PVA aqueous solution, the time is 24h;
3) pretreated polyurethane foam is immersed in the alumina slurry, extruding makes evenly to be coated with inside and outside the foam and is covered with aluminium oxide repeatedly; The foam that will soak full slurry then takes out, and with the dull and stereotyped crushed foam redundant sizing agent of draining, only keeps the alumina slurry that applies on the foam muscle; Through low temperature drying, discharge foam and sintering and obtain aluminium oxide foam ceramic matrix.
3. according to claim 2ly on aluminium oxide foam pottery, prepare TiO
2The technology of film is characterized in that, in the step 3), low temperature drying technology adopts 1 ℃/min to be warmed up to 40 ℃, and insulation 1h is raised to 80 ℃ with 1 ℃/min again, and insulation 1h is raised to 120 ℃ with 0.5 ℃/min again, insulation 2h.
4. according to claim 2ly on aluminium oxide foam pottery, prepare TiO
2The technology of film is characterized in that, in the step 3); Said release foam and the concrete technology of sintering are: adopt that heating rate is 2 ℃/min between 0 ~ 200 ℃; Heating rate is 1 ℃/min between 200 ℃ ~ 600 ℃, is warmed up to 1550 ℃ of insulation 3h with 5 ℃/min again, and stove is chilled to room temperature.
5. according to claim 1ly on aluminium oxide foam pottery, prepare TiO
2The technology of film is characterized in that, in the step (3), the number of times of the said infiltration of negative pressure repeatedly is 5 times, and the infiltration time is 20min at every turn.
6. according to claim 1ly on aluminium oxide foam pottery, prepare TiO
2The technology of film is characterized in that, in the step (3), the heat treatment of the aluminium oxide foam ceramic matrix that is adsorbed with Ti colloidal sol is specially: the speed with 2 ℃/min in the air heat-treatment furnace is heated to 60 ℃ from room temperature, insulation 10min; Speed with 2 ℃/min is heated to 70 ℃ again, insulation 10min; And then be raised to the heat treatment temperature in 550 ~ 1200 ℃ of scopes, insulation 60min with the speed of 2 ℃/min; Cool to room temperature at last with the furnace.
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| CN102941020A (en) * | 2012-11-06 | 2013-02-27 | 南京工业大学 | High-flux sheet type TiO2Preparation method of nanofiltration membrane |
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| CN105924138A (en) * | 2016-04-28 | 2016-09-07 | 十九冶成都建设有限公司 | Preparation method of fine-aperture foamed ceramic |
| CN106116672A (en) * | 2016-06-29 | 2016-11-16 | 梅庆波 | A kind of indoor air purification method for preparing foamed ceramics |
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| CN107008240A (en) * | 2017-04-18 | 2017-08-04 | 南京理工大学 | Nano crystal titanium dioxide light catalyst of aluminum oxide open celled foam ceramic load Si doping and preparation method thereof |
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| CN107586118A (en) * | 2017-09-08 | 2018-01-16 | 福州名谷纳米科技有限公司 | One kind load TiO2Foamed ceramics and its preparation method and application |
| CN110871058A (en) * | 2018-08-30 | 2020-03-10 | 广东粤能净环保科技有限公司 | Photocatalytic unit and photocatalytic method thereof |
| CN110871060A (en) * | 2018-08-30 | 2020-03-10 | 广东粤能净环保科技有限公司 | Foamed ceramic carrier, titanium dioxide photocatalyst and preparation method thereof |
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| CN102941020A (en) * | 2012-11-06 | 2013-02-27 | 南京工业大学 | High-flux sheet type TiO2Preparation method of nanofiltration membrane |
| CN104681907B (en) * | 2015-02-09 | 2017-11-21 | 中国电子科技集团公司第二十三研究所 | Overall teflon insulation electroplate outer conductor radio-frequency cable and processing method |
| CN105402806A (en) * | 2015-10-30 | 2016-03-16 | 广东美的制冷设备有限公司 | Positive temperature coefficient (PTC) heating purifier, manufacturing method thereof and electric appliance |
| CN105924138A (en) * | 2016-04-28 | 2016-09-07 | 十九冶成都建设有限公司 | Preparation method of fine-aperture foamed ceramic |
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