CN111589428B - Composite material for purifying air and preparation method thereof - Google Patents

Composite material for purifying air and preparation method thereof Download PDF

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Publication number
CN111589428B
CN111589428B CN202010421781.7A CN202010421781A CN111589428B CN 111589428 B CN111589428 B CN 111589428B CN 202010421781 A CN202010421781 A CN 202010421781A CN 111589428 B CN111589428 B CN 111589428B
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silica gel
modified
filtering
modified silica
particles
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CN111589428A (en
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林本成
袭著革
田蕾
刘焕亮
来文庆
李哲
闫峻
刘晓华
石玥
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Environmental Medicine and Operational Medicine Institute of Military Medicine Institute of Academy of Military Sciences
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Environmental Medicine and Operational Medicine Institute of Military Medicine Institute of Academy of Military Sciences
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising 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
    • B01D53/02—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
    • 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
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s

Abstract

The invention relates to the technical field of indoor environmental pollution control, in particular to a composite material for purifying air, which comprises a filtering support material, and activated carbon particles and modified silica gel particles which are attached to the filtering support material, wherein the modified silica gel particles comprise a silica gel carrier and amino-terminated hyperbranched polyamidoamine grafted on the silica gel carrier. The surface of the modified silica gel particles is grafted with the terminal amino HPAMAM, so that the silica gel surfaces contain sufficient terminal amino, and the terminal amino can generate condensation reaction with aldehydes and ketones to capture and fix a large number of aldehydes and ketones molecules, so that the modified silica gel has excellent capability of adsorbing aldehydes and ketones; the active carbon has the performance of adsorbing hydrocarbons and benzene series, and the two are used together, thereby achieving the purpose of basically removing main organic pollutants in the ship cabin. The invention also relates to a preparation method of the composite material.

Description

Composite material for purifying air and preparation method thereof
Technical Field
The invention relates to the technical field of indoor environmental pollution control, in particular to a composite material for purifying air and a preparation method thereof.
Background
Volatile Organic Compounds (VOCs) are various organic compounds having a boiling point of 50 to 260 c at normal temperature, according to the definition of the World Health Organization (WHO). In China, VOCs refer to organic compounds with saturated vapor pressure of more than 70Pa at normal temperature and boiling point of below 260 ℃ at normal pressure, or all organic compounds with vapor pressure of more than or equal to 10Pa and volatility at 20 ℃. Most VOCs have unpleasant special odor and have toxic, irritant, teratogenic and carcinogenic effects, and particularly benzene, toluene, formaldehyde and the like cause great harm to human health.
The ship cabin is a special manned artificial environment, and due to personnel activities, non-metallic material release, mechanical equipment operation and the like, VOCs in the cabin air have the particularity, and the type of the VOCs is different from the atmospheric environment, the residential indoor environment or the labor sanitary environment. According to literature detection data and early-stage exploratory investigation, the method comprises the following steps: the more severely contaminated materials in the cabin are in turn: benzene series > aldehyde ketones (carbonyl-containing organic matter) > hydrocarbons > halogenated hydrocarbons > other organic pollutants. It is seen that benzene series and aldehydes and ketones are the main pollutants in the cabin air of ships. However, the present purification materials based on activated carbon can only purify benzene series, and cannot purify aldehydes and ketones, especially small molecular carbonyl substances (formaldehyde, acetaldehyde, acrolein, acetone, etc.). As an improvement means, various modification treatments have been carried out on activated carbon, but there are technical problems that: the modification treatment of the activated carbon simultaneously sacrifices the porous active sites in the activated carbon, and the physical adsorption performance of the modified activated carbon is reduced although the adsorption capacity of the modified activated carbon to a special substance is enhanced. In addition, most of modified activated carbon cannot play a good role in purifying carbonyl substances in terms of the existing activated carbon modification technology.
Disclosure of Invention
Technical problem to be solved
In view of the problems in the prior art, the invention provides a composite material for purifying air, which simultaneously adopts activated carbon and modified silica gel as functional materials for purifying air, wherein the modified silica gel is prepared by grafting amino-terminated Hyperbranched Polyamidoamine (HPAMAM) on the existing silica gel, so that the surface of the silica gel contains sufficient active terminal amino groups, and the active terminal amino groups and aldoketones generate condensation reaction so as to capture and fix a large amount of aldoketone volatile substances, so that the modified silica gel has excellent ability of adsorbing the aldoketone substances; the activated carbon has the performance of adsorbing hydrocarbon organic matters and benzene series, and most of kinds of pollution gas in the cabin of the ship can be eliminated by jointly using the modified silica gel and the activated carbon. The invention also relates to a preparation method of the composite material.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
in a first aspect, the present invention provides a composite material for purifying air, which comprises a filter support material, and activated carbon particles and modified silica gel particles attached to the filter support material, wherein the modified silica gel particles comprise a silica gel support and an amino-terminated hyperbranched polyamidoamine grafted to the silica gel support.
As a preferred embodiment of the invention, the molecular weight of the amino-terminated hyperbranched polyamidoamine is 5000-8000, the branching Degree (DB) is more than or equal to 0.4, and the total amine value is more than 0.069mol/g. The amino-terminated hyperbranched polyamidoamine meeting the condition is used as a modifier, so that abundant terminal amino groups can be obtained on the surface of a silica gel carrier, and the silica gel carrier has an excellent effect of chemically capturing carbonyl (aldehyde ketone) substances.
As a preferred embodiment of the invention, wherein the particle size of the silica gel carrier is 30-60 meshes, and the specific surface area is 300-600m 2 The pore volume is 0.6-1.1 mL/g. The silica gel meeting the condition is used as a carrier to be modified, the modification is easier to complete by an immersion method, the modification process is simplified, the modification yield is improved, and the modified silica gel adsorbent is grafted with amino-terminated hyperbranched polyamidoamine on the surface, has rich micropores for physically adsorbing and capturing VOCs, and also has larger specific surface area and rich poresThe active sites of (2) capture the more polar (e.g., phenolic hydroxyl or carboxyl-containing) substances in the VOCs by virtue of the silicon hydroxyl groups.
As a preferred embodiment of the invention, the activated carbon particles are coal-based carbon, the particle size is 30-60 meshes, and the CTC value (carbon tetrachloride adsorption value) is more than or equal to 90%. The CTC value is a carbon tetrachloride adsorption value and is used for expressing the adsorption capacity of the activated carbon to gas substances, and the higher the index is, the stronger the adsorption capacity of the activated carbon is.
As a preferred embodiment of the present invention, the mass ratio of the amino-terminated hyperbranched polyamidoamine (amino-terminated hpaam) to the silica gel carrier is 1 to 10:50. the purpose of meeting the requirement of the mass ratio is that on one hand, the amino-terminated hyperbranched polyamidoamine can occupy a larger space, so that the grafting amount is limited, and on the other hand, a plurality of vacancies are left on the surface of the modified silica gel carrier for capturing and fixing other VOCs gas molecules except carbonyl substances by physical adsorption and bonding of silicon hydroxyl.
In a second aspect, the present invention provides a method for preparing a composite material for purifying air, the method comprising:
the method comprises the following steps: preparing modified silica gel particles, which comprises the following steps:
s1, adding amino-terminated HPAMAM, a coupling agent and a surfactant into water, and dispersing to prepare a modified impregnation liquid;
s2, putting the silica gel carrier to be modified into the modified impregnation liquid, uniformly stirring, and standing for a preset time to obtain a modified silica gel emulsion;
s3, drying the silica gel emulsion at 60-150 ℃ until the water content is 5-25% to obtain modified silica gel particles;
step two: mixing the modified silica gel particles and the activated carbon particles according to a certain proportion to obtain an adsorption mixture, and dispersedly adhering and fixing the adsorption mixture on a filtering support material by using an adhesive to obtain a composite material for purifying air;
or the filtering and supporting material is a material with the surface containing hot-melt polymer, and the adsorption mixture is adhered to the filtering and supporting material in a hot-pressing compounding mode to prepare the composite material for purifying air;
or dispersedly fixing the modified silica gel particles on the first filter support material, dispersedly fixing the activated carbon particles on the second filter support material, and then compounding the first filter support material and the second filter support material into a whole.
According to a preferred embodiment of the present invention, in step S1, the coupling agent is a silane coupling agent, preferably one or a mixture of KH550, KH560 and KH 570; the surfactant is a nonionic surfactant, such as fatty acid monoglyceride and glyceryl monostearate, sorbitan fatty acid, polysorbate, polyoxyethylene fatty acid ester (maize), polyoxyethylene fatty alcohol ether (benez), polyoxyethylene-polyoxypropylene copolymer (poloxamer), pluronic, and the like, and is preferably one or a mixture of several of nonylphenol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, cetyl alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, and dodecyl polyoxyethylene ether.
According to a preferred embodiment of the invention, in step S1, the molecular weight of the amino-terminated hyperbranched polyamidoamine is 5000-8000, the branching Degree (DB) is more than or equal to 0.4, and the total amine value is more than 0.069mol/g.
According to the preferred embodiment of the present invention, in step S2, the particle size of the silica gel carrier to be modified is 30-60 mesh, and the specific surface area is 300-600m 2 The pore volume is 0.6-1.1 mL/g.
According to a preferred embodiment of the present invention, in step S1, the modified impregnation solution contains 1% to 10% by mass of the amino-terminated hpaam, 0.5% to 5% by mass of the coupling agent, and 0.1% to 2% by mass of the surfactant. And preferably, the amino-terminated HPAMAM: coupling agent: the mass ratio of the surfactant is 10.
According to a preferred embodiment of the invention, in step S2, the standing time is 1-24h, and the mass ratio of the silica gel carrier to be modified to the modified impregnation solution is 1:2. preferably, the standing time is 4-10h.
According to a preferred embodiment of the present invention, in step S3, the drying is performed in an air heating bath at 80 ℃ to 120 ℃ until the water content is 5% to 20%, more preferably 10% to 20%, to obtain the modified silica gel particles.
According to the preferred embodiment of the invention, in the second step, the activated carbon particles are coal-based carbon, the particle size is 30-60 meshes, and the CTC value is more than or equal to 90%.
According to a preferred embodiment of the invention, in the second step, the modified silica gel particles and the activated carbon particles are mixed according to a mass ratio of 1.
According to the preferred embodiment of the invention, the filtering support material is a non-woven fabric filtering support net, the adhesive is preferably a hot melt adhesive, the hot melt adhesive is one or more of vinyl acetate, epoxy acrylate and polyethylene terephthalate, and the addition amount is as follows: the mass ratio of the hot melt adhesive to the adsorption mixture is 1.
During preparation, the hot melt adhesive is heated and melted, the adsorption mixture and the hot melt adhesive are uniformly mixed, and then the mixture is spread on the non-woven fabric filter support net to prepare the composite material for purifying air after cooling and solidification; or uniformly dispensing glue on the non-woven fabric filter support net, spreading the adsorption mixture on the non-woven fabric filter support net before the glue is not solidified, cooling and solidifying, blowing to remove the non-bonded adsorption mixture, and performing supplementary bonding according to the condition. Or the filtering support material is a material with the surface containing hot-melt polymer, and the adsorption mixture is bonded and attached to the filtering support material in a hot-pressing compounding mode to prepare the composite material for purifying air; or the filtering and supporting material is a material with the surface containing hot-melt polymer, the modified silica gel particles and the activated carbon particles are respectively attached to the first filtering and supporting material and the second filtering and supporting material in a hot-pressing mode, and then the first filtering and supporting material and the second filtering and supporting material are compounded into a whole.
Wherein, the spreading should be as uniform as possible. In addition, by adjusting the weight of the adsorption mixture sprayed on the filter support material in a unit area (adjusting the dosage ratio of the activated carbon particles to the modified silica gel particles), series products with different gram weights in unit area and different specifications can be prepared and formed according to different pollution degrees and different proportions of pollutants in the environment to be purified in actual production, and the series products have different strength adsorption performances on aldehydes, ketones, hydrocarbons and benzene series and are particularly suitable for air purification in cabins of ships.
(III) advantageous effects
The composite material for air purification of the invention combines the modified silica gel particles and the activated carbon particles, wherein the modified silica gel particles are grafted and modified by the amino-terminated HPAMAM, the modified silica gel particles are used for adsorbing carbonyl substance molecules, and the activated carbon is used for adsorbing hydrocarbon organic matters and benzene series matters, thereby achieving the purpose of basically removing main organic pollutants in the ship cabin.
When the silica gel is modified, the modified silica gel particles are prepared by taking amino-terminated HPAMAM (hyperbranched polymer polyamidoamine) as a grafting modifier and forming abundant active amino-terminated groups on the surface of the existing silica gel, and the amino-terminated groups can efficiently and largely capture free carbonyl substance molecules in the air through an amine-aldehyde condensation reaction; meanwhile, the silica gel is used as an adsorbent carrier, a large number of micropores on the surface of the silica gel also have physical adsorption, a large number of silicon hydroxyl groups on the surface of silica gel particles also have strong polarity, and the micropores and the silicon hydroxyl groups can cooperatively participate in capturing substances with strong polarity (such as phenolic hydroxyl groups or carboxyl groups) in the VOCs.
Furthermore, the modified silica gel particles and the activated carbon are mixed according to a certain proportion to form an adsorption mixture, and the adsorption mixture is further processed to prepare a composite material for purifying air (or is respectively attached to a filtering support material and then is compounded into a whole), is used for adsorbing a large amount of carbonyl compounds, hydrocarbon free molecules and benzene series, can be used for improving the indoor air quality, and particularly solves the pollution problem of main organic matters in the cabin of a ship.
The invention adopts the silica gel modification method of the 'dipping method', has very simple steps, mild conditions, easy control, no use of toxic and harmful substances, environment-friendly process and suitability for large-scale production and application.
Drawings
FIG. 1 shows DSC curves of the modified silica gel, the silica gel to which only the silane coupling agent is bonded, and the unmodified silica gel of example 1.
FIG. 2 is a TG curve of the modified silica gel, the silica gel to which only the silane coupling agent was attached, and the unmodified silica gel of example 1.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
The overall thought of the invention is as follows: modified silica gel particles grafted and modified by amino-terminated HPAMAM hyperbranched polymers are mixed with activated carbon particles according to a certain proportion to form a purification functional material, and the purification functional material is attached to a filtering support base material and used for adsorbing free molecules of carbonyl, hydrocarbon and benzene series in a cabin of a ship so as to achieve the aim of basically removing main organic pollutants in the cabin of the ship.
The method for modifying the silica gel comprises the following steps: the modified silica gel has the performance of adsorbing and fixing aldehyde and ketone substance molecules.
Based on the technical conception, the invention provides the technical schemes of the composite material for purifying the air, the preparation method of the composite material for purifying the air and the like. Preferably, the molecular weight of the amino-terminated hyperbranched polyamidoamine is 5000-8000, the branching Degree (DB) is more than or equal to 0.4, and the total amine value is more than 0.069mol/g.
Preferably, the modified silica gel particles comprise a silica gel support and an amino-terminated HPAMAM grafted onto the silica gel support.
Further preferably, the silica gel carrier to be modified has the particle size of 30-60 meshes and the specific surface area of 300-600m 2 The pore volume is 0.6-1.1 mL/g.
Preferably, the mass ratio of the terminal amino HPAMAM to the silica gel to be modified is 1-10:50.
preferably, the activated carbon particles are coal-based carbon, the particle size is 30-60 meshes, and the CTC value is more than or equal to 90%.
Preferably, the mass ratio of the activated carbon particles to the modified silica gel particles is 1-2.
In the process of preparing the modified silica gel particles, a dipping modification method is mainly adopted: firstly, preparing a modified impregnation liquid, adding a certain mass of amino-terminated HPAMAM, a coupling agent and a surfactant into water during preparation of the modified impregnation liquid, and stirring to obtain a uniform modified impregnation liquid; then immersing the silica gel particles to be modified into the modified impregnation liquid, stirring and standing for 1-24h, preferably 4-10h, to obtain modified silica gel emulsion; drying the water to the water content of about 5-25% to obtain the modified silica gel particles. Preferably, the drying moisture is carried out in an air heating bath at 80 ℃ to 120 ℃ to a moisture content of 5% to 20%, more preferably 10% to 20%, to obtain the modified silica gel particles.
Preferably, the coupling agent used is a silane coupling agent, preferably one or a mixture of KH550, KH560 and KH 570; the surfactant is nonionic surfactant, such as polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl (lauryl) ether, polyoxyethylene cetyl (cetyl), polyoxyethylene nonyl phenyl ether, polyoxyethylene octylphenyl ether, or mixture of more than one of polyoxyethylene lauryl phenyl ether.
Preferably, the prepared modified impregnation liquid has the mass concentration of the amino-terminated HPAMAM of 1-10%, the mass concentration of the coupling agent of 0.5-5% and the mass concentration of the surfactant of 0.1-2%, and preferably, the concentration of the coupling agent and the surfactant is higher when the content of the amino-terminated HPAMAM is higher, wherein the content of the amino-terminated HPAMAM: coupling agent: the mass ratio of the surfactant is 10.
The composite material for purifying air is prepared by mixing the prepared modified silica gel particles and activated carbon particles according to a certain proportion to form an adsorption mixture, and further dispersing and attaching the adsorption mixture on a filter support material, wherein the filter support material is provided with micropores which can be penetrated by air. Preferably, the filter support material may be a non-woven filter support web. Or dispersing and attaching the prepared modified silica gel particles and the prepared activated carbon particles on the first and second filter supporting materials respectively, and then compounding the first and second filter supporting materials into a whole.
An adhesive may be used in dispersedly attaching the adsorbent mixture to the filter support material. Hot melt adhesives are preferred for use in the present invention. The hot melt adhesive does not need to introduce other additives or curing agents, and the preparation process is simpler. Alternatively, the surface of the filter support material contains a low-melting-point high-molecular polymer (e.g., made of low-melting-point chemical fibers and high-melting-point chemical fibers, or the surface contains a low-melting-point polymer film), and the adsorption mixture sprayed on the filter support material can be directly compounded/bonded onto the filter support material by means of a hot-pressing compounding technique.
Preferably, the selected hot melt adhesive is one or more of vinyl acetate, epoxy acrylate and polyethylene terephthalate. Firstly, heating and melting hot melt adhesive, uniformly mixing the modified silica gel particles and the hot melt adhesive, then spreading the mixture on the non-woven fabric filter support net, and cooling and solidifying the mixture to prepare the air-purifying composite material, wherein the mass ratio of the hot melt adhesive to the adsorption mixture is 1.
For ease of understanding, the features and properties of the present invention will now be further described with reference to specific examples.
Example 1
The embodiment provides a preparation method of a composite material for air purification, which comprises the following steps:
the method comprises the following steps: the modified silica gel particles were prepared as follows:
step 1, sequentially putting amino-terminated HPAMAM hyperbranched polymer, a silane coupling agent KH550 and a surfactant dodecyl polyoxyethylene ether into water. The mass concentrations of HPAMAM, KH550 and dodecyl polyoxyethylene ether are respectively 10%, 5% and 2%, and the modified impregnation liquid is obtained by uniformly stirring in a physical stirring or magnetic stirring manner.
And 2, adding 1 part by mass of silica gel into 2 parts by mass of modified impregnation liquid, continuously stirring uniformly, fully impregnating and standing for 8 hours to obtain modified silica gel emulsion.
And 3, drying the modified silica gel emulsion obtained in the step 2 in a converter type air heating bath at 120 ℃ until the water content is 5% to obtain modified silica gel particles c for later use.
According to the method, when the modified impregnation solution is prepared in the step 1, the HPAMAM and the KH550 are not added, then 1 part by mass of silica gel is added into 2 parts by mass of the impregnation solution, and the treatment is carried out according to the method of the steps 2 to 3, so as to obtain the treated silica gel a.
According to the method, when the modified impregnation solution is prepared in the step 1, the KH550 is not added, and then 1 part by mass of silica gel is added to 2 parts by mass of the impregnation solution and treated according to the method of the step 2 to the step 3, so that the treated silica gel b is obtained.
The results of differential scanning calorimetry analysis and thermogravimetric analysis of the modified silica gel particles c, silica gel a and silica gel b are shown in fig. 1 and fig. 2, respectively.
Since the organic components on the surface of the modified silica gel particles are decomposed at high temperature, the thermogravimetric analysis curve of the silica gel particles has obvious weight loss (figure 2). Therefore, the content of the organic component on the surface of the modified silica gel particle c can also be roughly determined by thermal re-analysis.
As shown by the thermogravimetric analysis curve of fig. 2: compared with the blank silica gel a, the modified silica gel particles c and silica gel b begin to lose weight above 200 ℃, mainly due to the reduction of organic components on the surface. The surface of silica gel b modified by KH550 had a small amount of weight loss, while the weight loss of silica gel c (modified silica gel particles c) grafted with HPAMAM was very significant. Correspondingly, in fig. 1, 2 distinct exothermic peaks appear on the DSC curve of the modified silica gel particle c, wherein the exothermic peak at 200 ℃ is caused by the combustion of the terminal amino group HPAMAM, the exothermic peak at 350 ℃ is mainly caused by the combustion of the silane coupling agent KH550, and the unmodified silica gel a appears without thermal effect. Thermogravimetric analysis showed that the silica gel surface was grafted with about 20wt% of hpaam.
The above analysis shows that the amino-terminated HPAMAM is successfully grafted on the surface of the silica gel after the treatment by the method of the steps (1) to (3).
Step two: preparation of composite Material
Uniformly mixing 5 parts by mass of the modified silica gel particles and 5 parts by mass of powdered activated carbon (coal carbon, the granularity is 30-60 meshes, and the CTC value is more than or equal to 90 percent) to obtain adsorption mixed powder. Heating 1 part by mass of polyethylene terephthalate, adding the adsorption mixed powder into the polyethylene terephthalate, uniformly mixing, spreading on a non-woven fabric filter support net, and cooling to prepare the air-purifying composite material.
The composite material for purifying air prepared by the embodiment can chemically capture and fix aldehyde ketone free molecules, can partially adsorb phenols or carboxylic acid substances with larger polarity, can also physically adsorb and fix hydrocarbons and benzene substances, and can be used for removing main organic pollutants in a cabin of a ship.
Example 2
The embodiment provides a preparation method of a composite material for purifying air, which comprises the following steps:
the method comprises the following steps: the modified silica gel particles were prepared as follows:
step 1, sequentially putting amino-terminated HPAMAM hyperbranched macromolecules, a silane coupling agent KH560 and a surfactant nonylphenol polyoxyethylene ether into water. The mass concentrations of HPAMAM, KH560 and nonylphenol polyoxyethylene ether are respectively 1%, 0.5% and 0.1%, and the modified impregnation liquid is obtained by uniformly stirring in a physical stirring or magnetic stirring mode.
And 2, adding 1 part by mass of silica gel into 2 parts by mass of modified impregnation liquid, continuously stirring uniformly, fully impregnating and standing for 4 hours to obtain modified silica gel emulsion.
And 3, drying the modified silica gel emulsion obtained in the step 2 in a converter type air heating bath at the temperature of 80 ℃ until the water content is 20% to obtain modified silica gel particles for later use.
Step two: preparation of composite Material
Heating and melting 1 part by mass of vinyl acetate, and dividing into 2 parts; respectively adding 5 parts by mass of the modified silica gel particles and 10 parts by mass of powdered activated carbon (coal carbon, the granularity is 30-60 meshes, and the CTC value is more than or equal to 90 percent) into 0.5 part by mass of vinyl acetate, uniformly mixing, respectively spreading on a non-woven fabric filter support net, cooling to prepare a first filter material and a second filter material, and bonding the back sides of the first filter material and the second filter material together to obtain the composite material for purifying air.
Example 3
The embodiment provides a preparation method of a composite material for purifying air, which comprises the following steps:
the method comprises the following steps: the modified silica gel particles were prepared as follows:
step 1, sequentially putting amino-terminated HPAMAM hyperbranched macromolecules, a silane coupling agent KH560 and a surfactant octylphenol polyoxyethylene ether into water. The mass concentrations of HPAMAM, KH560 and octylphenol polyoxyethylene ether are respectively 5%, 2.5% and 0.5%, and the modified impregnation liquid is obtained by uniformly stirring in a physical stirring or magnetic stirring manner.
And 2, adding 1 part by mass of silica gel into 2 parts by mass of modified impregnation liquid, continuously stirring uniformly, fully impregnating and standing for 8 hours to obtain modified silica gel emulsion.
And 3, drying the modified silica gel emulsion obtained in the step 2 in a converter type air heating bath at 100 ℃ until the water content is 10% to obtain modified silica gel particles for later use.
Step two: preparation of composite Material
Heating 2 parts by mass of epoxy acrylate, mixing 10 parts by mass of the modified silica gel particles and 15 parts by mass of powdered activated carbon (coal carbon with the granularity of 30-60 meshes and the CTC value of more than or equal to 90%) to form mixed powder, adding the mixed powder into the epoxy acrylate, uniformly mixing, spreading the mixed powder on a non-woven fabric filter support net, and cooling to prepare the air-purifying composite material.
The nonwoven fabric filter support webs used in examples 1-3 were of the same pore size, material, thickness and surface dimensions. The unmodified silica gel support used in examples 1 to 3 had a particle size of 30 to 60 mesh and a specific surface area of 300 to 600m 2 The pore volume is 0.6-1.1 mL/g; the molecular weight of the modifier HPAMAM is 5000-8000, the branching Degree (DB) is not less than 0.4, and the total amine value>0.069mol/g。
The air-purifying composite materials prepared in examples 1 to 3 were installed in an air purifier (test purifier: dingxin (YJ-37) was used)7) And the state of the instrument: 3 th) at 30m 3 The test is carried out in a closed environment cabin, and the test standard is executed according to GB18801-2015 air purifier. The aldehyde ketone sampling and detection standard is executed according to HJ/T400-2016 & lt & ltmethod for sampling and measuring volatile organic compounds and aldehyde ketone substances in a vehicle & gt.
Testing the instrument: formaldehyde and acetone are treated by adopting a high performance liquid chromatograph shimadzu LC-20A; toluene and n-hexyl were analyzed by gas chromatography-mass spectrometer Agilent 5975C/7890A. The test results are shown in the following table:
Figure BDA0002497225680000121
the CADR is a Clean Air output Rate (Clean Air Delivery Rate), and a higher CADR value indicates a higher purification performance of the purifier. As can be seen from the filter screens of the embodiments 1 to 3, the composite material has strong adsorption and purification effects on carbonyl molecules such as formaldehyde and acetone and hydrocarbon molecules such as toluene and n-hexane. In addition, the higher the grafting concentration of the amino-terminated HPAMAM and the larger the adhesion amount on the non-woven fabric filter support net, the higher the adsorption/purification efficiency of the composite material for purifying air on the aldehyde ketone molecules.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (5)

1. The preparation method of the composite material for purifying the air is characterized in that the composite material comprises a filtering support material, and activated carbon particles and modified silica gel particles which are attached to the filtering support material, wherein the modified silica gel particles comprise a silica gel carrier and ammonia-terminated groups grafted on the silica gel carrierHyperbranched polyamidoamines; the particle size of the silica gel carrier is 30-60 meshes, and the specific surface area is 300-600m 2 The pore volume is 0.6-1.1mL/g, and the mass ratio of the amino-terminated hyperbranched polyamidoamine to the silica gel carrier is 1-10:50; wherein the molecular weight of the amino-terminated hyperbranched polyamidoamine is 5000-8000, and the branching degree>0.4, total amine number>0.069mol/g；
The preparation method comprises the following steps:
the method comprises the following steps: preparing modified silica gel particles, which comprises the following steps:
s1, adding amino-terminated HPAMAM, a coupling agent and a surfactant into water, and dispersing to prepare a modified impregnation liquid;
s2, putting the silica gel carrier to be modified into the modified impregnation liquid, uniformly stirring, and standing for a preset time to obtain modified silica gel emulsion;
s3, drying the silica gel emulsion at 60-150 ℃ until the water content is 5-25% to obtain modified silica gel particles;
step two: mixing the modified silica gel particles and activated carbon particles according to a certain proportion to obtain an adsorption mixture; wherein the filtering support material is a non-woven filtering support net; uniformly dispensing glue on the non-woven fabric filter support net, scattering the adsorption mixture on the non-woven fabric filter support net before the glue is not cured, cooling and curing, blowing to remove the non-bonded adsorption mixture, and performing supplementary bonding according to conditions; or the filtering and supporting material is a material with the surface containing hot-melt polymer, and the adsorption mixture is bonded and attached to the filtering and supporting material in a hot-pressing compounding way to prepare the composite material for purifying air;
or the filtering and supporting material is a material with the surface containing hot-melt polymer, the modified silica gel particles and the activated carbon particles are respectively attached to the first filtering and supporting material and the second filtering and supporting material in a hot-pressing mode, and then the first filtering and supporting material and the second filtering and supporting material are compounded into a whole.
2. The preparation method of claim 1, wherein the activated carbon particles are coal-based carbon, the particle size is 30-60 meshes, and the CTC value is not less than 90%.
3. The preparation method according to claim 1, wherein in step S1, the coupling agent is one or more of KH550, KH560 or KH 570; the surfactant is one or a mixture of several of nonylphenol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, cetyl alcohol polyoxyethylene ether, octyl phenol polyoxyethylene ether and dodecyl polyoxyethylene ether.
4. The preparation method according to claim 1 or 3, wherein in step S1, the modified impregnation liquid contains 1 to 10 mass% of the amino-terminated HPAMAM, 0.5 to 5 mass% of the coupling agent, and 0.1 to 2 mass% of the surfactant.
5. The method according to claim 1, wherein the drying in step S3 is carried out in an air heating bath at 80 ℃ to 120 ℃ to a water content of 5% to 20% to obtain the modified silica gel particles.
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