CN112742365A - Preparation method of hollow porous photocatalyst carrier - Google Patents
Preparation method of hollow porous photocatalyst carrier Download PDFInfo
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- CN112742365A CN112742365A CN202011642576.XA CN202011642576A CN112742365A CN 112742365 A CN112742365 A CN 112742365A CN 202011642576 A CN202011642576 A CN 202011642576A CN 112742365 A CN112742365 A CN 112742365A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000005286 illumination Methods 0.000 claims abstract description 23
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005507 spraying Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 15
- 238000010926 purge Methods 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 239000001856 Ethyl cellulose Substances 0.000 claims description 10
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 10
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 10
- 229920001249 ethyl cellulose Polymers 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000012798 spherical particle Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229920000609 methyl cellulose Polymers 0.000 claims description 5
- 239000001923 methylcellulose Substances 0.000 claims description 5
- 235000010981 methylcellulose Nutrition 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 11
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract description 8
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000011796 hollow space material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 241000233866 Fungi Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
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- 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
- B01J21/12—Silica and alumina
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/657—Pore diameter larger than 1000 nm
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0063—Granulating
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/345—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of ultraviolet wave energy
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Abstract
The invention belongs to the field of photocatalysis, and relates to a preparation method of a hollow porous photocatalyst carrier. The method solves the blank of the hollow mesoporous type carrier, converts the ethanol solubility and the hydrolysis characteristic of aluminum isopropoxide into aluminum hydroxide, and simultaneously converts the aluminum hydroxide into active oxidation in the constant-temperature illumination treatment process to leave an intermolecular mesoporous structure.
Description
Technical Field
The invention belongs to the field of photocatalysis, and relates to a preparation method of a hollow porous photocatalyst carrier.
Background
The photocatalyst is also called a photocatalyst, and is a generic name of a semiconductor material having a photocatalytic function represented by nano-sized titanium dioxide. A typical photocatalytic material is titanium dioxide, which generates a substance having a strong oxidizing property (e.g., hydroxyl radical, oxygen, etc.) under light irradiation, and is useful for decomposing organic compounds, partially inorganic compounds, bacteria, viruses, etc. In daily life, the photocatalyst can effectively degrade toxic and harmful gases in the air, such as formaldehyde and the like, and efficiently purify the air; meanwhile, various bacteria can be effectively killed, and toxin released by the bacteria or fungi can be decomposed and harmlessly treated.
In the actual use process, the titanium dioxide has a good degradation effect on low molecular organic matters and has a high degradation speed, but in the case of high molecular materials, the titanium dioxide has a low degradation speed, and even the catalyst is inactivated due to high molecular coverage. Therefore, the mesoporous photocatalyst becomes one of the research hotspots. However, there is no report on a mesoporous photocatalyst support.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a hollow mesoporous photocatalyst carrier, which solves the blank of the hollow mesoporous photocatalyst carrier, converts aluminum isopropoxide into aluminum hydroxide by utilizing the ethanol solubility and hydrolysis characteristics of the aluminum isopropoxide, and simultaneously converts the aluminum hydroxide into active oxidation in the constant-temperature illumination treatment process to leave an intermolecular mesoporous structure.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a hollow mesoporous photocatalyst carrier takes alumina and silica as surface shell structures, the surface shell structures are mesoporous structures, and the center of the carrier is hollow.
The preparation method comprises the following steps:
step 1, adding ethyl cellulose into absolute ethyl alcohol, performing low-temperature ultrasonic treatment for 10-40min, and performing constant-temperature granulation to form methyl cellulose spherical particles, wherein the mass ratio of the ethyl cellulose to the absolute ethyl alcohol is 10:3-5, the low-temperature ultrasonic treatment temperature is 10-20 ℃, the ultrasonic frequency is 100-200kHz, the constant-temperature granulation temperature is 80-90 ℃, and the pressure is 0.13-0.15 MPa;
step 2, adding aluminum isopropoxide into absolute ethyl alcohol, uniformly stirring at a low temperature, adding ethyl silicate, and performing low-temperature ultrasonic treatment until the ethyl silicate is completely dispersed to form a mixed alcohol solution; the concentration of the aluminum isopropoxide in the absolute ethyl alcohol is 5-10g/L, the low-temperature stirring speed is 1000-2000r/min, the temperature is 5-10 ℃, the adding amount of the ethyl silicate is 25-40% of the mass of the aluminum isopropoxide, the low-temperature ultrasonic temperature is 2-8 ℃, and the ultrasonic frequency is 40-80 kHz;
step 3, spraying the mixed alcohol solution on the surface of the spherical particles, drying at constant temperature for 10-20min, standing at constant temperature in a reaction kettle containing water vapor for 30-60min, and heating and drying to obtain coating particles; the spraying amount of the spraying is 15-30mL/cm2The constant-temperature drying temperature is 80-90 ℃, and the spraying amount of the spraying is formed by coating in a mode of repeatedly spraying and drying for 10-20 times; the volume content of the water vapor in the reaction kettle in the air is 3-8%, the constant-temperature standing temperature is 110-130 ℃, and the temperature for heating and drying is 110-120 ℃;
step 4, placing the coated particles into a light reaction kettle for light treatment for 2-5h, and purging with nitrogen for 1-4h to obtain a hollow mesoporous photocatalyst carrier; the volume content of oxygen in the air of the illumination reaction kettle is 40-60%, the illumination treatment adopts ultraviolet illumination treatment, and the surface illumination intensity is 10-20mW/cm2The temperature is 150-160 ℃, the temperature of the nitrogen purging is 110-120 ℃, and the purging speed is 1-3 mL/min.
From the above description, it can be seen that the present invention has the following advantages:
1. the method solves the blank of the hollow mesoporous type carrier, converts the ethanol solubility and the hydrolysis characteristic of aluminum isopropoxide into aluminum hydroxide, and simultaneously converts the aluminum hydroxide into active oxidation in the constant-temperature illumination treatment process to leave an intermolecular mesoporous structure.
2. According to the invention, ethyl silicate is used as a silicon source dopant and forms a bond with active alumina in a hydrolysis process to form a shell structure, and meanwhile, the light transmittance of the silicon dioxide machine can ensure that light enters the hollow space and the photocatalytic reaction is carried out.
Detailed Description
The present invention is described in detail with reference to examples, but the present invention is not limited to the claims.
Example 1
A hollow mesoporous photocatalyst carrier takes alumina and silica as surface shell structures, the surface shell is a mesoporous structure, the center of the carrier is hollow:
the preparation method comprises the following steps:
step 1, adding ethyl cellulose into absolute ethyl alcohol, performing low-temperature ultrasonic treatment for 10min, and performing constant-temperature granulation to form methyl cellulose spherical particles, wherein the mass ratio of the ethyl cellulose to the absolute ethyl alcohol is 10:3-5, the temperature of the low-temperature ultrasonic treatment is 10 ℃, the ultrasonic frequency is 100kHz, the temperature of the constant-temperature granulation is 80 ℃, and the pressure is 0.13 MPa;
step 2, adding aluminum isopropoxide into 1L of absolute ethyl alcohol, uniformly stirring at a low temperature, adding ethyl silicate, and performing low-temperature ultrasonic treatment until the mixture is completely dispersed to form a mixed alcohol solution; the concentration of the aluminum isopropoxide in the absolute ethyl alcohol is 5-10g/L, the low-temperature stirring speed is 1000r/min, the temperature is 5 ℃, the adding amount of the ethyl silicate is 25% of the mass of the aluminum isopropoxide, the low-temperature ultrasonic temperature is 2 ℃, and the ultrasonic frequency is 40 kHz;
step 3, spraying the mixed alcohol solution on the surface of the spherical particles, drying at constant temperature for 10min, standing at constant temperature in a reaction kettle containing water vapor for 30min, and heating and drying to obtain coated particles; the spraying amount of the spraying is 15mL/cm2The constant-temperature drying temperature is 80 ℃, and the spraying amount of the spraying is formed by coating in a mode of repeatedly spraying and drying for 10 times; the volume content of the water vapor in the reaction kettle in the air is 3%, the constant-temperature standing temperature is 110 ℃, and the temperature for heating and drying is 110 ℃;
step 4, placing the coated particles into a light reaction kettle for light treatment for 2 hours, and purging with nitrogen for 1 hour to obtain a hollow mesoporous photocatalyst carrier; the volume content of oxygen in the air of the illumination reaction kettle is 40%, the illumination treatment adopts ultraviolet illumination treatment, and the surface illumination intensity is 10mW/cm2The temperature is 150 ℃, the temperature of the nitrogen purging is 110 ℃, and the purging speed is 1 mL/min.
The diameter of the catalyst carrier prepared by the embodiment is 2mm, the diameter of the hollow part is 1.4mm, the structure is stable, and the micron-sized mesopores are formed on the surface.
Example 2
A hollow mesoporous photocatalyst carrier takes alumina and silica as surface shell structures, the surface shell structures are mesoporous structures, and the center of the carrier is hollow.
The preparation method comprises the following steps:
step 1, adding ethyl cellulose into absolute ethyl alcohol, performing low-temperature ultrasonic treatment for 40min, and performing constant-temperature granulation to form methyl cellulose spherical particles, wherein the mass ratio of the ethyl cellulose to the absolute ethyl alcohol is 2:1, the temperature of the low-temperature ultrasonic treatment is 20 ℃, the ultrasonic frequency is 200kHz, the temperature of the constant-temperature granulation is 90 ℃, and the pressure is 0.15 MPa;
step 2, adding aluminum isopropoxide into absolute ethyl alcohol, uniformly stirring at a low temperature, adding ethyl silicate, and performing low-temperature ultrasonic treatment until the ethyl silicate is completely dispersed to form a mixed alcohol solution; the concentration of the aluminum isopropoxide in the absolute ethyl alcohol is 10g/L, the low-temperature stirring speed is 2000r/min, the temperature is 10 ℃, the adding amount of the ethyl silicate is 40 percent of the mass of the aluminum isopropoxide, the low-temperature ultrasonic temperature is 8 ℃, and the ultrasonic frequency is 80 kHz;
step 3, spraying the mixed alcohol solution on the surface of the spherical particles, drying at constant temperature for 20min, standing at constant temperature in a reaction kettle containing water vapor for 60min, and heating and drying to obtain coated particles; the spraying amount of the spraying is 30mL/cm2The constant-temperature drying temperature is 90 ℃, and the spraying amount of the spraying is formed by coating in a mode of repeatedly spraying and drying for 20 times; the volume content of the water vapor in the reaction kettle in the air is 8%, the constant-temperature standing temperature is 130 ℃, and the temperature for heating and drying is 120 ℃;
step 4, placing the coated particles into a light reaction kettle for light treatment for 5 hours, and purging with nitrogen for 4 hours to obtain a hollow mesoporous photocatalyst carrier; the volume content of oxygen in the air of the illumination reaction kettle is 60%, the illumination treatment adopts ultraviolet illumination treatment, and the surface illumination intensity is 20mW/cm2The temperature is 160 ℃, the temperature of the nitrogen purging is 120 ℃, and the purging speed is 3 mL/min.
The diameter of the catalyst carrier prepared by the embodiment is 3mm, the diameter of the hollow part is 2.5mm, the structure is stable, and the micron-sized mesopores are formed on the surface.
Example 3
A hollow mesoporous photocatalyst carrier takes alumina and silica as surface shell structures, the surface shell structures are mesoporous structures, and the center of the carrier is hollow.
The preparation method comprises the following steps:
step 1, adding ethyl cellulose into absolute ethyl alcohol, performing low-temperature ultrasonic treatment for 30min, and performing constant-temperature granulation to form methyl cellulose spherical particles, wherein the mass ratio of the ethyl cellulose to the absolute ethyl alcohol is 5:2, the temperature of the low-temperature ultrasonic treatment is 15 ℃, the ultrasonic frequency is 150kHz, the temperature of the constant-temperature granulation is 85 ℃, and the pressure is 0.14 MPa;
step 2, adding aluminum isopropoxide into 1L of absolute ethyl alcohol, uniformly stirring at a low temperature, adding ethyl silicate, and performing low-temperature ultrasonic treatment until the mixture is completely dispersed to form a mixed alcohol solution; the concentration of the aluminum isopropoxide in the absolute ethyl alcohol is 8g/L, the low-temperature stirring speed is 1500r/min, the temperature is 8 ℃, the adding amount of the ethyl silicate is 35 percent of the mass of the aluminum isopropoxide, the low-temperature ultrasonic temperature is 6 ℃, and the ultrasonic frequency is 60 kHz;
step 3, spraying the mixed alcohol solution on the surface of the spherical particles, drying at constant temperature for 15min, standing at constant temperature in a reaction kettle containing water vapor for 50min, and heating and drying to obtain coated particles; the spraying amount of the spraying is 20mL/cm2The constant-temperature drying temperature is 85 ℃, and the spraying amount of the spraying is formed by coating in a mode of repeatedly spraying and drying for 15 times; the volume content of the water vapor in the reaction kettle in the air is 6%, the constant-temperature standing temperature is 120 ℃, and the temperature for heating and drying is 115 ℃;
step 4, placing the coated particles into a light reaction kettle for light treatment for 4 hours, and purging with nitrogen for 3 hours to obtain a hollow mesoporous photocatalyst carrier; the volume content of oxygen in the air of the illumination reaction kettle is 50%, the illumination treatment adopts ultraviolet illumination treatment, and the surface illumination intensity is 15mW/cm2The temperature was 155 ℃, the temperature of the nitrogen purge was 115 ℃, and the purge rate was 2 mL/min.
The diameter of the catalyst carrier prepared by the embodiment is 2.5mm, the diameter of the hollow part is 1.9mm, the structure is stable, and the micron-sized mesopores are formed on the surface.
In summary, the invention has the following advantages:
1. the method solves the blank of the hollow mesoporous type carrier, converts the ethanol solubility and the hydrolysis characteristic of aluminum isopropoxide into aluminum hydroxide, and simultaneously converts the aluminum hydroxide into active oxidation in the constant-temperature illumination treatment process to leave an intermolecular mesoporous structure.
2. According to the invention, ethyl silicate is used as a silicon source dopant and forms a bond with active alumina in a hydrolysis process to form a shell structure, and meanwhile, the light transmittance of the silicon dioxide machine can ensure that light enters the hollow space and the photocatalytic reaction is carried out.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (10)
1. A hollow mesoporous photocatalyst carrier is characterized in that: the alumina and the silicon dioxide are used as surface shell structures, the surface shell layers are of mesoporous structures, and the center of the carrier is hollow.
2. The hollow mesoporous type photocatalyst carrier according to claim 1, characterized in that: the preparation method of the carrier comprises the following steps:
step 1, adding ethyl cellulose into absolute ethyl alcohol, performing low-temperature ultrasonic treatment for 10-40min, and granulating at constant temperature to form methyl cellulose spherical particles;
step 2, adding aluminum isopropoxide into absolute ethyl alcohol, uniformly stirring at a low temperature, adding ethyl silicate, and performing low-temperature ultrasonic treatment until the ethyl silicate is completely dispersed to form a mixed alcohol solution;
step 3, spraying the mixed alcohol solution on the surface of the spherical particles, drying at constant temperature for 10-20min, standing at constant temperature in a reaction kettle containing water vapor for 30-60min, and heating and drying to obtain coating particles;
and 4, placing the coated particles into a light reaction kettle for light treatment for 2-5h, and purging with nitrogen for 1-4h to obtain the hollow mesoporous photocatalyst carrier.
3. The hollow mesoporous type photocatalyst carrier according to claim 2, characterized in that: the mass ratio of the ethyl cellulose to the absolute ethyl alcohol in the step 1 is 10:3-5, the low-temperature ultrasonic temperature is 10-20 ℃, and the ultrasonic frequency is 100-200 kHz.
4. The hollow mesoporous type photocatalyst carrier according to claim 2, characterized in that: the temperature of the constant-temperature granulation in the step 1 is 80-90 ℃, and the pressure is 0.13-0.15 MPa.
5. The hollow mesoporous type photocatalyst carrier according to claim 2, characterized in that: the concentration of the aluminum isopropoxide in the absolute ethyl alcohol in the step 2 is 5-10g/L, the low-temperature stirring speed is 1000-2000r/min, and the temperature is 5-10 ℃.
6. The hollow mesoporous type photocatalyst carrier according to claim 2, characterized in that: the adding amount of the ethyl silicate in the step 2 is 25-40% of the mass of the aluminum isopropoxide, the low-temperature ultrasonic temperature is 2-8 ℃, and the ultrasonic frequency is 40-80 kHz.
7. The hollow mesoporous type photocatalyst carrier according to claim 2, characterized in that: the spraying amount of the spraying in the step 3 is 15-30mL/cm2The constant temperature drying temperature is 80-90 ℃, and the spraying amount of the spraying is formed by coating in a mode of repeatedly spraying and drying for 10-20 times.
8. The hollow mesoporous type photocatalyst carrier according to claim 2, characterized in that: the volume content of the water vapor in the reaction kettle in the step 3 in the air is 3-8%, the temperature for constant temperature standing is 110-.
9. The hollow mesoporous type photocatalyst carrier according to claim 2, characterized in that: the volume content of oxygen in the air of the illumination reaction kettle in the step 4 is 40-60%, and ultraviolet light is adopted for illumination treatmentIrradiating with surface illumination intensity of 10-20mW/cm2The temperature is 150-160 ℃.
10. The hollow mesoporous type photocatalyst carrier according to claim 2, characterized in that: the temperature of the nitrogen purging in the step 4 is 110-120 ℃, and the purging speed is 1-3 mL/min.
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