CN107774241B - TiO 22Tourmaline composite photocatalyst and TiO2Tourmaline gauze - Google Patents
TiO 22Tourmaline composite photocatalyst and TiO2Tourmaline gauze Download PDFInfo
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- CN107774241B CN107774241B CN201710218890.7A CN201710218890A CN107774241B CN 107774241 B CN107774241 B CN 107774241B CN 201710218890 A CN201710218890 A CN 201710218890A CN 107774241 B CN107774241 B CN 107774241B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 18
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- 229940070527 tourmaline Drugs 0.000 claims abstract description 70
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- 239000000243 solution Substances 0.000 claims abstract description 35
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
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- 238000001354 calcination Methods 0.000 claims abstract description 8
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 38
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- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
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- 239000012080 ambient air Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 1
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Images
Classifications
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/30—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
Abstract
The invention provides a TiO2Tourmaline composite photocatalyst and TiO2The preparation method of the photocatalyst comprises adding glacial acetic acid into anhydrous ethanol, and stirring; slowly adding tetrabutyl titanate, and stirring to obtain a tetrabutyl titanate solution; adding tourmaline powder into the other part of absolute ethyl alcohol for ultrasonic treatment to obtain a tourmaline powder solution; dripping tetrabutyl titanate solution into the tourmaline solution, and stirring; obtaining a mixed solution; uniformly mixing absolute ethyl alcohol, deionized water and concentrated hydrochloric acid, then dropwise adding the mixture into the mixed solution, stirring to form gray sol, and then stirring at a certain temperature to form gel; drying, grinding and calcining the gel to form TiO2Tourmaline catalyst powder. The invention solves the bottleneck problem in the application of two photocatalysts of activity and fixation; the air negative ion releasing agent has the environmental additional function of releasing air negative ions, long service life, simple and convenient operation, low application cost, effective improvement of air quality and obvious practical application prospect.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to TiO2Tourmaline composite photocatalyst and TiO2Tourmaline gauze.
Background
With the rapid development of building and decoration industries, the wide application of various novel materials greatly increases the content of volatile organic pollutants in indoor air, and causes the pollution problem of the indoor air to be increasingly serious. Among them, formaldehyde (HCHO) is determined by the world health organization to be carcinogenic and teratogenic substances, has great harm to human health, and is more important for indoor air pollution treatment. Traditional method physical adsorption method and chemical method for air formaldehyde treatmentThe oxidation method, the biological method and the like generally have the problems of limited removal capability, easy generation of secondary pollution, high cost and the like. The photocatalytic technology has less secondary pollution and mild catalytic reaction conditions, and can completely oxidize and decompose organic matters into CO at normal temperature and normal pressure2And H2O has more development prospect.
Among the numerous photocatalytic materials, TiO2The technology has the advantages of no selectivity, stable performance, safety, no toxicity and low cost, draws wide attention in the aspect of environmental purification, is applied to the treatment of pollutants such as dyes, pesticides, surfactants, organic resins, halogenated compounds, oily wastewater and the like, and has more obvious advantages particularly when the concentration of the organic pollutants is high or the organic pollutants are difficult to degrade by a conventional method. The mechanism of the semiconductor photocatalytic reaction is as follows: when irradiated with light having an energy greater than the forbidden bandwidth, electrons in the Valence Band (VB) are excited onto the Conduction Band (CB) to form conduction band electrons (e-), while holes (h +) remain in the valence band, which are capable of reacting with OH adsorbed on the surface of the catalyst-Or H2O reacts to generate high-activity OH, various organic matters are indiscriminately oxidized, and photo-generated electrons can also react with O2Active oxygen free radicals are generated to participate in oxidation-reduction reaction. However, the technology has certain limitations in practical application: the efficiency of the photocatalytic reaction is not high due to the high recombination rate of the photoproduction electrons and the holes; the catalyst has weak adsorption capacity on volatile organic pollutants; the powder catalyst is inconvenient to use. Therefore, TiO is the most studied currently2Based on the method, the recombination rate of photon-generated carriers is reduced and the photocatalytic performance is improved by the means of technologies such as metal ion and rare earth ion doping, semiconductor compounding, noble metal deposition, external field (thermal field, microwave, ultrasonic and electric field) assisted photocatalysis and the like, or TiO is used2Immobilization (immobilization of a photocatalyst using glass, clay, hollow glass spheres, metal base, or the like as a carrier) results in a decrease in the specific surface area of the catalyst after immobilization, a decrease in the adsorption and light absorption efficiency of the catalyst, and a decrease in the activity of the catalyst.
Disclosure of Invention
In view of the above, the present invention is directed to a TiO compound2Tourmaline compoundPhotocatalyst and TiO2Tourmaline gauze, which overcomes the defects of the prior art and solves the problem of indoor formaldehyde pollution.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
TiO 22A tourmaline composite photocatalyst, the preparation of the photocatalyst comprises the following steps,
1) adding a certain amount of glacial acetic acid into absolute ethyl alcohol, and stirring to uniformly mix; slowly adding tetrabutyl titanate, and stirring to obtain a tetrabutyl titanate solution;
2) adding a proper amount of tourmaline powder into another part of absolute ethyl alcohol for ultrasonic treatment to obtain a tourmaline powder solution;
3) dripping the tetrabutyl titanate solution obtained in the step 1) into the tourmaline solution obtained in the step 2), and stirring; obtaining a mixed solution;
4) uniformly mixing absolute ethyl alcohol, deionized water and concentrated hydrochloric acid;
5) dropwise adding the solution obtained in the step 4) into the mixed solution obtained in the step 3), stirring to form gray sol, and then stirring at a certain temperature to form gel;
6) drying, grinding and calcining the gel to form TiO2Tourmaline composite photocatalyst powder.
Preferably, the amount of tetrabutyl titanate and glacial acetic acid corresponding to each 0.012-0.23 g of tourmaline powder is 8-12 ml and 4-5 ml respectively.
Preferably, in the step 1), the volume ratio of the glacial acetic acid to the absolute ethyl alcohol is as follows: (4-5) to (20-25); adding glacial acetic acid into absolute ethyl alcohol, and stirring for 10-20 min; adding tetrabutyl titanate and stirring for 20-30 min; preferably, after the glacial acetic acid is added into the absolute ethyl alcohol, stirring for 10 min; tetrabutyl titanate is added and stirred for 30 min.
Preferably, in the step 2), the addition amount of the tourmaline powder is 0.012-0.23 g per 30mL of absolute ethyl alcohol; adding tourmaline powder into absolute ethyl alcohol, and then carrying out ultrasonic treatment for 20-30 min; preferably, 30 min; preferably, the tourmaline powder is obtained after pretreatment and comprises the following steps of adding distilled water into a tourmaline raw material, ultrasonically dispersing for 1-1.5 h, then adding 1-2 mol/L dilute hydrochloric acid solution, ultrasonically dispersing for 1-1.5 h, standing for 12-24 h, finally repeatedly washing with distilled water until the tourmaline powder is neutral, and drying at 80-100 ℃ for later use.
Preferably, in the step 3), the tetrabutyl titanate solution obtained in the step 1) is dripped into the tourmaline solution obtained in the step 2) at the speed of 8-10 ml/min; and after the dropwise adding, stirring for 1-1.5 h at the stirring speed of 180-200 r/min.
Preferably, in the step 4), the volume ratio of the absolute ethyl alcohol to the deionized water is (20-25 ml) to (8-12 ml); after mixing, the pH value of the solution is 1.7-2;
preferably, in the step 5), the solution obtained in the step 4) is dripped into the mixed solution obtained in the step 3) at the speed of 3-5 ml/min, and stirring is carried out at the stirring speed of 180-200 r/min in the dripping process; after dropwise adding, continuously stirring for 1-2 h at a stirring speed of 180-200 r/min; preferably, 2 h; after the gray sol is formed, gelling for 2-3 h at the temperature of 40-60 ℃ and the stirring speed of 30-40 rpm;
in the step 6), the drying temperature is 80-100 ℃, and the drying time is 10-12 h; the calcining temperature is 450-550 ℃, and the calcining time is 2-4 h.
The invention also provides a method for preparing the TiO compound2TiO prepared by tourmaline composite photocatalyst2The tourmaline gauze comprises the following steps,
1) dissolving ethyl cellulose in absolute ethyl alcohol as a binder under the condition of 70-90 ℃ water bath;
2) soaking the gauze in the binder in the step 1) for 3-5 min, taking out, opening meshes of the gauze, and then, TiO2Spraying tourmaline composite photocatalyst powder onto gauze, and air drying at room temperature to obtain TiO2Tourmaline gauze; preferably, the impregnated gauze has its mesh opened by blowing.
Preferably, in the step 1), 1-2 g of ethyl cellulose is added to 50mL of absolute ethyl alcohol.
The present invention also provides TiO as described above2Tourmaline composite photocatalyst or TiO as described above2Application of tourmaline gauze in removing formaldehyde.
The method for assisting photocatalysis by using an external electric field has obvious effect, and the principle is that the e-flows to the cathode through an external circuit by applying the anode bias voltage, so that the photoinduced electrons and holes are prevented from being compounded, more photoproduction holes h + exist in the system, more OH is generated, and the efficiency of light quanta is improved. However, this method requires an external power source on the one hand and TiO on the other hand2The electrodes are made, and it is technically difficult to improve the space-time yield on a large scale due to the limitation of the unit active area of the membrane electrode. The natural mineral tourmaline is the only mineral with thermoelectric effect and piezoelectric effect in nature, and has unique heteropolar symmetrical structure. The tourmaline physically exhibits spontaneous polarity, and has polarization effect such that its surface thickness is 10 μm4- 107When free electrons exist on the surface or around the surface of the high electric field with the V/m, the high electric field can be quickly attracted and firmly captured by the anode of the tourmaline, so that the free electrons lose the free movement capability, the recombination probability of titanium dioxide photo-generated electrons and holes is greatly reduced, and the removal rate of formaldehyde is improved. In addition, the self-generating polarity of the tourmaline also enables the tourmaline to have unique environmental functional attributes of radiating far infrared rays, releasing air negative ions and the like.
The invention designs and utilizes polyvinyl chloride PVC net (screen window material) as a substrate to prepare TiO from the characteristics of natural electric field synergistic enhancement and indoor gaseous pollution treatment2The tourmaline composite photocatalysis net is a reticular material which is convenient for the circulation of gas, and the pressure change of the net can also strengthen the polarity of the tourmaline and enhance the micro electric field to improve the catalysis effect while the pollutant is transferred with high-efficiency mass; the product is more beneficial to light absorption when used as a window screen, so as to directly benefit the sunlight to exert the degradation capability, and the product has higher economical efficiency and practicability for degrading indoor gaseous pollutants such as formaldehyde.
Compared with the prior art, the TiO provided by the invention2Tourmaline composite photocatalyst and TiO2Tourmaline gauze, which has the following advantages:
1) the green minerals are used as main raw materials, and aiming at the defects of the traditional photocatalytic material, the permanent self-generating field of the electric mineral tourmaline is utilized to promote the separation of photoproduction electrons and holes, the adsorption mass transfer is strengthened, the safe, stable and efficient novel mineral-based composite photocatalytic material is obtained in a mode without additional field assistance, and the limitation of the utilization of the traditional mineral resources is broken through.
2) The method develops a suitable application mode aiming at indoor gas-phase pollutants, adopts window screening materials for immobilization, ensures the contact surface of pollutant mass transfer and directly receives light, strengthens the electrical property by means of the circulation of gas, improves the catalytic efficiency, applies the method to the treatment of volatile organic pollutants in the ambient air, and solves the bottleneck problem in the application of two active and fixed photocatalysts;
3) the air negative ion releasing agent has the environmental additional function of releasing air negative ions, long service life, simple and convenient operation, low application cost, effective improvement of air quality, obvious practical application prospect and multiple benefits of environmental benefit, economic benefit and social benefit.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with the description, serve to explain the invention without limitation. In the drawings:
FIG. 1 is TiO2SEM picture of (a);
fig. 2 is an SEM picture of tourmaline;
FIG. 3 is an SEM photograph of a Ti/T (1%) composite catalyst with tourmaline of 1% synthesized in example 2
FIG. 4 TiO of different tourmaline contents2Tourmaline gauze and pure TiO2Comparative graph of gauze versus formaldehyde degradation performance.
FIG. 5 is TiO2Stability test chart of tourmaline gauze
FIG. 6 shows different masses of TiO2Comparison of tourmaline gauze on formaldehyde degradation performance.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
1) Preparation of photocatalyst powder
Adding 4ml of glacial acetic acid into 30ml of absolute ethyl alcohol by adopting a sol-gel method, magnetically stirring for 10min to uniformly mix, and then slowly adding 10ml of tetrabutyl titanate and stirring for 30min to obtain a tetrabutyl titanate solution;
meanwhile, adding a proper amount of tourmaline powder into 20ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 30min to obtain a tourmaline powder solution; slowly dripping tetrabutyl titanate solution into the tourmaline powder solution, and stirring for 1h with strong force to obtain a mixed solution;
uniformly mixing 20ml of absolute ethyl alcohol, 10ml of deionized water and concentrated hydrochloric acid to ensure that the pH value of the solution is about 1.7, slowly dripping the solution into the obtained mixed solution of tetrabutyl titanate and tourmaline under strong stirring, strongly stirring for 2h to form gray sol, and then stirring in a water bath at 40 ℃ for 2h to form gel. Drying the gel at 80 ℃ for 12h, grinding and calcining at 500 ℃ for 2h to obtain TiO2A photocatalyst powder.
2) Preparation of catalyst gauze
Adding 1g of ethyl cellulose into 50ml of absolute ethyl alcohol, and dissolving in a water bath at 80 ℃ to obtain ethyl cellulose sol serving as a binder. Cutting the pretreated gauze into 5cm × 5cm pieces, soaking in binder for several minutes, taking out, opening the meshes of gauze by blowing, spraying catalyst powder on gauze uniformly, and air drying at room temperature to obtain firmly-loaded TiO2Gauze, immobilized TiO2The mass was 0.168 g.
Example 1:
adding TiO into 20ml of absolute ethyl alcohol2Tourmaline with the mass of 0.5 percent is subjected to ultrasonic treatment for 30min to obtain tourmaline powder solution.
Example 2:
adding TiO into 20ml of absolute ethyl alcohol2Tourmaline with the mass of 1 percent is subjected to ultrasonic treatment for 30min to obtain tourmaline powder solution.
TiO2Tourmaline and TiO2SEM images of/1% tourmaline as shown in figure 1, figure 2 and figure 3.
Example 3:
adding TiO into 20ml of absolute ethyl alcohol22 percent of tourmaline by mass, and then performing ultrasonic treatment for 30min to obtain tourmaline powder solution.
Example 4:
adding TiO into 20ml of absolute ethyl alcohol2Tourmaline with the mass of 5 percent is subjected to ultrasonic treatment for 30min to obtain tourmaline powder solution.
Example 5:
adding TiO into 20ml ethanol 210 percent of tourmaline by mass, and then performing ultrasonic treatment for 30min to obtain tourmaline powder solution.
Determination of TiO prepared according to the invention2Gauze and TiO2The degradation performance of the tourmaline gauze on formaldehyde gas is as follows:
the test device adopted by the invention is a cylindrical flange glass reactor. Firstly, the rotor is put into a reactor, and then 20 mul of formaldehyde solution with certain concentration is put into the reactor to ensure that the concentration of the formaldehyde in the reactor is 100mg/m3The ultraviolet lamp fixed with the catalyst gauze is assembled with the cylindrical container and sealed. The reactor is placed in a magnetic stirring water bath kettle at 40 ℃ for 2 hours until the reactor is uniformly diffused, and then sampling is carried out once. Then turning on the ultraviolet lamp, sampling every 10min until 60min, and measuring TiO2Gauze and TiO2The degradation performance of the tourmaline gauze on formaldehyde gas. The determination method adopts a national standard GB/T18204.26-2000 phenol reagent spectrophotometry, and develops color at a constant temperature of 25 ℃.
1) Tourmaline to TiO2Influence of photocatalytic degradation of formaldehyde gas
O.168g of pure TiO immobilized by using binder method2On a gauze, in addition, TiO in equal mass2Different contents of tourmaline are immobilized on gauze with different qualities of composite photocatalyst, and different contents of tourmaline to TiO are measured2The results of the experiment are shown in fig. 4. The result shows that the TiO of the tourmaline is loaded2To nailThe degradation rate of aldehyde is almost 100 percent, which is higher than that of pure TiO2The degradation rate of the tourmaline to the formaldehyde shows that the tourmaline has the effect of degrading TiO2The photocatalysis of (1) has a promoting effect.
2)TiO2Stability test of tourmaline gauze for degrading formaldehyde gas
TiO with tourmaline content of 1%2Tourmaline gauze pair 100mg/m3The degradation rate of formaldehyde was measured in four replicates and the results are shown in FIG. 5. The results show that TiO2The tourmaline gauze has good stability and can be repeatedly used.
3) TiO of different quality2Influence of tourmaline gauze on Formaldehyde degradation Performance
TiO with tourmaline content of 1% and the mass of 0.048g, 0.128g, O.170g, 0.220g and 0.232g respectively supported on the gauze2Tourmaline composite photocatalyst and method for measuring TiO with different qualities2The effect of tourmaline gauze on formaldehyde degradation performance, and the experimental results are shown in fig. 6. The result shows that the degradation rate of formaldehyde gradually increases along with the increase of the catalyst within a certain range until the catalyst is about 0.232g, and at the moment, the catalyst on the surface of the gauze is completely loaded, and the degradation rate is maximum and reaches 100%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, equivalents, improvements and the like, which are within the spirit and principle of the present invention, should be included in the scope of the present invention.
Claims (10)
1. TiO 22Tourmaline gauze, which is characterized in that: comprises the following steps of (a) carrying out,
1) dissolving ethyl cellulose in absolute ethyl alcohol as a binder under the condition of 70-90 ℃ water bath;
2) soaking the gauze in the binder in the step 1) for 3-5 min, taking out, opening meshes of the gauze, and then, TiO2Spraying tourmaline composite photocatalyst powder onto gauze, and air drying at room temperature to obtain TiO2Tourmaline gauze; the impregnated gauze is opened through a blowing method;
the TiO is2The preparation of the tourmaline composite photocatalyst comprises the following steps,
a) adding a certain amount of glacial acetic acid into absolute ethyl alcohol, and stirring to uniformly mix; slowly adding tetrabutyl titanate, and stirring to obtain a tetrabutyl titanate solution;
b) adding a proper amount of tourmaline powder into the other part of absolute ethyl alcohol for ultrasonic treatment to obtain a tourmaline powder solution;
c) dripping the tetrabutyl titanate solution obtained in the step a) into the tourmaline solution obtained in the step b), and stirring; obtaining a mixed solution;
d) uniformly mixing absolute ethyl alcohol, deionized water and concentrated hydrochloric acid;
e) dropwise adding the solution obtained in the step d) into the mixed solution obtained in the step c), stirring to form gray sol, and then stirring at a certain temperature to form gel;
f) drying, grinding and calcining the gel to form TiO2Tourmaline composite photocatalyst powder.
2. The TiO of claim 12Tourmaline gauze, which is characterized in that: the amount of tetrabutyl titanate and glacial acetic acid corresponding to every 0.012-0.23 g of tourmaline powder is 8-12 ml and 4-5 ml respectively.
3. The TiO of claim 12Tourmaline gauze, which is characterized in that: in the step a), the volume ratio of the glacial acetic acid to the absolute ethyl alcohol is as follows: (4-5) to (20-25); adding glacial acetic acid into absolute ethyl alcohol, and stirring for 10-20 min; adding tetrabutyl titanate and stirring for 20-30 min.
4. The TiO of claim 12Tourmaline gauze, which is characterized in that: in the step a), adding glacial acetic acid into absolute ethyl alcohol, and stirring for 10 min; tetrabutyl titanate is added and stirred for 30 min.
5. The TiO of claim 12Tourmaline gauze, which is characterized in that: in step b), every 30mLThe content of the tourmaline powder added into the water ethanol is 0.012-0.23 g; adding tourmaline powder into absolute ethyl alcohol, and then carrying out ultrasonic treatment for 20-30 min; the tourmaline powder is obtained after pretreatment and comprises the following steps of adding distilled water into a tourmaline raw material, ultrasonically dispersing for 1-1.5 h, then adding 1-2 mol/L dilute hydrochloric acid solution, ultrasonically dispersing for 1-1.5 h, standing for 12-24 h, finally repeatedly washing with distilled water until the tourmaline powder is neutral, and drying at 80-100 ℃ for later use.
6. The TiO of claim 12Tourmaline gauze, which is characterized in that: in the step c), the tetrabutyl titanate solution obtained in the step a) is dripped into the tourmaline solution obtained in the step b) at the speed of 8-10 ml/min; and after the dropwise addition is finished, stirring the mixed solution for 1-1.5 h at the stirring speed of 180-200 r/min.
7. The TiO of claim 12Tourmaline gauze, which is characterized in that: in the step d), the volume ratio of the absolute ethyl alcohol to the deionized water is (20-25 ml) to (8-12 ml); after mixing, the pH of the solution is 1.7-2.
8. The TiO of claim 12Tourmaline gauze, which is characterized in that: in the step e), the solution obtained in the step d) is dropwise added to the mixed solution obtained in the step c) at the speed of 3-5 ml/min, and stirring is carried out at the stirring speed of 180-200 r/min in the dropwise adding process; after dropwise adding, continuously stirring for 1-2 h at a stirring speed of 180-200 r/min; after the gray sol is formed, gelling for 2-3 h at the temperature of 40-60 ℃ and the stirring speed of 30-40 rpm;
in the step f), drying at the temperature of 80-100 ℃ for 10-12 h; the calcining temperature is 450-550 ℃, and the calcining time is 2-4 h.
9. The TiO of claim 12Tourmaline gauze, which is characterized in that: in the step 1), 1-2 g of ethyl cellulose is added into every 50mL of absolute ethyl alcohol.
10. The E.E. 1E9 the TiO of any one of2Application of tourmaline gauze in removing formaldehyde.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1522954A (en) * | 2003-09-10 | 2004-08-25 | 河北工业大学 | Tourmaline/titanium dioxide composite collosol and preparing method and use thereof |
| CN102836729A (en) * | 2012-09-06 | 2012-12-26 | 中国地质大学（北京） | Preparation of TiO2/schorlite composite photo-catalytic material |
| CN102895972A (en) * | 2012-10-17 | 2013-01-30 | 陕西科技大学 | Method for preparing negative ion material used for organic pollutant and sewage treatment and having photo-catalysis performance |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101302571B1 (en) * | 2011-07-04 | 2013-09-02 | 이상철 | Environment-Friendly Multi-functional Natural Paint and the Manufacturing Method Thereof |
| CN104492674B (en) * | 2014-11-20 | 2017-02-01 | 东南大学 | Method for preparing graphene-based air conditioner filter net by spraying method |
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| CN205876146U (en) * | 2016-06-08 | 2017-01-11 | 中健一生（北京）国际医学科技有限公司 | Antifog haze window screening of static separation |
-
2017
- 2017-04-01 CN CN201710218890.7A patent/CN107774241B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1522954A (en) * | 2003-09-10 | 2004-08-25 | 河北工业大学 | Tourmaline/titanium dioxide composite collosol and preparing method and use thereof |
| CN102836729A (en) * | 2012-09-06 | 2012-12-26 | 中国地质大学（北京） | Preparation of TiO2/schorlite composite photo-catalytic material |
| CN102895972A (en) * | 2012-10-17 | 2013-01-30 | 陕西科技大学 | Method for preparing negative ion material used for organic pollutant and sewage treatment and having photo-catalysis performance |
Non-Patent Citations (4)
| Title |
|---|
| 余力.超声助电气石类芬顿及电气石负载TiO2光催化降解水中双酚A的研究.《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》.2015, * |
| 气相中乙酸乙酯光解的光子效率: 波长和催化剂的影响;方雪慧等;《环境科学》;20150630;第36卷(第6期);2010页1.1部分 * |
| 电气石对纳米二氧化钛结构及光催化性能的影响;高如琴等;《硅酸盐学报》;20140731;第42卷(第7期);920页摘要 * |
| 超声助电气石类芬顿及电气石负载TiO2光催化降解水中双酚A的研究;余力;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20150215;35页3.2.1.2部分 * |
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