CN109248672B - Composite material and preparation method and application thereof - Google Patents

Composite material and preparation method and application thereof Download PDF

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CN109248672B
CN109248672B CN201810692386.5A CN201810692386A CN109248672B CN 109248672 B CN109248672 B CN 109248672B CN 201810692386 A CN201810692386 A CN 201810692386A CN 109248672 B CN109248672 B CN 109248672B
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porous material
adsorbent
photocatalyst
slurry
combination
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CN109248672A (en
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郭玉
杨倩
周永
彭树文
马海瑛
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Honeywell Performance Materials and Technologies China Co Ltd
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Honeywell Performance Materials and Technologies China Co Ltd
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    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • 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
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    • 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
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
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    • 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
    • B01J20/165—Natural alumino-silicates, e.g. zeolites
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    • 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
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7027—Aromatic hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/06—Polluted air

Abstract

The invention relates to a composite material and a preparation method and application thereof. The composite material comprises: a porous material as a support; a first adsorbent attached to the outer surface and within the pores of the porous material; and a photocatalyst-second adsorbent combination attached to an outer surface of the porous material. The composite material according to the present invention can rapidly and effectively adsorb one or more VOCs and continuously perform a photocatalytic reaction to degrade the VOCs adsorbed in the porous material, thereby having the ability to continuously and rapidly treat VOCs.

Description

Composite material and preparation method and application thereof
Technical Field
The invention belongs to the field of air purification and treatment. In particular, the invention relates to a composite material and a preparation method and application thereof.
Background
Air pollution is becoming serious with the densification of buildings, the sharp increase in the number of automobiles, the increase in industrial emissions, and the like. Contaminants in the air include Volatile Organic Compounds (VOCs) such as formaldehyde, benzene, toluene, and the like.
With the improvement of the requirements on the living quality and the enhancement of the awareness of environmental protection, people have higher and higher concern on trace gaseous pollutants in the air. In order to remove these harmful substances to maintain a comfortable living environment, many air cleaning devices have been developed.
CN2568189Y discloses a nano photocatalytic air purification accessory, in which several ultraviolet germicidal lamps are installed in a housing in parallel arrangement, layered carriers prepared with transparent porous nano-photocatalyst films are installed on the upper and lower sides of the ultraviolet germicidal lamps, reflective materials are adhered on the inner wall of the housing for fixing the ultraviolet germicidal lamps, and power plugs are connected with the ultraviolet germicidal lamps, the layered carriers prepared with the nano-photocatalyst films are structural layers with three-dimensional network structures, and meanwhile, adsorption layers are arranged on the upper and lower surfaces of the carriers.
CN1162211C discloses a photocatalytic air purification net with a multilayer structure, which comprises a carrier, an adhesive layer, an activated carbon layer and TiO in sequence from inside to outside2A photocatalyst layer.
Their basic principle is primarily the adsorption or photocatalytic degradation of certain volatile organic compounds by the materials contained therein.
Adsorption removes one or more VOCs, but there is a dynamic balance with respect to temperature and concentration, etc., and adsorption does not reduce the environmental VOCs to zero, and the adsorbed VOCs are released after the temperature is reduced. Furthermore, the adsorption capacity is limited and needs to be replaced regularly.
Photocatalytic degradation can completely remove one or more VOCs and degrade them to CO2And water, but the degradation rate is too slow. Therefore, it is highly desirable to develop a new material that can rapidly and efficiently adsorb one or more VOCs and continuously dispose of the adsorbed VOCs.
Disclosure of Invention
The object of the present invention is to provide a new material which can rapidly and efficiently adsorb one or more VOCs and continuously dispose of the adsorbed VOCs.
The problems to be solved by the invention are solved by the following technical scheme:
according to a first aspect of the present invention, there is provided a composite material, characterized in that it comprises:
a porous material as a support;
a first adsorbent attached to the outer surface and within the pores of the porous material; and
a photocatalyst-second sorbent combination attached to an outer surface of the porous material.
According to a second aspect of the present invention, there is provided a method for preparing the above composite material, characterized in that it comprises the steps of:
I) attaching the first adsorbent into the pores and onto the outer surface of the porous material; and
II) attaching the photocatalyst-second adsorbent combination to the outer surface of the porous material.
According to a third aspect of the present invention there is provided the use of the above composite material for purifying air.
According to a fourth aspect of the present invention, there is provided an air cleaning device comprising the above composite material.
The composite material according to the present invention can rapidly and effectively adsorb one or more VOCs such as formaldehyde, benzene, toluene, etc. and continuously perform a photocatalytic reaction to degrade the VOCs adsorbed in the porous material, thereby having the ability to continuously and rapidly treat VOCs.
Drawings
The invention will be described hereinafter with reference to the accompanying drawings, in which:
FIG. 1 shows Ga prepared in example 12O3-HiSivTM1000 combined TEM images.
FIG. 2 is a photograph of the modules used in the tests of examples 2-4.
FIG. 3 is a graph showing the adsorption curves of composites prepared in examples 2 to 4 for toluene.
Detailed description of the preferred embodiments
The technical solutions of the present invention are described in detail below to more fully embody the aspects of the present invention and further objects, features, and advantages.
According to a first aspect of the present invention, there is provided a composite material, characterized in that it comprises:
a porous material as a support;
a first adsorbent attached to the outer surface and within the pores of the porous material; and
a photocatalyst-second sorbent combination attached to an outer surface of the porous material.
The porosity of the porous material is preferably 60% to 98%.
The porous material preferably has an open porosity of at least 90%, for example 95-98%.
In the present specification and claims, the open porosity means the ratio of the volume of pores communicating with the outside to the total volume of pores.
The pore diameter of the porous material is 0.1-10 mm.
The porous material is preferably selected from nickel foam, aluminum foam, polymer foam, aluminum honeycomb, ceramic honeycomb, and the like.
The polymer foam may be selected from among polyvinylidene fluoride (PVDF) foam, polyvinyl chloride (PVC) foam, and epoxy resin foam, among others.
In the present invention, the porous material allows the loading of the first adsorbent to be sufficiently high to allow rapid and efficient absorption of volatile organic compounds in the environment.
The loading amount of the first adsorbent is 50g/m2-500g/m2Preferably 100g/m2-500g/m2More preferably 300-350g/m2Based on the total surface area of the porous material.
The first adsorbent and the second adsorbent may be selected independently of each other from zeolites.
The zeolite may be any zeolite used for adsorption, such as ZSM-5 zeolite, Na-Y type zeolite, 5A zeolite, 10X zeolite, 13X zeolite, and the like.
The silicon to aluminum ratio (SiO) of the zeolite2/Al2O3Molar ratio) may be 10 to 500, preferably 18 to 300, more preferably 20 to 200.
The pore size of the zeolite may be in the range of 0.6 nm to 1.3 nm, preferably 0.6 to 1.0 nm, more preferably 0.7 to 0.9 nm. The pore size described herein is the average pore size obtained by the BET method.
It is believed that the above-mentioned silica to alumina ratio is selected to have a favorable affinity for VOCs, while the above-mentioned pore size is selected to favor adsorption of certain larger VOC molecules, such as benzene and toluene, among others.
Although a zeolite in a fibrous, columnar, or the like shape may be used, the zeolite is generally used in a particulate form.
The zeolite has a particle size (D50) of 0.5 microns to 100 microns, preferably 1 micron to 50 microns, more preferably 1 micron to 20 microns.
The zeolite has a specific surface area (BET) of 300m2/g-1000m2Per g, preferably 400m2/g-900m2A/g, more preferably 500m2/g-800m2/g。
The zeolite may be FAU-type and/or BEA-type zeolite.
Preferably, the zeolite adsorbent is a Na-Y type zeolite.
The zeolite is stable in both acidic and basic environments, for example, in the pH range of 4-9.
Preferably, the zeolite is HiSivTM 1000。HiSivTM1000 is a commercial adsorbent for UOP LLC. As a powder, HiSivTM1000 (D50) is 4 μm (dynamic light scattering), the specific surface area is > 550m2(BET), average pore diameter of 0.75 nm, and Si/Al ratio of 30.
In some embodiments, the first adsorbent and the second adsorbent are different zeolites.
In some embodiments, the first and second adsorbents are both the same zeolite.
In the photocatalyst-second adsorbent combination, it is preferred that the photocatalyst is present on the surface of the second adsorbent. Advantageously, the photocatalyst particles do not clog the pores of the adsorbent, which helps to adsorb contaminants.
In some embodiments, the photocatalyst is present in the form of nanoparticles.
In the present application, nanoparticles refer to particles having a particle size of not more than 100 nm.
In some embodiments, the photocatalyst nanoparticles have a particle size of 3 nm to 50 nm, preferably 3 nm to 30 nm, more preferably 4nm to 20 nm, and even more preferably 5 nm to 10 nm.
The photocatalyst may be selected from gallium sesquioxide (Ga)2O3) Titanium dioxide (TiO)2) Zinc oxide (ZnO), tin oxide (SnO)2) Zirconium oxide (ZrO)2) And combinations thereof.
In some embodiments, the photocatalyst is a gallium sesquioxide, preferably β -Ga2O3。
In some embodiments, the photocatalyst-second sorbent combination is a physical mixture of a photocatalyst and a second sorbent.
In some embodiments, the photocatalyst-second sorbent combination is obtained by forming a photocatalyst in situ on the surface of the second sorbent.
For example, with gallium trioxide as the photocatalyst, the photocatalyst-second adsorbent combination can be prepared by: providing a suspension comprising a gallium precursor, a second adsorbent and an organic solvent capable of dissolving said gallium precursor, wherein the organic solvent is miscible with water; adding an aqueous base solution to the suspension to generate Ga (OH) in situ on the second adsorbent3(ii) a And separating the carrier having Ga (OH) supported thereon3And calcining to obtain the photocatalyst-second adsorbent combination.
In the present application, miscible means that the two liquids are soluble in each other in any ratio.
The gallium precursor may be a gallium salt including, for example, gallium nitrate, gallium chloride, gallium sulfate, gallium bromide, gallium acetate, gallium formate, gallium acetylacetonate, and the like.
The organic solvent may be selected from ethanol, methanol, isopropanol, ethylene glycol, butylene glycol, glycerol, tetrahydrofuran, dimethylformamide, dimethylsulfoxide and dimethylacetamide.
To provide a suspension comprising a gallium precursor, a second adsorbent and an organic solvent, the gallium precursor may be dissolved in the organic solvent and then the second adsorbent is added; or the second adsorbent can be added into the organic solvent, and then the gallium precursor is added; or the gallium precursor can be dissolved in an organic solvent and the second adsorbent dispersed in the organic solvent, and then the two are combined; or the gallium precursor and the second adsorbent may be added to the organic solvent at least partially simultaneously. To aid in the dissolution of the gallium precursor and/or the dispersion of the second adsorbent, stirring may be performed.
The base may be selected from the group consisting of ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, diethylmethylamine, ethyldimethylamine, isopropanolamine, diisopropanolamine, triisopropanolamine, aminopropanol, ethanolamine, diethanolamine, diethylenetriamine, triethylenetetramine, hydroxyethylethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and hexamethylenediamine, preferably the base is ammonia. When the base is ammonia, the concentration of the aqueous ammonia solution may be 5 wt.% to 28 wt.%.
The calcination may be carried out at a temperature of 600 ℃ to 800 ℃, more preferably 600 ℃ to 700 ℃.
In general, the calcination can be carried out using any equipment capable of meeting the temperature requirements.
In some embodiments, the calcining is performed in a muffle furnace.
Optionally, the wet solids are dried to remove water prior to calcination. Drying to remove water may be performed using a dryer, such as a vacuum dryer. Water may also be removed by heating the wet solid. Generally, there is no requirement for heating temperature and heating time as long as water can be removed. For example, the heating temperature may be 80 ℃ to 200 ℃ and the heating time may be 0.1 to 10 hours.
Optionally, after drying, the solid obtained after drying is pulverized before calcination. The pulverization can be carried out, for example, using a mill or a jet mill.
The amount of gallium precursor in the suspension is 5-50% based on the total weight of gallium precursor and organic solvent, and/or the amount of second adsorbent in the suspension is 2-20% based on the total weight of second adsorbent and organic solvent.
The inventors have found that the photodegradation efficiency of the photocatalyst-second sorbent combination obtained by forming the photocatalyst in situ on the surface of the second sorbent is superior to the physical mixture of photocatalyst and sorbent.
The loading capacity of the photocatalyst-second adsorbent combination is 10g/m2-100g/m2Preferably 20g/m2-80g/m2More preferably 20g/m2-60g/m2Based on the total surface area of the porous material.
The photocatalyst-second adsorbent combination has a specific surface area (BET) of 250m or more2A ratio of the total amount of the components to the total amount of the components is preferably 300m or more2/g。
In the photocatalyst-second adsorbent combination, the content of the photocatalyst is not particularly limited and may be adjusted as needed by those skilled in the art.
In some embodiments, the amount of photocatalyst, e.g., gallium oxide nanoparticles, is 10% to 70%, preferably 20% to 60%, more preferably 30% to 60% of the combined weight of the photocatalyst-second sorbent.
In some embodiments, the photocatalyst-second sorbent combination is gallium sesquioxide (Ga)2O3) -a zeolite.
In some embodiments, the photocatalyst-second sorbent combination is Ga2O3-HiSivTM1000。
The photocatalyst-second adsorbent combination can degrade the absorbed one or more VOCs, such as formaldehyde, benzene, toluene, and the like, and eventually decompose into carbon dioxide and water. Since the adsorbed VOC is continuously degraded by the photocatalyst-second adsorbent combination, the concentration of the organic substances adsorbed on the surface of the composite material is continuously decreased, there is a difference in the concentration of the organic substances between the inside and the outside of the porous material, the adsorbed VOC inside the porous material is slowly released to the surface to be degraded, the environment is purified, and complete decomposition (high mineralization rate) of the VOC means that the composite material can be completely regenerated, thereby enabling long-term use.
According to a second aspect of the present invention, there is provided a method for preparing the above composite material, characterized in that it comprises the steps of:
I) attaching the first adsorbent into the pores and onto the outer surface of the porous material; and
II) attaching the photocatalyst-second adsorbent combination to the outer surface of the porous material.
In some embodiments, the first adsorbent is attached to the outer surface and within the pores of the porous material by:
i) providing a first slurry comprising the first adsorbent, a first solvent, and a first inorganic binder;
ii) impregnating the porous material in the first slurry;
iii) separating the porous material from the first slurry; and
iv) removing the first solvent.
The first solvent is water or an organic solvent or a mixture thereof, and the organic solvent is selected from ethanol, methanol, isopropanol, ethylene glycol, butanediol, glycerol, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide and dimethylacetamide.
The first inorganic binder is preferably an aluminum phosphate binder.
In the first slurry, the concentration of the first adsorbent is 14% to 40% by weight of the total weight of the first slurry.
In the first slurry, the concentration of the first inorganic binder is 14% to 40% by weight of the total weight of the first slurry.
In some embodiments, the first solvent is removed by drying.
The drying is carried out by baking at 60 ℃ to 150 ℃ for 30 to 100 minutes, for example at 100 ℃ for 60 minutes.
In these embodiments, it is preferred that the first adsorbent is attached to the entire surface of the porous material.
In some embodiments, the photocatalyst-second sorbent combination is attached to the outer surface of the porous material by:
i) providing a second slurry comprising the photocatalyst-second sorbent combination, a second solvent, and a second inorganic binder;
ii) coating the second slurry onto the outer surface of the porous material;
iii) removing the second solvent; and
iv) calcining the porous material to cure the inorganic binder.
The second solvent is water or an organic solvent or a mixture thereof, and the organic solvent is selected from ethanol, methanol, isopropanol, ethylene glycol, butanediol, glycerol, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide and dimethylacetamide.
The second inorganic binder is preferably an aluminum silicate binder.
The concentration of the photocatalyst-second sorbent combination in the second slurry is 30% to 60% by total weight of the second slurry.
In the second slurry, the concentration of the second inorganic binder is 30% to 60% based on the total weight of the second slurry.
The coating can be carried out by adopting a brush, a knife coater, a spray gun and a spray coater.
In some embodiments, the second solvent is removed by drying.
The drying is carried out by baking at 60 ℃ to 150 ℃ for 10 to 60 minutes, for example at 100 ℃ for 20 minutes.
The calcination may be performed at a temperature of 250 ℃ to 500 ℃, more preferably at a temperature of 300 ℃ to 400 ℃ for 2 to 8 hours, to cure the inorganic binders, including the first inorganic binder (if any) and the second inorganic binder.
Thus, according to a third aspect of the present invention, there is provided the use of the above-described composite material for purifying air.
For example, the contaminants may be adsorbed by flowing air containing the contaminants through the composite material and decomposed by the photocatalyst under irradiation of light.
According to a fourth aspect of the present invention, there is provided an air cleaning device comprising the above composite material.
The air purification device comprises the composite material and a device emitting light. For example, the composite material may be disposed or coated on the support member. Air containing contaminants may flow through the composite. The light-emitting device irradiates the composite material to provide catalytic activity. The light-emitting device may be an ultraviolet lamp commonly used in the art, for example, an ultraviolet lamp emitting ultraviolet light (254 nm).
The air cleaning device may be used, for example, indoors, in vehicles such as airplanes, etc.
The terms "comprising" and "including" as used herein encompass the case where other elements not explicitly mentioned are also included or included and the case where they consist of the mentioned elements.
Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that can vary depending upon the desired properties to be obtained.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the event that a definition of a term in this specification conflicts with a meaning commonly understood by those skilled in the art to which the invention pertains, the definition set forth herein shall govern.
Examples
The concept and technical effects of the present invention will be further described with reference to the following examples so that those skilled in the art can fully understand the objects, features and effects of the present invention. It should be understood that the examples are illustrative only and are not intended to limit the scope of the present invention.
Example 1
Preparation of photocatalyst-second adsorbent combination
480g of hydrated gallium nitrate are dissolved in 2L of ethanol, and 80g of HiSiv are addedTM1000 and at 200rpmStirring was carried out for 1 hour to obtain a dispersion A. 0.8L of aqueous ammonia (25 wt.% to 28 wt.%) was mixed with 1.2L of water to give solution B. Solution B was added dropwise to dispersion A at a rate of 20mL/min until the pH reached 8.5. The mixture was stirred at 200rpm for an additional 1 hour. The mixture was filtered to isolate a white solid, washed once with 500mL of ethanol and washed with water until there was no ammonia odor. The resulting wet solid was dried at 150 ℃ for 4 hours to completely remove water. The resulting dry solid was pulverized with a pulverizer to provide a powder, and then the resulting powder was calcined in a muffle furnace at 600 ℃ for 5 hours at a heating rate of 2 ℃/min. Naturally cooling after calcining to obtain Ga2O3-HiSivTM1000 for standby.
Ga determination by EDS spectrometer2O3The content was 53.7 wt.%. The particle size distribution was measured by a Malvern Mastersizer 3000 and the results are summarized in Table 1.
Table 1: HiSivTM1000 and Ga2O3-HiSivTM1000 combined particle size distribution
D10(μm) D50(μm) D90(μm)
HiSivTM1000 1.37 3.70 11.7
Ga2O3-HiSivTM1000 combination 0.979 3.17 10.4
The results in table 1 show that the particle size distribution of the second adsorbent did not change significantly after the photocatalyst was supported.
For HiSivTM1000 and Ga2O3-HiSivTMThe specific surface area, pore size and pore volume were measured (BET) for 1000 combinations and the results are summarized in table 2.
Table 2: HiSivTM1000 and Ga2O3-HiSivTM1000 combined specific surface area, pore diameter and pore volume
SBET(m2/g) Pore size (nm) Pore volume (cm)3/g)
HiSivTM1000 598 0.75 0.2111
Ga2O3-HiSivTM1000 combination 308 0.75 0.1078
The results in Table 2 show that Ga2O3Nanoparticle unblocked HiSivTM1000 pores, or Ga2O3The nanoparticles are grown in HiSivTM1000. Ga, determined by TEM (Transmission Electron microscope, JEM2000EX)2O3-HiSivTMGa in 1000 combination2O3The size of the particles is 5-10 nm, see fig. 1.
Supporting a first adsorbent
40g HiSiv are weighedTM1000. 40g of the aluminium phosphate binder and 180g of water were mixed in a high speed mixer at 3000rpm for a period of 30 seconds to 1 minute. And uniformly mixing to obtain slurry. The slurry was poured into a vessel, and a foamed nickel sheet (3mm in thickness, 95% in porosity, 98% in open porosity, 0.5-3mm in pore size) was completely immersed in the slurry, and then the foamed nickel sheet was pulled out of the slurry at a speed of 400 mm/min. And putting the foamed nickel sheet fully soaked with the slurry into an oven at 100 ℃ for baking for 60 minutes.
The HiSiv in the foam nickel sheet is calculated by weighing the weight difference before and after the foam nickel sheetTM1000 in an amount of 100g/m2Based on the total surface area of the porous material.
Supported photocatalyst-second adsorbent combination
40g or more of the prepared Ga was weighed2O3-HiSivTM1000. 40g of the aluminium phosphate binder and 20g of water were mixed in a high speed mixer at 3000rpm for a period of 30 seconds to 1 minute. And uniformly mixing to obtain slurry. The slurry is uniformly sprayed on the HiSiv-loaded substrateTM1000 and the nickel foam sheets were placed in a 100 c oven for 20 minutes. Ga in the foamed nickel sheet is calculated by weighing the weight difference of the foamed nickel sheet before and after2O3-HiSivTM1000 in an amount of 20g/m2With the porous materialTotal surface area of the charge.
And finally, placing the foamed nickel in a muffle furnace for calcination at the temperature of 350 ℃ for 5 hours.
Adsorption Performance test
Taking a load of 20g/m2Ga of (2)2O3-HiSivTM1000 and 100g/m2HiSiv (R) ofTM1000 samples of foamed nickel (5 cm x 10cm area, 3mm thickness). The sample was then placed in the middle of a 500mL quartz reactor. The upper part of the reactor was provided in parallel with three 8w UV lamps (254 nm). The vessel was pretreated with artificial air (V (O2): V (N2) ═ 1: 4) for 5 minutes to remove gaseous impurities including CO2). Toluene gas was injected into the reactor at a concentration to achieve a toluene concentration of 100ppm by volume (volume predetermined by blank test). Then, the reactor was kept in the dark for 2 hours to adsorb toluene, and then the ultraviolet lamp was turned on. Toluene and CO were monitored by gas chromatography (GC-2014, Shimadzu) during the test2. The test conditions were: the humidity is 40-50%, and the temperature is 10 ℃. Toluene and CO were monitored by gas chromatography (GC-2014, Shimadzu) during the test2The concentration of (c) is varied. Toluene and CO2The change in concentration of (A) with time is shown in Table 3 below.
Table 3: toluene and CO2Change of concentration of (A) with time
0min 5min 120min 300min 720min
Toluene 100ppm 0ppm 0ppm 0ppm 0ppm
CO2 1.7ppm 1.7ppm 2.6ppm 26ppm 75ppm
The results in table 3 show that the composite material of the present invention can rapidly adsorb toluene and decompose it.
Examples 2 to 4
Supporting a first adsorbent
40g HiSiv are weighedTM1000 and 40g of aluminum phosphate binder and 40-160g of water were mixed in a high speed mixer at 3000rpm for 30 seconds to 1 minute. And uniformly mixing to obtain slurry. Due to the different weight of the water solvent mixture, slurries with different solid contents are obtained, and the solid content ranges from 17 wt.% to 33 wt.%. The slurry was poured into a vessel, and a foamed nickel sheet (3mm in thickness, 95% in porosity, 98% in open porosity, 0.5mm to 3mm in pore size) was completely immersed in the slurry, and then the foamed nickel sheet was pulled out of the slurry at a speed of 400 mm/min. And putting the foamed nickel sheet fully soaked with the slurry into a 100 ℃ oven to be baked for 30-60 minutes.
The HiSiv in the foam nickel sheet is calculated by weighing the weight difference before and after the foam nickel sheetTM100The loading amount of 0 is 200g/m2-500g/m2Based on the total surface area of the porous material. The amount of water, solids content and HiSiv used in the examplesTMThe loadings of 1000 are summarized in table 4 below.
Table 4: the amount of water, solids content and HiSiv used in examples 2-4TMLoad capacity of 1000
Figure BDA0001711586460000111
Supported photocatalyst-second adsorbent combination
40g of Ga prepared in example 1 were weighed2O3-HiSivTM1000. 40g of the aluminium phosphate binder and 20g of water were mixed in a high speed mixer at 3000rpm for a period of 30 seconds to 1 minute. And uniformly mixing to obtain slurry. The slurry was uniformly sprayed onto the surface of the nickel foam and the nickel foam pieces were placed in a 100 ℃ oven for 10 minutes. Ga in the foamed nickel is calculated by weighing the weight difference before and after the foamed nickel is weighed2O3-HiSivTM1000 in an amount of 20g/m2Based on the total surface area of the porous material.
And finally, placing the foamed nickel in a muffle furnace for calcination at the temperature of 350 ℃ for 5 hours.
Adsorption Performance test
Will be 0.78m2Total surface area loading HiSivTM1000 and Ga2O3-HiSivTM1000 of foamed nickel was loaded in a module as in fig. 2 and at 30m3The toluene was tested in the cabin for its CARD (clean air output ratio) value and the test results are summarized in table 5 below.
TABLE 5 different HiSivTMToluene adsorption Performance corresponding to 1000 Supports
Figure BDA0001711586460000112
FIG. 3 is a graph showing the adsorption curve of the prepared composite material to toluene.
From the above results, it can be seen that the composite material of the present invention can rapidly adsorb toluene.
The adsorption and decomposition ability of the composite material of the present invention is characterized by toluene, and those skilled in the art can understand that the composite material of the present invention can also adsorb formaldehyde, benzene, etc. and decompose them.
Although a few aspects of the present invention have been shown and discussed, it would be appreciated by those skilled in the art that changes may be made in this aspect without departing from the principles and spirit of the invention, the scope of which is therefore defined in the claims and their equivalents.

Claims (17)

1. A composite material, characterized in that it comprises:
a porous material as a support;
a first adsorbent attached to the outer surface and within the pores of the porous material; and
a photocatalyst-second adsorbent combination attached to the outer surface of the porous material,
wherein the first adsorbent is attached in the pores and on the outer surface of the porous material by:
i) providing a first slurry comprising the first adsorbent, a first solvent, and a first inorganic binder;
ii) impregnating the porous material in the first slurry;
iii) separating the porous material from the first slurry; and
iv) removing the first solvent;
attaching the photocatalyst-second adsorbent combination to the outer surface of the porous material by:
i) providing a second slurry comprising the photocatalyst-second sorbent combination, a second solvent, and a second inorganic binder;
ii) coating the second slurry onto the outer surface of the porous material;
iii) removing the second solvent; and
iv) calcining the porous material to cure the inorganic binder;
wherein the first and second adsorbents are independently selected from zeolites, the photocatalyst is selected from the group consisting of gallium sesquioxide, titanium dioxide, zinc oxide, tin oxide, zirconium oxide, and combinations thereof, and the porous material is selected from the group consisting of nickel foam, aluminum foam, polymer foam, aluminum honeycomb, and ceramic honeycomb.
2. The composite material according to claim 1, wherein the porous material has a porosity of 60% to 98%, an open porosity of at least 90% and a pore diameter of 0.1 to 10 mm.
3. The composite material of claim 1 or 2, wherein the first adsorbent is loaded at a level of 50g/m2-500g/m2Based on the total surface area of the porous material.
4. The composite material according to claim 1 or 2, wherein the loading of the first adsorbent is 100g/m2-500g/m2Based on the total surface area of the porous material.
5. The composite material of claim 1 or 2, wherein the first adsorbent is loaded at a level of 300g/m2-350g/m2Based on the total surface area of the porous material.
6. The composite of claim 1 or 2, wherein in the photocatalyst-second sorbent combination, a photocatalyst is present on the surface of the second sorbent.
7. The composite material according to claim 1 or 2, wherein the photocatalyst-second adsorbent combination is a digallium trioxide-zeolite.
8. The composite of claim 1 or 2, wherein the photocatalyst-second adsorbent combination is present at a loading of 10g/m2-100g/m2Based on the total surface area of the porous material.
9. The composite of claim 1 or 2, wherein the photocatalyst-second adsorbent combination is loaded at 20g/m2-80g/m2Based on the total surface area of the porous material.
10. The composite of claim 1 or 2, wherein the photocatalyst-second adsorbent combination is loaded at 20g/m2-60g/m2Based on the total surface area of the porous material.
11. A method for preparing a composite material according to any one of claims 1 to 10, characterized in that it comprises the following steps:
I) attaching the first adsorbent into the pores and onto the outer surface of the porous material; and
II) attaching the photocatalyst-second adsorbent combination to the outer surface of the porous material.
12. The method of claim 11, wherein the first sorbent is attached to the pores and outer surface of the porous material by:
i) providing a first slurry comprising the first adsorbent, a first solvent, and a first inorganic binder;
ii) impregnating the porous material in the first slurry;
iii) separating the porous material from the first slurry; and
iv) removing the first solvent.
13. The method of claim 11 or 12, wherein the photocatalyst-second sorbent combination is attached to the outer surface of the porous material by:
i) providing a second slurry comprising the photocatalyst-second sorbent combination, a second solvent, and a second inorganic binder;
ii) coating the second slurry onto the outer surface of the porous material;
iii) removing the second solvent; and
iv) calcining the porous material to cure the inorganic binder.
14. The method according to claim 13, wherein the first and/or second solvent is water or an organic solvent or a mixture thereof, the organic solvent being selected from the group consisting of ethanol, methanol, isopropanol, ethylene glycol, butylene glycol, glycerol, tetrahydrofuran, dimethylformamide, dimethylsulfoxide and dimethylacetamide.
15. The method as recited in claim 13 wherein the first inorganic binder and/or the second inorganic binder is an aluminum phosphate binder.
16. Use of a composite material according to any one of claims 1-10 for purifying air.
17. An air purification device comprising the composite material according to any one of claims 1-10.
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