CN109772260A - Gallic oxide-adsorbent composite material and its preparation method and application - Google Patents
Gallic oxide-adsorbent composite material and its preparation method and application Download PDFInfo
- Publication number
- CN109772260A CN109772260A CN201711104854.4A CN201711104854A CN109772260A CN 109772260 A CN109772260 A CN 109772260A CN 201711104854 A CN201711104854 A CN 201711104854A CN 109772260 A CN109772260 A CN 109772260A
- Authority
- CN
- China
- Prior art keywords
- composite material
- gallium
- carrier
- adsorbent
- nanometers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
-
- 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
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
Abstract
This application involves gallic oxide-adsorbent composite materials and its preparation method and application.The composite material includes zeolite adsorbents and the gallic oxide (Ga being supported on the zeolite adsorbents2O3) nano particle.The preparation method of the composite material include provide comprising gallium presoma, carrier and can dissolve gallium presoma organic solvent suspension, wherein the organic solvent can be miscible with water；The aqueous solution of alkali is added in the suspension to generate Ga (OH) in situ on carrier3；Load has Ga (OH) thereon with separation3Carrier and calcined to obtain the composite material.The composite material can be used for purifying air, such as in air purifier.
Description
Technical field
This invention relates generally to photochemical catalyst-adsorbent composite material with and its preparation method and application.Specifically, originally
Invention is related to gallic oxide-Zeolite composite materials, preparation method, the air cleaning unit comprising the composite material and institute
State purposes of the composite material for air cleaning.
Background technique
Today's society, air pollution become seriously, the pollutant effect people's health in air.Pollutant in air
Including volatile organic compounds (VOC), the VOC include formaldehyde, ammonia, hydrogen sulfide, benzene,toluene,xylene, paracide,
Ethylbenzene, styrene, acetaldehyde, cyclohexanone, isophorone, methanol, ethyl alcohol, phenol, acetone, ethyl acetate, n-butanol, methyl tert-butyl
Base ketone, n-butyl acetate, acetophenone, methyl ethyl ketone, isopropanol, methylene chloride, trichloro ethylene, n-hexane, acetic acid 2- methoxy
Base ethyl ester, nitrobenzene, bis- (2- methoxy ethyl) ethers, 1,3,5- trimethylbenzene etc..It can be made a return journey using air cleaning unit
Except the pollutant in air.In air cleaning unit, adsorbent such as active carbon can be set and carry out the physical absorption from air
Pollutant.But there are problems that adsorbent adsorption capacity is limited and needs to regularly replace using adsorbent.Photochemical catalyst is for example
TiO2Also be used to purify air.Although photochemical catalyst can decomposing pollutant to thoroughly removing pollutant, it is existing
There is, catalytic capability indifferent to the catalytic decomposition of aromatic series VOC and decline and discharge intermediate after use in photochemical catalyst
The problems such as equal.
The invention is intended to provide composite material, one or more existing in the prior art ask can be eliminated or improved
Topic.Composite material of the invention can for example have higher catalytic capability (especially to aromatic series VOC), can reuse
(using for a long time), and/or it is not present or is substantially not present intermediate release problem.It is described multiple the present invention also provides that can prepare
The method of condensation material.The method can not only prepare the composite material, and safety it is good, it is easy to operate, easily controllable,
It is reproducible, environmental-friendly.
Summary of the invention
One aspect of the present invention is related to photochemical catalyst-adsorbent composite material, it includes zeolite adsorbents and is supported on
Gallic oxide (Ga on the zeolite adsorbents2O3) nano particle, the wherein silica alumina ratio (SiO of the zeolite adsorbents2/Al2O3It rubs
Your ratio) it is about 10- about 500 and the aperture of the zeolite adsorbents is about 0.6 nanometer-about 1.3 nanometers.
In one embodiment, the gallic oxide nano particle is formed in zeolite adsorbents surface in situ.
According to an embodiment, the partial size of the gallic oxide nano particle can be about 3 nanometers-about 50 nanometers.
In one embodiment, the zeolite adsorbents can be FAU type zeolite or BEA type zeolite, preferably Na-Y
Type zeolite.In one embodiment, the specific surface area of the photochemical catalyst-adsorbent composite material, which is greater than, is equal to about 250m2/
g.In one embodiment, the amount of the gallic oxide nano particle is the photochemical catalyst-adsorbent composite material weight
The about 10%- about 60% of amount.In one embodiment, the gallic oxide nano particle includes β-Ga2O3Nano particle.
Another aspect of the present invention is related to a kind of preparing nanometer gallic oxide-carrier composite material method, the party
Method can be used for preparing nanometer gallic oxide-carrier composite material of such as the application.Generally, the method for the present invention includes
Following steps: provide comprising gallium presoma, carrier and can dissolve gallium presoma organic solvent suspension, wherein this is organic
Solvent can be miscible with water；The aqueous solution of alkali is added in the suspension to generate Ga (OH) in situ on carrier3；And separation
Load has Ga (OH) thereon3Carrier and calcined to obtain the composite material.In one embodiment, the gallium forerunner
Body is gallium salt, including such as gallium nitrate, gallium chloride, gallium sulfate, gallium bromide, acetic acid gallium, gallium formate and acetylacetone,2,4-pentanedione gallium etc..
In one embodiment, it is compound that the carrier used in the method for the invention can be photochemical catalyst-adsorbent of the invention
Zeolite adsorbents in material.In one embodiment, the organic solvent can be selected from ethyl alcohol, methanol, isopropanol, second two
Alcohol, butanediol, glycerol, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide and dimethyl acetamide.In one embodiment,
The alkali can be selected from ammonia, methyl amine, dimethyl amine, Trimethylamine, ethylamine, diethylamide, triethylamine, propyl amine, dipropyl
Base amine, tripropylamine, diethylmethyl amine, ethyldimethyl amine, isopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, aminopropan
Alcohol, ethanol amine, diethanol amine, diethylenetriamines, trien, hydroxyethyl ethylenediamine, tetramethylammonium hydroxide, tetrem
Base ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and hexamethylene diamine, the preferably described alkali is ammonia.When alkali is
When ammonia, the concentration of ammonia spirit can be about 5wt%- about 28wt%.In one embodiment, the calcining can about 600 DEG C-
About 800 DEG C of temperature carries out.In one embodiment, the amount of gallium presoma is based on gallium presoma and organic in the suspension
The total weight of solvent is total weight of the amount of carrier in about 5%- about 50% and/or the suspension based on carrier and organic solvent
It is about 2%- about 20%.
An additional aspect of the present invention is related to air cleaning unit comprising photochemical catalyst-adsorbent of the invention is compound
Material.The invention further relates to the purposes that photochemical catalyst-adsorbent composite material of the invention is used to purify air.
Detailed description of the invention
Fig. 1 is the EDS energy spectrum diagram of the composite material of embodiment 1；
Fig. 2 is the composite material of embodiment 1 and the size distribution of HiSiv 1000；
Fig. 3 is the TEM image of the composite material of embodiment 1；
Fig. 4 is the SEM image of the composite material of embodiment 1；
Fig. 5 is the XRD diagram picture of the composite material of embodiment 1；
Fig. 6 is the Ga of embodiment 22O3The TEM image of nano particle；
Fig. 7 is toluene absorption and the degradation figure of the composite material of embodiment 1；
Fig. 8 is Ga prepared by embodiment 22O3The toluene of nano particle adsorbs and degradation figure；
Fig. 9 is Ga prepared by embodiment 22O31:1 (weight ratio) physical mixture of 1000 zeolite of nano particle and HiSiv
Toluene absorption and degradation figure；
Figure 10 is toluene absorption and the degradation figure of the composite material of embodiment 1；
Figure 11 is the composite material and business TiO of embodiment 12Toluene absorption and degradation property comparison；
Figure 12 shows the repeat performance of the composite material of embodiment 1；
Figure 13 is toluene absorption and the degradation figure of HiSiv 1000；
Figure 14 is Ga2O3Content is the TEM image of the composite material of 30wt%；
Figure 15 is Ga2O3Content is the TEM image of the composite material of 40wt%；
Figure 16 is Ga2O3Content is toluene absorption and the degradation figure of the composite material of 30wt%；
Figure 17 is Ga2O3Content is toluene absorption and the degradation figure of the composite material of 40wt%；
Figure 18 is toluene absorption and the degradation figure of sample 8；
Figure 19 is toluene absorption and the degradation figure of sample 9；With
Figure 20 is the gas chromatogram shown with the presence or absence of intermediate.
Specific embodiment
The invention discloses a kind of photochemical catalyst-adsorbent composite material, which includes zeolite adsorbents and bears
Gallic oxide (the Ga being loaded on the zeolite adsorbents2O3) nano particle, the wherein silica alumina ratio (SiO of the zeolite adsorbents2/
Al2O3Molar ratio) it is about 10- about 500 and the aperture of the zeolite adsorbents is about 0.6 nanometer-about 1.3 nanometers.
Gallic oxide (Ga2O3) it is known to be a kind of oxide semiconductor material.The inventors found that three oxidations two
Gallium, especially β-Ga2O3, photochemical catalyst is potentially acted as carrying out degradation of contaminant in air cleaning.Therefore, the present invention provides
Gallic oxide-adsorbent composite material can be used for purifying air, remove the pollutant in air, such as volatility has
Machine compound (VOC).As the example of VOC, it can be mentioned that alcohol, ether, aldehyde, ketone, ester, aliphatic hydrocarbon, aromatic hydrocarbon, halogenated hydrocarbons etc., example
Such as formaldehyde, ammonia, hydrogen sulfide, benzene,toluene,xylene, paracide, ethylbenzene, styrene, acetaldehyde, cyclohexanone, isophorone, first
Alcohol, ethyl alcohol, phenol, acetone, ethyl acetate, n-butanol, methyl iso-butyl ketone (MIBK), n-butyl acetate, acetophenone, methyl ethyl ketone,
Isopropanol, methylene chloride, trichloro ethylene, n-hexane, 2-Methoxyethyl acetate, nitrobenzene, bis- (2- methoxy ethyl) ethers, 1,
3,5- trimethylbenzene etc..
In the present invention, nano particle refers to that partial size is no more than 100 nanometers of particle.
In the present invention, the adsorbent can be used for the adsorbent of air cleaning.According to an embodiment, described
Adsorbent can be zeolite adsorbents.According to an embodiment, the silica alumina ratio (SiO of the zeolite adsorbents2/Al2O3Molar ratio)
It is about 10- about 500, preferably from about 18- about 300, more preferably from about 20- about 200.According to another embodiment, the zeolite adsorbents
Aperture be about 0.6 nanometer-about 1.3 nanometers, about 1.0 nanometers of preferably from about 0.6-, about 0.9 nanometer of more preferably from about 0.7-；Wherein should
Aperture is the average pore size obtained using BET method.It is believed that select above-mentioned silica alumina ratio to have it is advantageous to the affine of VOC
Property, and above-mentioned aperture is selected to be conducive to adsorb certain biggish VOC molecules, such as benzene and toluene etc..
In one embodiment, the zeolite adsorbents in the present invention are FAU type and/or BEA type zeolite.At one
In preferred embodiment, the zeolite adsorbents are Na-Y type zeolites.
According to an embodiment, the zeolite adsorbents of the invention are all stable in acid and alkaline environment,
It such as in the pH range of about 4- about 9 is stable.Zeolite adsorbents with such acid/base stability are resistant to the present invention
Composite material preparation process in reaction condition, be conducive to the stability and repeatability of preparation process and product.
Although the zeolite adsorbents of the shapes such as threadiness, column can be used, the zeolite adsorbents usually with
Particle shape formula uses.According to an embodiment, the partial size (D50) of the zeolite adsorbents is about 0.5 micron-about 100 microns, excellent
About 1 micron-about 50 microns, more preferably from about 1 micron-about 20 microns of choosing.According to an embodiment, the ratio of the zeolite adsorbents
Surface area (BET) is about 300m2/ g- about 1000m2/ g, preferably from about 400m2/ g- about 900m2/ g, more preferably from about 500m2/ g- is about
800m2/g。
Zeolite adsorbents according to a preferred embodiment, in photochemical catalyst-adsorbent composite material of the invention
It is HiSivTM 1000。HiSivTM1000 be the commodity adsorbent of UOP LLC.As powder, HiSivTM1000 partial size
It (D50) is about 4 microns (dynamic light scattering method), specific surface area > 550m2/ g (BET), average pore size are about 0.75nm, silica alumina ratio
It is about 30.
In photochemical catalyst-adsorbent composite material of the invention, gallic oxide photochemical catalyst exists in granular form
In on adsorbent surface.Gallic oxide particle does not block the hole of adsorbent, and this is favourable, because this facilitates absorption dirt
Contaminate object.In one embodiment, the gallic oxide exists with form of nanoparticles.In one embodiment, described
The partial size of gallic oxide nano particle is about 3 nanometers-about 50 nanometers, and preferably from about 3 nanometers-about 30 nanometers, more preferably from about 4 receive
About 20 nanometers of meter -, still more preferably about 5 nanometers-about 10 nanometers.
It is a discovery of the invention that the composite material of the invention can be realized and (be degraded to the degradable of the VOC of absorption
CO2+H2O) to complete recovered zeolite adsorbent agent.It is believed that this is because Ga2O3It is enough to provide with broad-band gap (4.8eV)
Oxidation/reduction ability decomposes VOC.But simultaneously, Ga2O3Band gap it is not wide because wide band gap needs higher purple
Outer light energy excites Ga2O3.Higher UV energy may generate ozone in use, and this is unfavorable.
In one embodiment, the gallic oxide nano particle of the invention includes β-Ga2O3Nano particle.According to
Believe β-Ga2O3Nano particle stability with higher and with common photochemical catalyst such as TiO2VOC is directed to compared to being capable of providing
More excellent catalytic performance, for aromatic series VOC.
In one embodiment of the invention, photochemical catalyst-adsorbent composite material specific surface area of the invention
(BET) it is more than or equal to about 250m2/ g, preferably greater than or equal to about 300m2/g。
In photochemical catalyst-adsorbent composite material of the invention, it is not particularly limited the content of photochemical catalyst, this field
Technical staff, which can according to need, to be adjusted.In one embodiment, the amount of photochemical catalyst, such as gallic oxide nanometer
The amount of particle, it is more excellent for the photochemical catalyst-adsorbent composite material weight about 10%- about 60%, preferably from about 20%- about 50%
Select about 30%- about 50%.
In one embodiment of the invention, the gallic oxide nano particle in composite material of the present invention is in zeolite
What surface in situ was formed.Such as it can deposition gallium presoma be of the invention to obtain by using gallium presoma and on the zeolite surface
Composite material, as described in following method part.
Another aspect of the present invention is related to photochemical catalyst-adsorbent composite material of the present invention for purifying sky
The purposes of gas.Such as it can be by making the air comprising pollutant flow through the photochemical catalyst-adsorbent composite material, thus dirty
Dye object is adsorbed, and is decomposed under the irradiation of ultraviolet light by photochemical catalyst.
Nanometer gallic oxide-Zeolite composite materials of the invention have excellent air cleaning performance.Of the invention answers
Condensation material has the advantages that simultaneously commonly used in both the adsorbent of air cleaning and photochemical catalyst, including quickly to reduce VOC dense
Degree (adsorbent absorption) and VOC can be decomposed completely (photochemical catalyst mineralising, is completely decomposed into H2O and CO2), thus better than independent
Adsorbent or individual photochemical catalyst.The complete decomposition (high mineralization rate) of VOC is meant to regenerate the composite wood completely
Material, is enable to be used for a long time.Mineralising, which refers to, to be completely broken down as H2O and CO2；Mineralization rate refers to that the VOC being mineralized is accounted for
The ratio of VOC total amount.Such as by taking toluene as an example, the calculating of mineralization rate in the following ways: CO2Increment obtain mineralising divided by 7
Toluene amount, and measure mineralization rate divided by initial toluene in turn.
In addition, the disposal efficiency is better than present invention discover that in-situ composite of the invention can generate synergy
The physical mixture of photochemical catalyst and adsorbent.It is believed that using the porous zeolite adsorbents with strong adsorption capacity as Ga2O3
Carrier in situ can preferably prevent the reunion of nano particle, and can be realized pollutant targeting enrichment, make photocatalysis
Material is more effectively carried out light degradation, improves photochemical catalyst efficiency.
In addition, unexpectedly, nanometer gallic oxide of the invention is shown for mineralization ability, such as toluene
Write the photochemical catalyst nano-titanium dioxide for being better than the prior art, such as Evonik Degussa limited liability company (Evonik
Degussa P25).
The invention further relates to can prepare nanometer gallic oxide-carrier composite material method of the invention.
Preparation nanometer gallic oxide-carrier composite material method of the invention may comprise steps of: provide packet
Presoma containing gallium, carrier and can dissolve gallium presoma organic solvent suspension, wherein the organic solvent can be mixed with water
It is molten；The aqueous solution of alkali is added in the suspension to generate Ga (OH) in situ on carrier3；Load has Ga thereon with separation
(OH)3Carrier and calcined to obtain the composite material.It is miscible in the present invention to refer to that two kinds of liquid be in any proportion
Mutual phased soln.
In the preparation process in accordance with the present invention, described above is not limited to for loading the carrier of nanometer gallic oxide
Zeolite used in invention photochemical catalyst-adsorbent composite material, also can be used other carriers.Other carriers include natural mine
Object such as diatomite, sepiolite, montmorillonite, frog stone, kaolin etc.；Adsorbent except zeolite adsorbents of the invention；Glass
Such as glass fibre, bead, sheet glass etc.；Ceramics are such as ceramic particle.Those skilled in the art can be according to specifically answering
Suitable carrier is selected with demand.Such as by selecting zeolite adsorbents of the invention to be available for sky as carrier
The composite material with synergy of gas purification.Therefore, although present invention is generally directed to use zeolite adsorbents as carrier
Preparation nanometer gallic oxide-carrier composite material method of the invention described, but those skilled in the art understand that
Other materials can be used as carrier.
For the gallium presoma, the present invention be there is no particular requirement that, if it can be used in method of the invention simultaneously
Nanometer gallic oxide particle is provided in situ on carrier.In one embodiment, the gallium presoma is the salt of gallium.It is described
Gallium salt can be dissolved in organic solvent.As an example, gallium salt can be gallium nitrate, gallium chloride, gallium sulfate, gallium bromide, acetic acid gallium,
Gallium formate, acetylacetone,2,4-pentanedione gallium and their combination.Preferably, using gallium nitrate and gallium chloride.Gallium nitrate can be with hydrate
(Ga(NO3)3.nH2O) form provides.In the method for the invention, it can directly use nitric hydrate gallium as gallium presoma.It is right
In gallium chloride, gallium chloride can be directly used, can also react to form solution and then evaporation removing by gallium metal and hydrochloric acid
Excessive HCl and water obtain gallium chloride.
Include gallium presoma, carrier and the suspension of organic solvent of gallium presoma can be dissolved (carrier is not to provide
Dissolution is to be used as suspended material presence), it needs using organic solvent.Method of the invention is for the organic solvent without spy
It does not require, as long as the organic solvent can dissolve gallium presoma and the organic solvent can be miscible with water.As an example,
The organic solvent can be selected from ethyl alcohol, methanol, isopropanol, ethylene glycol, propylene glycol, butanediol, glycerol, tetrahydrofuran, diformazan
Base formamide, dimethyl sulfoxide, dimethyl acetamide and their mixture.In one embodiment, it is preferred to be made using ethyl alcohol
For organic solvent.
Generally, those skilled in the art with unrestricted choice and can adjust the amount of gallium presoma in the suspension, as long as
It can obtain the nanometer gallic oxide-carrier composite material with required property.According to an embodiment, the suspension
The amount of middle gallium presoma is about 5%- about 50%, preferably from about 5%- about 40% based on the total weight of gallium presoma and organic solvent, more excellent
Select about 8%- about 30%.According to an embodiment, the amount of gallium presoma is based on gallium presoma and organic solvent in the suspension
Total weight be at least about 9%, at least about 10%, at least about 11%, at least about 12%, at least about 13%, at least about 14%, at least about
15%, at least about 16%, at least about 17%, at least about 18%, at least about 19%, or at least about 20%, and no more than about 50%, or not
More than about 40%, or no more than about 30%.Inventor has found that the gallium forerunner of higher concentration can be used in method of the invention
Body simultaneously still obtains a nanometer gallic oxide particle.This is favourable, because the dosage of organic solvent can be reduced.
Generally, those skilled in the art can be with carrier such as zeolite adsorbents in unrestricted choice and the adjustment suspension
Amount, as long as the nanometer gallic oxide-carrier composite material with required property can be obtained.According to an embodiment,
Total weight of the carrier such as zeolite based on carrier and organic solvent in the suspension is about 2%- about 20%, for example, about
4%- about 10%.
In order to provide the suspension for including gallium presoma, carrier and organic solvent, gallium presoma can be dissolved in organic
Carrier is simultaneously then added in solvent；Or carrier can be added in organic solvent, gallium presoma is then added；Or it can incite somebody to action
Gallium presoma be dissolved in organic solvent and by support dispersion in organic solvent, then the two is merged；Or it can will be before gallium
Body and carrier is driven at least partly to be added in organic solvent simultaneously.In order to facilitate the dissolution of gallium presoma and/or the dispersion of carrier,
It can be stirred.The offer process can carry out under normal conditions, such as carry out under room temperature and atmospheric pressure conditions.
According to an embodiment, the carrier can be adsorbent, such as be commonly used for the absorption of air purification field
Agent.According to an embodiment, the carrier is zeolite adsorbents.
According to an embodiment, the partial size of the zeolite adsorbents is about 0.5 micron-about 100 microns, and preferably from about 1 is micro-
About 50 microns of meter -, more preferably from about 1 micron-about 20 microns.According to an embodiment, the specific surface area of the zeolite adsorbents
It (BET) is about 300m2/ g- about 1000m2/ g, preferably from about 400m2/ g- about 900m2/ g, more preferably from about 500m2/ g- about 800m2/g。
According to an embodiment, for the zeolite adsorbents as carrier, the silica alumina ratio (SiO of the zeolite adsorbents2/
Al2O3Molar ratio) it is about 10- about 500, preferably from about 18- about 300, more preferably from about 20- about 200.According to an embodiment, the boiling
The aperture of stone adsorbent is about 0.6 nanometer-about 1.3 nanometers, and about 1.0 nanometers of preferably from about 0.6-, more preferably from about 0.7- about 0.9 receives
Rice.
In one embodiment, the zeolite adsorbents used in the methods of the invention are FAU type and/or BEA type
Zeolite.In a preferred embodiment, the zeolite adsorbents are Na-Y type zeolites.
According to an embodiment, the zeolite adsorbents of the invention are all stable in acid and alkaline environment,
It such as in the pH range of about 4- about 9 is stable.Be conducive to preparation of the present invention with the stability in acid and alkaline environment
The progress of method, because can suffer from acid and/or alkaline environment during preparation method of the invention.Such as in present invention side
It include that the aqueous solution of alkali is added in the suspension in method, this pH that will lead to suspension becomes alkalinity.
According to a preferred embodiment, the zeolite adsorbents used in the methods of the invention are HiSivTM 1000。
HiSivTM1000 be the commodity adsorbent of UOP LLC.As powder, HiSivTM1000 partial size D50 is about 4 microns of (dynamics
Light scattering method), specific surface area > 550m2/ g (BET), average pore size are about 0.75nm, and silica alumina ratio is about 30.
After obtaining the suspension in the method for the present invention, the aqueous solution of alkali can be added in the suspension to come in carrier
Ga (OH) is generated on surface in situ3.The aqueous solution of the alkali can be by obtaining alkali is soluble in water.The aqueous solution of alkali of the invention is not
Include organic solvent.It generally, can be in carrier example when can be used in any aqueous solution addition suspension when alkali
As Ga (OH) is generated on zeolite surface in situ3Alkali.Organic bases such as amine etc. can be used.As the example of these alkali,
It can be mentioned that ammonia, methyl amine, dimethyl amine, Trimethylamine, ethylamine, diethylamide, triethylamine, propyl amine, dipropylamine,
Tripropylamine, diethylmethyl amine, ethyldimethyl amine, isopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, aminopropanol, second
Hydramine, diethanol amine, diethylenetriamines, trien, hydroxyethyl ethylenediamine, tetramethylammonium hydroxide, tetraethyl hydrogen
Amine-oxides, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, hexamethylene diamine and their combination.
In one embodiment of the invention, the alkali is ammonia.It is preferable to use ammonia as alkali in the method for the invention.When
When using ammonia as alkali, ammonium hydroxide can be directly used, such as commercially available concentration is the ammonium hydroxide of about 25%- about 28%.But
An embodiment according to the present invention, the concentration of the ammonium hydroxide used can be about 5wt%- about 28wt%, and preferably from about 5wt- is about
20wt%, more preferably from about 8wt%- about 14wt%.The lower ammonium hydroxide of concentration can for example be obtained by the way that high concentration ammonium hydroxide is diluted with water.
According to an embodiment, the concentration of ammonium hydroxide no more than about 26wt%, about 25wt%, about 24wt%, about 23wt%, about 22wt%, about
21wt%, about 20wt%, about 19wt%, about 18wt%, about 17wt%, about 16wt%, about 15wt%, about 14wt%, about 13wt%, about
12wt%, about 11wt%, or about 10wt%.According to an embodiment, the concentration of ammonium hydroxide is at least about 2wt%, about 3wt% or about
4wt%。
When the aqueous solution of alkali such as ammonium hydroxide to be added in the suspension, the addition speed of the aqueous solution of alkali can control
Degree, such as can be by the way of being added dropwise.An embodiment according to the present invention, the aqueous solution of alkali such as ammonium hydroxide is by with slow
Speed be added in the suspension, and can be stirred during the addition process.
When there is no Ga (OH)3When continuing to generate on carrier, the addition of the aqueous solution of alkali can be stopped.Of the invention one
In a embodiment, at least about 8 can be reached in pH of suspension, when for example, about 8- about 9, preferably from about 8- about 8.5 stops the water of alkali
The addition of solution.In one embodiment of the invention, mixture one can be stirred after the aqueous solution for stopping being added alkali
The section time, for example, about 0.1- about 3 hours.Later, can filtering the suspension, (load has Ga (OH) thereon to separate solid3
Carrier).After filtration, the solid of separation can be washed.For washing, can first with offer suspension the step of in use
Organic solvent such as ethanol washing, be then washed with water.When using ammonium hydroxide, ammonia odor disappearance can be washed with water to.
Later, washed solid can be calcined to obtain the nanometer gallic oxide-carrier composite material.
Optionally, in one embodiment, before being calcined, the wet solid after washing is dried to remove water.It can be used
Drier such as vacuum desiccator removes water to be dried.Water can also be removed by heating wet solid.Generally, to heating
Temperature and heating time do not require, as long as water can be removed.For example, heating temperature can be about 200 DEG C of about 80-, when heating
Between can be about 0.1- about 10 hours.Optionally, after drying, before being calcined, powder is carried out to the solid obtained after drying
It is broken.Grinding machine or jet mill can be used for example to be crushed.
Calcining in the method for the present invention can be by the Ga (OH) on carrier3It is converted into Ga2O3.In one embodiment, originally
The calcining of invention is carried out in about 1000 DEG C of about 400- of temperature.According to a preferred embodiment, the calcining is about 600
DEG C-about 800 DEG C of temperature carries out, and more preferably from about 600 DEG C-about 700 DEG C.According to an embodiment, using about 600 DEG C-about 800
DEG C, preferably from about 600 DEG C-about 700 DEG C of calcination temperature, to obtain β-Ga2O3To provide better air pollutants catalytic decomposition
Performance.Generally, the calcining can be carried out using any equipment that can satisfy temperature requirement.According to an embodiment,
The calcining can carry out in Muffle furnace.Method of the invention is not specifically limited calcination time, can only obtain institute
Need Ga2O3；Such as calcination time can be about 0.5- about 20 hours.Heating rate when being calcined can be by art technology
Personnel's unrestricted choice, such as can be about 20 DEG C/min of about 0.1 DEG C/min-.It, can be with natural cooling to obtain after calcining
Nanometer gallic oxide-carrier composite material.
The method for preparing composite material of the invention good can control Ga in the composite material prepared2O3Nano particle
Granularity, and safety is good, easy to operate, easily controllable, reproducible, environmental-friendly.For example, because the present invention uses alkali
Aqueous solution, allow to avoid using organic solvent, thus to environmental benefits, and improve safety.In addition, of the invention
Method is because of in-situ preparation Ga2O3Nano particle, so in Ga2O3There is high bond strength between nano particle and carrier.
Another aspect of the present invention is related to air cleaning facility.Use the air cleaning of adsorbent and/or photochemical catalyst
Equipment is as known in the art.Air cleaning facility as known in the art can be used in the present invention, and only it includes this hairs
Bright photochemical catalyst-adsorbent composite material.The air cleaning facility of the invention includes the photochemical catalyst-of the invention
The equipment of adsorbent composite material and emitting ultraviolet light.For example, photochemical catalyst-the adsorbent composite material can be set or
Coating is on the supporting member.Air comprising pollutant can flow through the photochemical catalyst-adsorbent composite material.The transmitting
The equipment of ultraviolet light irradiates the photochemical catalyst-adsorbent composite material to provide catalytic activity.The equipment of emitting ultraviolet light
It can be ultraviolet lamp usually used in this field, such as the ultraviolet lamp of emitting ultraviolet light (254nm).The air cleaning facility
Such as can be used for the indoor, vehicles such as aircraft etc..An additional aspect of the present invention is related to composite material of the invention
For purifying the purposes of air.
Hereinafter, further illustrating the present invention by embodiment.
Embodiment
Following embodiment is intended to describe rather than limit the invention in any way.
Chemicals
Ethyl alcohol Sinopharm Chemical Reagent Co., Ltd.
Ammonium hydroxide (25%-28%) Sinopharm Chemical Reagent Co., Ltd.
Nitric hydrate gallium Suzhou Kang Peng Chemical Co., Ltd.
1000 Praxair Technology, Inc of HiSiv (UOP LLC)
Degussa P25 Evonik Degussa limited liability company, TiO2
Instrument and equipment
FESEM: HITACHI S-4700
TEM: JEM2000EX
EDS: JEOL JSM IT-300 & EDAX Octane Plus
Granularity: Malvern Mastersizer 3000
XRD: Rigaku D/MAX 2550
GC:Shimadzu GC-2014 or upper Nereid section gas chromatograph GC122
BET: Micromeritics ASAP2420。
The preparation of the gallic oxide-Zeolite composite materials of the present invention of embodiment 1
The nitric hydrate gallium of 480g is dissolved in 2L ethyl alcohol, 80g HiSiv 1000 is then added and is stirred 1 hour in 200rpm,
Obtain solution A.0.8L ammonium hydroxide (25% ~ 28%) is mixed with 1.2L water to obtain solution B.With the speed of 20mL/min by solution
B is added drop-wise in solution A until pH value reaches 8.5.Continue with 200rpm stirring mixture 1 hour.It is white to separate to filter mixture
Color solid, it is primary with 500mL ethanol washing, it is washed with water until without ammonia odor.It is small in 150 DEG C of wet solids being dried to obtain 4
When to completely remove water.With the dry solid that pulverizer crushes to provide powder, then calcined in Muffle furnace at 600 DEG C
The powder arrived 5 hours, heating speed are 2 DEG C/min.Natural cooling after calcining obtains HiSiv 1000- of the invention
Ga2O3Composite material.
The HiSiv 1000-Ga2O3The Ga of composite material2O3Content is measured by EDS energy disperse spectroscopy；See Fig. 1.It surveys
Obtain Ga2O3Content is 53.7wt%.
The HiSiv1000-Ga2O3The particle diameter distribution of composite material is measured with Malvern Mastersizer 3000,
It is shown in Figure 2.As can be seen that significant change does not occur for particle diameter distribution.
1 particle diameter distribution of table
| D10(μm) | D50(μm) | D90(μm) | |
| HiSiv 1000 | 1.37 | 3.70 | 11.7 |
| HiSiv 1000-Ga2O3Composite material | 0.979 | 3.17 | 10.4 |
To HiSiv 1000 and HiSiv 1000-Ga2O3Specific surface area, aperture and the pore volume of composite material are surveyed
It measures (BET), is shown in Table 2.
Table 2
| SBET(m2/g) | Aperture (nm) | Pore volume (cm3/g) | |
| HiSiv 1000 | 598 | 0.75 | 0.2111 |
| Ga2O31000 composite material of-HiSiv | 308 | 0.75 | 0.1078 |
It is in table 2 statistics indicate that Ga2O3The hole of the unplugged HiSiv 1000 of nano particle, in other words Ga2O3Nano particle is
It is grown on the surface of HiSiv 1000.
The HiSiv 1000-Ga2O3The TEM image of composite material is shown in Figure 3, and SEM image is shown in Figure 4.It can be true
It is fixed, HiSiv 1000-Ga2O3Ga in composite material2O3The size of particle is about 10 nanometers of about 5-.
The HiSiv 1000-Ga2O3The XRD diagram case of composite material is shown in Figure 5.1000 He of HiSiv is also shown in Fig. 5
β-Ga2O3XRD diagram case.Fig. 5 shows HiSiv 1000-Ga2O3There are β-Ga in composite material2O3。
Embodiment 2 (comparison) Ga2O3The preparation of nano particle
Embodiment 1 is repeated, does not use 1000 zeolite of HiSiv only.Ga is obtained after the completion of calcining2O3Powder of nanometric particles.
The Ga2O3The TEM image of powder is shown in Figure 6.By Fig. 6 it was determined that obtained Ga2O3The partial size of nano particle
For tens nanometer.
The toluene absorption of the composite material of the present invention of embodiment 3/degradation test
The HiSiv 1000-Ga that will be prepared in 0.1g embodiment 12O3Composite powder is directly laid on 11cm2Glass dish
On.Then the glass dish is placed on to the centre of the quartz reactor of 500mL.There are three 8W for the upper parallel setting of the reactor
Ultraviolet lamp (254nm).With artificial air (V (O2):V(N2)=1:4) pre-process the container 5 minutes to remove gaseous impurities,
Including CO2.Certain density toluene gas is injected in the reactor and reaches by volume that (volume passes through 100ppm toluene concentration
Skip test predefines).Then, which is kept adsorbing toluene within 2 hours in the dark, then opens ultraviolet lamp.
Toluene and CO are monitored by gas-chromatography (GC-2014, Shimadzu) during the test2Concentration variation.Toluene and CO2Concentration
It is shown in Figure 7 to change (mineralization rate).
Fig. 7 shows the HiSiv 1000-Ga of the application2O3Composite material can adsorb rapidly toluene and use ultraviolet lamp
Toluene is decomposed after irradiation.After about 7 hours, reach about 100% mineralization rate.
Embodiment 4
The Ga that will be prepared in 0.1g embodiment 22O3The Ga prepared in nano particle, 0.2g embodiment 22O3Nano particle and
It is prepared in the 1:1 weight ratio physical mixture (the two adds ethyl alcohol to grind) and 0.187g embodiment 1 of HiSiv1000 zeolite
HiSiv 1000-Ga2O3(three contains 0.1g Ga to composite material2O3) be dispersed in 2mL ethyl alcohol respectively, it is then coated with
On 8cm × 8cm glass plate.It is stayed overnight in an oven in 70 DEG C of dry glass plates.By glass plate be put into 1.85L with two
In the quartz reactor of a 11W ultraviolet lamp (254nm).Reactor is vacuumized and injects toluene to obtain about 200ppm (volume)
Toluene concentration (volume is determined by skip test), is then injected into compressed air to adjust pressure to atmospheric pressure.Make each material
It absorbs toluene 3 hours, then opens ultraviolet lamp.With gas chromatograph (the upper Nereid equipped with methane reborner and fid detector
Section GC122) detect toluene and CO2Concentration.
The test result of three kinds of materials is shown in Fig. 8, Fig. 9 and Figure 10.It can be seen that this from Fig. 8, Fig. 9 and Figure 10
The HiSiv 1000-Ga in situ of invention2O3Composite material has highest active (being shown by mineralization rate).
Embodiment 5
The test of embodiment 3 is repeated, but the material tested is the HiSiv 1000-Ga prepared in 0.1g embodiment 1 respectively2O3
Composite material and 0.1g Degussa P25.Toluene and CO2Concentration variation be shown in Figure 11.
As can be seen that the toluene concentration reduction speed of composite catalyzing material of the invention is fast, mineralization rate is significantly higher than business
TiO2(Degussa P25)。
6 reusability of embodiment
The HiSiv 1000-Ga that will be prepared in 0.2g embodiment 12O3Composite material is dispersed in 2mL ethyl alcohol, is then coated with
On 8cm × 8cm glass plate.It is stayed overnight in an oven in 70 DEG C of dry glass plates.There are two the bands that glass plate is put into 1.85L
In the quartz reactor of 11W ultraviolet lamp (254nm).Reactor is vacuumized and injects toluene to obtain 300ppm (volume) toluene
Concentration (volume is determined by skip test), is then injected into compressed air to adjust pressure to atmospheric pressure.Then it opens ultraviolet
Lamp.Inject same amount of toluene within every 12 hours.Every 6 hours be equipped with methane reborner and fid detector gas chromatograph
(upper Nereid section GC122) detection CO2Concentration.Test result is shown in Figure 12.
As seen from Figure 12, after 10 cycles, the performance of composite material of the present invention is maintained.
The toluene absorption of 7 HiSiv 1000 of embodiment/degradation test
Repeat embodiment 4 in test, only use 0.2g HiSiv 1000, and by toluene concentration be set as 500ppm and
It absorbs toluene 2.5 hours, then opens ultraviolet lamp.The test result of HiSiv 1000 is shown in Figure 13.
As seen from Figure 13, HiSiv 1000 is typical adsorbent, can adsorb toluene, but is unable to mineralising first
Benzene.
Embodiment 8
Embodiment 1 is repeated, lowers gallium nitrate dosage and is prepared for Ga2O3Content is the HiSiv 1000-Ga of 30wt% and 40wt%2O3
Composite material.The TEM image of the two is shown in Figure 14 and Figure 15.Both composite materials are used for the first in embodiment 3
Benzene absorption/degradation test, is as a result shown in Figure 16 and Figure 17.
9 repeatability of embodiment
It repeats preparation process 7 times (160g/ batch) of embodiment 1 and repeats the preparation of embodiment 1 with 1/10th ratio
Process 30 times (16g/ batch), obtain the product of 37 batches.7 batch (samples are randomly choosed from this 37 batch products
Ga 1-7) is measured as in Example 12O3Content.As a result it is shown in the following table 3.
Table 3
| Sample number into spectrum | wt% (Ga2O3) |
| 1 | 49.7 |
| 2 | 50.2 |
| 3 | 49.3 |
| 4 | 49.5 |
| 5 | 53.7 |
| 6 | 44.4 |
| 7 | 47.0 |
In addition, randomly choosing 2 batches (sample 8 and 9) from this 37 batch products carries out toluene according to embodiment 3
Absorption/degradation test.As a result it is shown in Figure 18 and Figure 19.
The release of 10 intermediate of embodiment
By the HiSiv 1000-Ga of 0.5g embodiment 12O3Compound material ultrasound is dispersed in 4ml ethyl alcohol, then uniformly coating
On the glass substrate of 10cm × 10cm, then dried in 80 DEG C of baking oven.The sample strip is placed in one to follow equipped with gas
In ring and the 8L reactor of 1 23W ultraviolet lamp tube (254nm).System is evacuated to 2 min of vacuum, is passed through the first of about 1000 ppm
Benzene/N2For gas to normal pressure, reinjecting the air with steam to system pressure is 0.02MPa.It is inhaled in the case where without illumination
Attached 2.5h, then opens ultraviolet lamp.It is dense by gas-chromatography (Shimadzu GC2010) on-line period test toluene every 0.5h
Degree.
Figure 20 shows three Typical gas chromatograph curves；Wherein 0 h of a., the toluene initially injected；B. 2.5 h, greatly
About reach adsorption equilibrium/opening ultraviolet lamp；C. 6.5h, ultraviolet light irradiation is after 4 hours.As seen from Figure 20, no intermediate is released
It puts.
Claims (21)
1. a kind of photochemical catalyst-adsorbent composite material, it includes zeolite adsorbents and be supported on the zeolite adsorbents three
Aoxidize two gallium (Ga2O3) nano particle, the wherein silica alumina ratio (SiO of the zeolite adsorbents2/Al2O3) it is 10-500, preferably 18-
300, more preferable 20-200, and the aperture of the zeolite adsorbents is 0.6 nanometer -1.3 nanometers, it is preferably 0.6-1.0 nanometers, more excellent
Select 0.7-0.9 nanometers.
2. photochemical catalyst-adsorbent composite material as described in claim 1, wherein the gallic oxide nano particle be
What the zeolite adsorbents surface in situ was formed.
3. such as the described in any item photochemical catalyst-adsorbent composite materials of claim 1-2, wherein the gallic oxide nanometer
The partial size of particle is 3 nanometers -50 nanometers, and preferably 3 nanometers -30 nanometers, more preferable 4 nanometers -20 nanometers, still more preferably 5 receive
- 10 nanometers of rice.
4. photochemical catalyst-adsorbent composite material as described in any one of claims 1-3, wherein the zeolite adsorbents are selected from
FAU type and BEA type zeolite, preferably Na-Y type zeolite.
5. photochemical catalyst-adsorbent composite material according to any one of claims 1-4, wherein the zeolite adsorbents are in 4-
9 pH range is stable.
6. photochemical catalyst-adsorbent composite material as described in any one in claim 1-5 the, wherein photochemical catalyst-absorption
The specific surface area of agent composite material, which is greater than, is equal to 250m2/ g, preferably greater than or equal to 300m2/g。
7. photochemical catalyst-adsorbent composite material as claimed in any one of claims 1 to 6, wherein the gallic oxide nanometer
The amount of particle is the photochemical catalyst-adsorbent composite material weight 10%-60%, preferably 20%-50%, more preferable 30%-50%.
8. such as the described in any item photochemical catalyst-adsorbent composite materials of claim 1-7, wherein the gallic oxide nanometer
Particle includes β-Ga2O3Nano particle.
9. a kind of prepare nanometer gallic oxide-carrier composite material method comprising following steps:
There is provided comprising gallium presoma, carrier and can dissolve gallium presoma organic solvent suspension, the wherein organic solvent
It can be miscible with water；
The aqueous solution of alkali is added in the suspension to generate Ga (OH) in situ on carrier3；With
Load has Ga (OH) thereon for separation3Carrier and calcined to obtain the composite material.
10. preparation nanometer gallic oxide-carrier composite material method as claimed in claim 9, wherein the gallium forerunner
Body is gallium salt, and the preferably described gallium salt is selected from gallium nitrate, gallium chloride, gallium sulfate, gallium bromide, acetic acid gallium, gallium formate and levulinic
Ketone gallium.
11. such as the described in any item preparation nanometer gallic oxide-carrier composite material methods of claim 9-10, wherein institute
Stating carrier is adsorbent, and the preferably described adsorbent is zeolite.
12. preparation nanometer gallic oxide-carrier composite material method as claimed in claim 11, wherein the zeolite
Silica alumina ratio (SiO2/Al2O3) be 10-500, preferably 18-300, more preferable 20-200, and the aperture of the zeolite be 0.6 nanometer-
It is 1.3 nanometers, preferably 0.6-1.0 nanometers, 0.7-0.9 nanometers more preferable.
13. such as the described in any item preparation nanometer gallic oxide-carrier composite material methods of claim 11-12, wherein
The zeolite is selected from FAU type and BEA type zeolite, preferably Na-Y type zeolite.
14. such as the described in any item preparation nanometer gallic oxide-carrier composite material methods of preceding claims 9-13,
Described in organic solvent be selected from ethyl alcohol, methanol, isopropanol, ethylene glycol, butanediol, glycerol, tetrahydrofuran, dimethylformamide,
Dimethyl sulfoxide, dimethyl acetamide and their mixture, preferred alcohol.
15. such as the described in any item preparation nanometer gallic oxide-carrier composite material methods of preceding claims 9-14,
Described in alkali be selected from ammonia, methyl amine, dimethyl amine, Trimethylamine, ethylamine, diethylamide, triethylamine, propyl amine, dipropyl
Base amine, tripropylamine, diethylmethyl amine, ethyldimethyl amine, isopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, aminopropan
Alcohol, ethanol amine, diethanol amine, diethylenetriamines, trien, hydroxyethyl ethylenediamine, tetramethylammonium hydroxide, tetrem
Base ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, hexamethylene diamine and their mixture, preferably its
Described in alkali be ammonia, and the concentration of ammonia spirit is 5wt%-28wt%, preferably 5wt-20wt%, more preferable 8wt%-14wt%.
16. such as the described in any item preparation nanometer gallic oxide-carrier composite material methods of preceding claims 9-15,
Described in calcining 600 DEG C -800 DEG C temperature carry out.
17. such as the described in any item preparation nanometer gallic oxide-carrier composite material methods of preceding claims 9-16,
Described in suspension the amount of gallium presoma based on the total weight of gallium presoma and organic solvent be 5%-50%, preferably 5%-40%,
More preferable 8%-30%.
18. such as the described in any item preparation nanometer gallic oxide-carrier composite material methods of preceding claims 9-17,
Described in suspension the amount of carrier based on the total weight of carrier and organic solvent be 2%-20%, preferably 4%-10%.
19. such as the described in any item preparation nanometer gallic oxide-carrier composite material methods of preceding claims 9-18,
It is middle that the aqueous solution of alkali is added in the suspension until pH of suspension reaches at least 8, preferably reach 8-8.5.
20. a kind of air purifier, it includes the described in any item photochemical catalyst-adsorbent composite materials of claim 1-8.
21. the purposes that the described in any item photochemical catalyst-adsorbent composite materials of claim 1-8 are used to purify air.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711104854.4A CN109772260A (en) | 2017-11-10 | 2017-11-10 | Gallic oxide-adsorbent composite material and its preparation method and application |
| PCT/CN2018/111766 WO2019091285A1 (en) | 2017-11-10 | 2018-10-25 | Gallium trioxide-adsorbent composite material, preparation method therefor, and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711104854.4A CN109772260A (en) | 2017-11-10 | 2017-11-10 | Gallic oxide-adsorbent composite material and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109772260A true CN109772260A (en) | 2019-05-21 |
Family
ID=66437571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711104854.4A Pending CN109772260A (en) | 2017-11-10 | 2017-11-10 | Gallic oxide-adsorbent composite material and its preparation method and application |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109772260A (en) |
| WO (1) | WO2019091285A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569856A (en) * | 2020-04-03 | 2020-08-25 | 清华-伯克利深圳学院筹备办公室 | In-Ga2O3Composite photocatalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102476807A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院大连化学物理研究所 | Preparation method of L zeolite containing gallium |
| CN102671651A (en) * | 2012-06-07 | 2012-09-19 | 浙江大学 | Method for preparing mesoporous beta-Ga2O3 nanorod photocatalyst by using PEG (polyethylene glycol) as template |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003171578A (en) * | 2001-12-06 | 2003-06-20 | Sumitomo Chem Co Ltd | Coating liquid and photocatalyst functional product |
| CN103086420B (en) * | 2012-12-27 | 2014-11-26 | 清华大学 | Nanometer gallium oxide and application thereof |
-
2017
- 2017-11-10 CN CN201711104854.4A patent/CN109772260A/en active Pending
-
2018
- 2018-10-25 WO PCT/CN2018/111766 patent/WO2019091285A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102476807A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院大连化学物理研究所 | Preparation method of L zeolite containing gallium |
| CN102671651A (en) * | 2012-06-07 | 2012-09-19 | 浙江大学 | Method for preparing mesoporous beta-Ga2O3 nanorod photocatalyst by using PEG (polyethylene glycol) as template |
Non-Patent Citations (4)
| Title |
|---|
| 《工业安全技术手册》编辑委员会编: "《工业安全技术手册》", 31 August 1989, 上海科学技术出版社 * |
| MARYAM BORDBAR，等: "Reactivity of Ga2O3 Clusters on Zeolite ZSM-5 for the Conversion of Methanol to Aromatics", 《CATAL LETT》 * |
| YIDONG HOU，等: "Photocatalytic performance of α-, β-, and γ -Ga2O3 for the destruction of volatile aromatic pollutants in air", 《JOURNAL OF CATALYSIS》 * |
| 姚运先编: "《室内环境污染控制》", 30 June 2007, 中国环境科学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569856A (en) * | 2020-04-03 | 2020-08-25 | 清华-伯克利深圳学院筹备办公室 | In-Ga2O3Composite photocatalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019091285A1 (en) | 2019-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huang et al. | Catalytic oxidation of benzene over Mn modified TiO2/ZSM-5 under vacuum UV irradiation | |
| Shu et al. | Promotional role of Mn doping on catalytic oxidation of VOCs over mesoporous TiO2 under vacuum ultraviolet (VUV) irradiation | |
| Mishra et al. | Effect of g-C3N4 loading on TiO2/Bentonite nanocomposites for efficient heterogeneous photocatalytic degradation of industrial dye under visible light | |
| Huang et al. | Photocatalytic oxidation of gaseous benzene under VUV irradiation over TiO2/zeolites catalysts | |
| WO2018068729A1 (en) | Air purification composite catalyst and preparation method thereof | |
| Zhang et al. | Preparation of photocatalytic TiO2 coatings of nanosized particles on activated carbon by AP-MOCVD | |
| Zhu et al. | The degradation of formaldehyde using a Pt@ TiO2 nanoparticles in presence of visible light irradiation at room temperature | |
| Yuan et al. | Surface characteristics and photocatalytic activity of TiO2 loaded on activated carbon fibers | |
| CN105473221A (en) | Catalysts for oxidation of carbon monoxide and/or volatile organic compounds | |
| TWI433815B (en) | Stable sub-micron titania sols | |
| US11241671B2 (en) | Monolithic composite photocatalysts | |
| Suraja et al. | Photocatalytic degradation of dye pollutant over Ti and Co doped SBA-15: Comparison of activities under visible light | |
| CN104772110A (en) | Visible-light response type air purifier photo-catalyst filter screen and preparation method thereof | |
| WO2018176779A1 (en) | Mesoporous ozone oxidation catalyst and preparation and usage method therefor | |
| CN106381682A (en) | Nano-TiO2/activated carbon fibrofelt three-dimensional porous material high in adsorption and photocatalytic performance, and preparation method thereof | |
| CN109248672A (en) | A kind of composite material and preparation method and application | |
| Park et al. | Photodegradation of benzene, toluene, ethylbenzene and xylene by fluidized bed gaseous reactor with TiO 2/SiO 2 photocatalysts | |
| JP2005270734A (en) | Photocatalyst composite and organic substance converting method using the same | |
| CN109331817A (en) | It is a kind of for decomposing the catalysis material and preparation method of organic matter in air | |
| Wei et al. | Fabrication of the novel core-shell MCM-41@ mTiO2 composite microspheres with large specific surface area for enhanced photocatalytic degradation of dinitro butyl phenol (DNBP) | |
| Muniandy et al. | Carbon modified anatase TiO2 for the rapid photo degradation of methylene blue: A comparative study | |
| CN104147924A (en) | Novel photo-catalyst air purifying agent and preparation method | |
| CN111185090A (en) | Device for photocatalytic degradation of organic waste gas and application method thereof | |
| Lee et al. | Synthesis of bimodal porous structured TiO2 microsphere with high photocatalytic activity for water treatment | |
| CN109772260A (en) | Gallic oxide-adsorbent composite material and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190521 |