CN116081623A - Super-hydrophobic activated carbon material and preparation method and application thereof - Google Patents

Super-hydrophobic activated carbon material and preparation method and application thereof Download PDF

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CN116081623A
CN116081623A CN202310375907.5A CN202310375907A CN116081623A CN 116081623 A CN116081623 A CN 116081623A CN 202310375907 A CN202310375907 A CN 202310375907A CN 116081623 A CN116081623 A CN 116081623A
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activated carbon
hydrophobic
super
carbon material
hydrophobic substance
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CN116081623B (en
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吴孝敏
吕碧洪
申华臻
黄志伟
荆国华
钟林发
张哲然
苏清发
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Huaqiao University
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
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    • C01B32/372—Coating; Grafting; Microencapsulation
    • 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
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    • 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
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    • 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
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
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Abstract

The invention belongs to the technical field of activated carbon modification, and particularly relates to a super-hydrophobic activated carbon material, and a preparation method and application thereof. The super-hydrophobic activated carbon material provided by the invention comprises activated carbon and hydrophobic substances distributed on the surface and the pore wall of the activated carbon; the hydrophobic substance is modified polydivinylbenzene; the mass percentage of the hydrophobic substance in the super-hydrophobic activated carbon material is 0.1-3wt%. The surface of the activated carbon has a large number of polar functional groups, and the invention adopts a surface modification method to introduce hydrophobic substances to the surface of the activated carbon, thereby reducing the number of the polar functional groups on the surface of the activated carbon and improving the hydrophobicity of the surface of the activated carbon so as to improve the selective adsorption capacity of the activated carbon on nonpolar substances. Therefore, the super-hydrophobic activated carbon material provided by the invention has strong selectivity on the adsorption of target VOCs under the relative humidity of 10-80%, and has excellent adsorption performance.

Description

Super-hydrophobic activated carbon material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of activated carbon modification, and particularly relates to a super-hydrophobic activated carbon material, and a preparation method and application thereof.
Background
The active carbon is used as a common porous adsorption material, and the surface of the active carbon contains rich adsorption active sites, pore structures and huge surface area, and has chemical stability and thermal stability. Is widely applied to the fields of adsorption, separation, catalysis, electrons and the like. Also commonly used as a gas phase or liquid phase adsorbent, and has wide application in the fields of adsorption collection and Volatile Organic Compounds (VOCs) treatment.
However, the activated carbon surface is more likely to absorb water than other adsorbent materials due to the action of polar functional groups such as hydroxyl group (-OH), carboxyl group (-COOH), lactone group (=o) and the like. Therefore, the moist air has a great influence on the adsorption effect of the activated carbon. The water vapor preferentially gathers inside the activated carbon, thereby reducing the adsorption of other substances. More specifically, the activated carbon generates adsorption competition with the VOCs in the adsorption process, so that the saturated adsorption quantity of the adsorbent to the target VOCs is weakened, and the adsorption rate is reduced. In industrial flue gas purification, activated carbon materials are used for removing various pollutants (such as SO 2 、NO x Smoke, heavy metals, volatile organic compounds, etc.) effect is greatly reduced. In the aspect of household life, activated carbon absorbs water vapor in air or water drops to lose the adsorption effect. In the purification of VOCs in the organic pollution site, the water content of the soil is higher, and the activated carbon is absorbed due to high humidityInhibition by VOCs often results in a substantial reduction in the adsorption effect of the activated carbon.
Disclosure of Invention
The invention aims to provide a super-hydrophobic activated carbon material, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a super-hydrophobic active carbon material, which comprises active carbon and hydrophobic substances distributed on the surface and the wall of the active carbon; the hydrophobic substance is modified polydivinylbenzene;
the preparation method of the hydrophobic substance comprises the following steps: mixing divinylbenzene, methacrylic acid, water, azodiisobutyronitrile and tetrahydrofuran, and carrying out polymerization reaction to obtain the hydrophobic substance; the mass ratio of the divinylbenzene to the methacrylic acid is 10-25: 1-10;
the mass percentage of the hydrophobic substance in the super-hydrophobic activated carbon material is 0.1-3wt%.
Preferably, the activated carbon comprises coal-based activated carbon and/or wood-based activated carbon.
Preferably, the mass ratio of divinylbenzene to water is 10-25: 0.5-18;
the mass ratio of the divinylbenzene to the azodiisobutyronitrile is 10-25: 0.1 to 0.85.
Preferably, the polymerization reaction is carried out at a temperature of 65-110 ℃ for 6-48 hours.
The invention also provides a preparation method of the super-hydrophobic activated carbon material, which comprises the following steps:
and (3) dipping or spraying the activated carbon by adopting the hydrophobic substance emulsion, and drying to obtain the super-hydrophobic activated carbon material.
Preferably, the mass percentage of the hydrophobic substance in the hydrophobic substance emulsion is 0.1-6%;
the solvent in the hydrophobic substance emulsion comprises ethyl acetate and/or tetrahydrofuran.
Preferably, the temperature of the soaking is 15-50 ℃ and the time is 15-120 min.
Preferably, the drying temperature is 60-150 ℃ and the drying time is 1-24 hours.
The invention also provides the application of the super-hydrophobic activated carbon material in the technical scheme or the super-hydrophobic activated carbon material obtained by the preparation method in the technical scheme in the volatile organic compound adsorption.
The invention provides a super-hydrophobic active carbon material, which comprises active carbon and hydrophobic substances distributed on the surface and the wall of the active carbon; the hydrophobic substance is modified polydivinylbenzene; the mass percentage of the hydrophobic substance in the super-hydrophobic activated carbon material is 0.1-3wt%. The surface of the activated carbon is provided with a large number of polar functional groups, and the hydrophobic substance is introduced to the surface of the activated carbon by adopting a surface modification method, so that the hydrophobic substance is adsorbed on the surface of the activated carbon by virtue of Van der Waals force and acting force of hydrogen bonds, the number of the polar functional groups on the surface of the activated carbon is reduced, and the hydrophobicity of the surface of the activated carbon is improved, so that the selective adsorption capacity of the hydrophobic substance on nonpolar substances is improved. Therefore, the super-hydrophobic activated carbon material provided by the invention has strong selectivity on the adsorption of target VOCs under the relative humidity of 10-80%, and has excellent adsorption performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a graph showing the result of penetrating adsorption of toluene vapor under the conditions of humidity (rh=40%) by the superhydrophobic coconut shell activated carbon material of example 1;
fig. 2 is a graph showing the result of penetrating adsorption of toluene vapor under the condition of humidity (rh=30%) by the superhydrophobic wood-activated carbon material of example 2.
Detailed Description
The invention provides a super-hydrophobic active carbon material, which comprises active carbon and hydrophobic substances distributed on the surface and the wall of the active carbon; the hydrophobic substance is modified polydivinylbenzene;
the preparation method of the hydrophobic substance comprises the following steps: mixing divinylbenzene, methacrylic acid, water, azodiisobutyronitrile and tetrahydrofuran, and carrying out polymerization reaction to obtain the hydrophobic substance; the mass ratio of the divinylbenzene to the methacrylic acid is 10-25: 1-10;
the mass percentage of the hydrophobic substance in the super-hydrophobic activated carbon material is 0.1-3wt%.
In the present invention, the raw material components are commercially available products well known to those skilled in the art unless specified otherwise.
In the invention, the mass percentage of the hydrophobic substance in the super-hydrophobic active carbon material is 0.1-3 wt%, preferably 0.3-2.5%, more preferably 0.5-2%.
In the invention, the specific surface area of the super-hydrophobic activated carbon material is preferably 300-2000 m 2 Preferably 400 to 160 m 2 Preferably 500 to 1200 m/g 2 /g; the pore volume is preferably 0.1-1.0 cm 3 Preferably 0.2 to 0.8 cm/g 3 Preferably 0.2 to 0.5 cm/g 3 /g; the pore diameter is preferably 1.0 to 3.0nm, more preferably 1.5 to 2.5nm, and most preferably 1.7 to 2.3nm.
In the present invention, the activated carbon preferably includes coal activated carbon and/or woody activated carbon, more preferably includes woody activated carbon; the wood activated carbon preferably comprises one or more of firewood, wood chips, wood blocks, coconut shells and fruit shells, more preferably comprises one or more of firewood, wood blocks and coconut shells, and most preferably comprises firewood or coconut shells; when the active carbon is more than two of the specific choices, the proportion of the active carbon is not limited in any particular way, and any proportion is adopted; the particle size of the activated carbon is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the preparation method of the hydrophobic substance includes:
and mixing divinylbenzene, methacrylic acid, water, azodiisobutyronitrile and tetrahydrofuran, and carrying out polymerization reaction to obtain the hydrophobic substance.
In the invention, the mass ratio of the divinylbenzene to the methacrylic acid is 10-25: 1 to 10, preferably 15 to 25:1 to 10, more preferably 15 to 20: 2-6.
In the present invention, the methacrylic acid functions to enhance the hydrophobic effect of polydivinylbenzene.
In the invention, the mass ratio of divinylbenzene to water is preferably 10-25: 0.5 to 18, more preferably 15 to 25: 5-15, most preferably 15-20: 8-12.
In the invention, the mass ratio of the divinylbenzene to the azobisisobutyronitrile is preferably 10 to 25:0.1 to 0.85, more preferably 15 to 25:0.3 to 0.8, most preferably 15 to 20:0.4 to 0.6.
In the present invention, the water and azobisisobutyronitrile function to initiate and induce the progress of the polymerization reaction.
In the invention, the mass ratio of divinylbenzene to tetrahydrofuran is preferably 10-25: 100, more preferably 15 to 25:100, most preferably 15 to 20:100.
in the present invention, the tetrahydrofuran functions as a reaction solvent.
In the invention, the mixing time is preferably 1-6 hours, more preferably 2-5 hours, and most preferably 3-4 hours; the mixing is preferably performed by stirring; the temperature of the mixing is preferably room temperature; the stirring speed is not particularly limited, and may be carried out at a speed well known to those skilled in the art.
In the invention, the temperature of the polymerization reaction is preferably 65-110 ℃, more preferably 70-100 ℃, and most preferably 80-90 ℃; the time is preferably 6 to 48 hours, more preferably 10 to 40 hours, and most preferably 20 to 30 hours.
In the present invention, cooling is preferably further included after completion of the polymerization reaction; the cooling is preferably natural cooling; the natural cooling preferably includes evaporating the solvent.
The super-hydrophobic activated carbon material provided by the invention has strong selectivity on the adsorption of target VOCs under the relative humidity of 10-80%, and has excellent adsorption performance and durability. Specifically, the surface of the activated carbon is provided with a large number of polar functional groups, and the hydrophobic substance is introduced to the surface of the activated carbon by adopting a surface modification method, so that the hydrophobic substance is adsorbed on the surface of the activated carbon by virtue of Van der Waals force and acting force of hydrogen bonds, the number of polar functional groups on the surface of the activated carbon is reduced, and the hydrophobicity of the surface of the activated carbon is improved, so that the selective adsorption capacity of the hydrophobic substance on nonpolar substances is improved.
The invention also provides a preparation method of the super-hydrophobic activated carbon material, which comprises the following steps:
and (3) dipping or spraying the activated carbon by adopting the hydrophobic substance emulsion, and drying to obtain the super-hydrophobic activated carbon material.
In the present invention, the present invention also preferably includes drying the activated carbon before the impregnation or spraying; the drying temperature is preferably 80-150 ℃, more preferably 90-130 ℃, and most preferably 100-120 ℃; the time is preferably 2-24 hours, more preferably 5-20 hours, and most preferably 10-15 hours; the drying is preferably carried out using an oven.
In the invention, the mass percentage of the hydrophobic substance in the hydrophobic substance emulsion is preferably 0.1-6%, more preferably 1-5%, and most preferably 2-4%; the solvent in the hydrophobic substance emulsion preferably comprises ethyl acetate and/or tetrahydrofuran, more preferably tetrahydrofuran; when the solvent is more than two of the above specific choices, the invention does not have any special limitation on the proportion of the solvent, and any proportion is adopted; the hydrophobic substance emulsion is prepared by adopting an ultrasonic mixing mode; the process of ultrasonic mixing is not particularly limited in the present invention, and the hydrophobic substance emulsion may be uniformly dispersed in a manner well known to those skilled in the art.
In the invention, the temperature of the impregnation is preferably 15-50 ℃, more preferably 20-45 ℃, and most preferably 25-35 ℃; the time is preferably 15-120 min, more preferably 30-100 min, and most preferably 40-80 min; the heating mode of the dipping is preferably water bath heating; the process of heating in the water bath is not particularly limited in the present invention, and may be performed in a manner well known to those skilled in the art.
In the present invention, the spray is preferably an atomized spray; the atomization spraying process is not limited in any particular way, and the mass percentage of the modified polydivinylbenzene in the dried super-hydrophobic activated carbon material can reach 0.1-3wt% by adopting a mode well known to a person skilled in the art.
In the invention, the drying temperature is preferably 60-150 ℃, more preferably 80-140 ℃, and most preferably 100-120 ℃; the time is preferably 1-24 hours; when the drying is performed after the impregnation, the drying time is more preferably 5 to 15 hours, and most preferably 6 to 12 hours; when the drying is performed after the spraying, the drying time is more preferably 2 to 15 hours, and most preferably 3 to 9 hours.
The preparation method provided by the invention has little influence on the pore structure of the surface of the activated carbon, can not influence the adsorption characteristic of the activated carbon in an aqueous environment, and the obtained super-hydrophobic activated carbon has good hydrophobic performance and large pore volume, has stable material performance, and solves the problem that the adsorption capacity of the activated carbon to target organic matters is reduced due to competitive adsorption of water molecules in the application process. Meanwhile, the preparation method is suitable for modification treatment of different types of activated carbon, so that different types of super-hydrophobic activated carbon can be obtained, performance requirements of different occasions are met, the method has wide adaptability, the process is simple, the equipment requirement is low, the preparation condition is mild, the preparation cost is low, and the method is easy for large-scale production with high yield.
The invention also provides the application of the super-hydrophobic activated carbon material in the technical scheme or the super-hydrophobic activated carbon material obtained by the preparation method in the technical scheme in the volatile organic compound adsorption.
The process of the application is not particularly limited, and may be performed in a manner well known to those skilled in the art.
For further explanation of the present invention, the superhydrophobic activated carbon materials, the preparation method and the application thereof provided by the present invention are described in detail below with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1: and (3) pre-heating treatment of activated carbon: weighing 20g of coconut shell activated carbon sample, putting the sample into a baking oven with the temperature of 110 ℃, drying for 10 hours, and fully removing water for standby;
preparation of modified polydivinylbenzene: dissolving 5.6mL of divinylbenzene, 0.5mL of methacrylic acid, 4mL of water and 0.15g of azobisisobutyronitrile into 40mL of tetrahydrofuran, stirring at room temperature for 3h, transferring the mixed solution into a hydrothermal kettle, keeping at 100 ℃ for 24h, taking out the reaction kettle, naturally cooling, and volatilizing the solvent to obtain a modified polydivinylbenzene material;
preparing modified polydivinylbenzene emulsion: dispersing 0.2g of modified polydivinylbenzene in 4.8g of tetrahydrofuran, and uniformly mixing by ultrasonic to prepare modified polydivinylbenzene emulsion with the content of 4 wt%;
activated carbon modification: and spraying the preheated coconut shell activated carbon with the modified polydivinylbenzene emulsion of 4wt.% and uniformly spraying the coconut shell activated carbon on the surface of the activated carbon in an atomized form to form a film. And (3) drying the sprayed activated carbon at 120 ℃ for 4 hours to obtain the super-hydrophobic coconut shell activated carbon material with the mass percentage of the modified polydivinylbenzene of 1.2 percent.
The specific surface area of the superhydrophobic coconut shell activated carbon material and the characterization result of the untreated coconut shell activated carbon are shown in table 1:
TABLE 1 characterization results of superhydrophobic coconut activated carbon and unmodified coconut activated carbon
Specific surface area (m) 2 /g) Pore volume (cm) 3 /g) Aperture (nm)
Unmodified coconut shell activated carbon 1152.73 0.483 2.332
Super-hydrophobic coconut shell activated carbon 1117.49 0.465 2.278
As can be seen from Table 1, the specific surface area of the superhydrophobic coconut shell activated carbon material is equivalent to that of untreated coconut shell activated carbon, which shows that the process has little influence on the pore structure of the activated carbon surface.
The penetrating adsorption result of toluene vapor (toluene concentration is 500ppm and adsorbent material is 0.15 g) of the superhydrophobic coconut shell activated carbon material under the condition of humidity (RH=40%) is shown in the attached figure 1; as can be seen from fig. 1, the penetration adsorption time of the coconut shell activated carbon material to toluene vapor is quite equal to that of rh=0, which indicates that the super-hydrophobic coconut shell activated carbon shows stronger selectivity to target VOCs under the humidity (rh=40%) condition.
Example 2: and (3) pre-heating treatment of activated carbon: weighing 20g of wood activated carbon sample, putting the wood activated carbon sample into a baking oven with the temperature of 100 ℃, drying for 12 hours, and fully removing water for standby;
preparation of modified polydivinylbenzene: dissolving 5.2mL of divinylbenzene, 1.5mL of methacrylic acid, 4mL of water and 0.20g of azodiisobutyronitrile in 40mL of tetrahydrofuran, stirring for 4 hours at room temperature, transferring the mixed solution into a hydrothermal kettle, maintaining at 95 ℃ for 29 hours, taking out the reaction kettle, naturally cooling, and volatilizing the solvent to obtain a modified polydivinylbenzene material;
preparing modified polydivinylbenzene emulsion: dispersing 0.2g of modified polydivinylbenzene in 19.8g of ethyl acetate, and uniformly mixing by ultrasonic to prepare a modified polydivinylbenzene emulsion with the content of 1 wt%;
activated carbon modification: the wood activated carbon after the pre-heating treatment was immersed in the above 1wt.% modified polydivinylbenzene emulsion at a water bath temperature of 30 ℃ for 30min. And taking out the impregnated wood activated carbon, and drying the wood activated carbon in a drying oven at 100 ℃ for 8 hours to enable the modified polydivinylbenzene to be dried on the surface of the activated carbon to form a film, thus obtaining the super-hydrophobic wood activated carbon material with the mass percentage of the modified polydivinylbenzene being 1.8 percent.
The characterization results of the specific surface area of the super-hydrophobic wood activated carbon material and the untreated wood activated carbon are shown in table 2:
TABLE 2 characterization results of superhydrophobic woody activated carbon and unmodified woody activated carbon
Specific surface area (m) 2 /g) Pore volume (cm) 3 /g) Aperture (nm)
Unmodified wood activated carbon 568.23 0.305 1.783
Super-hydrophobic wood activated carbon 553.11 0.298 1.759
As can be seen from table 2, the specific surface area of the super-hydrophobic wood activated carbon material is equivalent to that of untreated wood activated carbon, which shows that the process has little influence on the pore structure of the activated carbon surface.
The penetrating adsorption result of toluene vapor (toluene concentration is 500ppm, adsorbent material 0.15 g) under the condition of superhydrophobic wood-based activated carbon material relative humidity (RH=30%) is shown in fig. 2; as can be seen from fig. 2, the penetration adsorption time of the wood activated carbon material to toluene vapor is quite equal to that of rh=0, which indicates that the super-hydrophobic wood activated carbon shows stronger selectivity to target VOCs under the humidity (rh=30%) condition.
Example 3: and (3) pre-heating treatment of activated carbon: weighing 10g of wood activated carbon and 10g of coal activated carbon sample, putting into a baking oven with the temperature of 105 ℃, drying for 11 hours, and fully removing water for later use;
configuration of modified polydivinylbenzene: dissolving 6.3mL of divinylbenzene, 4mL of water and 0.12g of azobisisobutyronitrile into 40mL of tetrahydrofuran, stirring for 2 hours at room temperature, transferring the mixed solution into a hydrothermal kettle, maintaining at 78 ℃ for 36 hours, taking out the reaction kettle, naturally cooling, and volatilizing the solvent to obtain a modified polydivinylbenzene material;
preparing modified polydivinylbenzene emulsion: dispersing 0.3g of modified polydivinylbenzene in 9.8g of ethyl acetate, and uniformly mixing by ultrasonic to prepare a modified polydivinylbenzene emulsion with the content of 3 wt%;
activated carbon modification: and spraying the preheated wood and coal activated carbon with the modified polydivinylbenzene emulsion of 3wt.% to uniformly spray the modified polydivinylbenzene emulsion on the surface of the activated carbon in an atomized form to form a film. And (3) drying the sprayed activated carbon at 80 ℃ for 5 hours to obtain the super-hydrophobic mixed activated carbon material with the mass percentage of modified polydivinylbenzene of 2.4 wt%.
The penetration adsorption time of the wood and coal activated carbon material on toluene vapor (toluene concentration is 500ppm, adsorbent is 0.15g, RH=50%) is equivalent to RH=0.
Example 4: and (3) pre-heating treatment of activated carbon: weighing 20g of coal activated carbon sample, putting the sample into a baking oven with the temperature of 130 ℃, drying for 6 hours, and fully removing water for later use;
configuration of modified polydivinylbenzene: dissolving 4.5mL of divinylbenzene, 2.8mL of methacrylic acid, 4mL of water and 0.22g of azodiisobutyronitrile in 40mL of tetrahydrofuran, stirring for 4 hours at room temperature, transferring the mixed solution into a hydrothermal kettle, maintaining at 90 ℃ for 30 hours, taking out the reaction kettle, naturally cooling, and volatilizing the solvent to obtain a modified polydivinylbenzene material;
preparing modified polydivinylbenzene emulsion: dispersing 0.2g of modified polydivinylbenzene in 19.8g of tetrahydrofuran, and uniformly mixing by ultrasonic to prepare modified polydivinylbenzene emulsion with the content of 1 wt%;
activated carbon modification: the preheated coal activated carbon is immersed in the 1wt.% modified polydivinylbenzene emulsion for 20min at a water bath temperature of 40 ℃. And taking out the impregnated coal activated carbon, and drying the impregnated coal activated carbon in a drying oven at 120 ℃ for 8 hours to enable the modified polydivinylbenzene to be dried on the surface of the activated carbon to form a film, thus obtaining the super-hydrophobic coal activated carbon material with the mass percentage of the modified polydivinylbenzene being 0.7wt%.
The breakthrough adsorption time of the coal activated carbon material on toluene vapor (toluene concentration is 500ppm, adsorbent 0.15g, RH=30%) is equivalent to RH=0.
From the above examples, the super-hydrophobic activated carbon material provided by the invention shows strong selectivity on the adsorption of target VOCs under the relative humidity of 10-80%, and has excellent adsorption performance and durability. Specifically, the surface of the activated carbon is provided with a large number of polar functional groups, and the hydrophobic substance is introduced to the surface of the activated carbon by adopting a surface modification method, so that the hydrophobic substance is adsorbed on the surface of the activated carbon by virtue of Van der Waals force and acting force of hydrogen bonds, the number of polar functional groups on the surface of the activated carbon is reduced, and the hydrophobicity of the surface of the activated carbon is improved, so that the selective adsorption capacity of the hydrophobic substance on nonpolar substances is improved.
The preparation method provided by the invention has little influence on the pore structure of the surface of the activated carbon, can not influence the adsorption characteristic of the activated carbon in an aqueous environment, and the obtained super-hydrophobic activated carbon has good hydrophobic performance and large pore volume, has stable material performance, and solves the problem that the adsorption capacity of the activated carbon to target organic matters is reduced due to competitive adsorption of water molecules in the application process. Meanwhile, the preparation method is suitable for modification treatment of different types of activated carbon, so that different types of super-hydrophobic activated carbon can be obtained, performance requirements of different occasions are met, the method has wide adaptability, the process is simple, the equipment requirement is low, the preparation condition is mild, the preparation cost is low, and the method is easy for large-scale production with high yield.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.

Claims (9)

1. A super-hydrophobic active carbon material is characterized by comprising active carbon and hydrophobic substances distributed on the surface and the wall of the active carbon; the hydrophobic substance is modified polydivinylbenzene;
the preparation method of the hydrophobic substance comprises the following steps: mixing divinylbenzene, methacrylic acid, water, azodiisobutyronitrile and tetrahydrofuran, and carrying out polymerization reaction to obtain the hydrophobic substance; the mass ratio of the divinylbenzene to the methacrylic acid is 10-25: 1-10;
the mass percentage of the hydrophobic substance in the super-hydrophobic activated carbon material is 0.1-3wt%.
2. The superhydrophobic activated carbon material of claim 1, wherein the activated carbon comprises coal-based activated carbon and/or wood-based activated carbon.
3. The super-hydrophobic activated carbon material according to claim 1, wherein the mass ratio of divinylbenzene to water is 10-25: 0.5-18;
the mass ratio of the divinylbenzene to the azodiisobutyronitrile is 10-25: 0.1 to 0.85.
4. The superhydrophobic activated carbon material of claim 1, wherein the polymerization reaction temperature is 65-110 ℃ and the polymerization reaction time is 6-48 h.
5. The method for preparing the super-hydrophobic activated carbon material according to any one of claims 1 to 4, which is characterized by comprising the following steps:
and (3) dipping or spraying the activated carbon by adopting the hydrophobic substance emulsion, and drying to obtain the super-hydrophobic activated carbon material.
6. The preparation method of claim 5, wherein the hydrophobic substance emulsion comprises 0.1-6% of hydrophobic substance by mass;
the solvent in the hydrophobic substance emulsion comprises ethyl acetate and/or tetrahydrofuran.
7. The method according to claim 5, wherein the temperature of the impregnation is 15-50 ℃ and the time is 15-120 min.
8. The method according to claim 5, wherein the drying temperature is 60-150 ℃ and the drying time is 1-24 hours.
9. The use of the superhydrophobic activated carbon material according to any one of claims 1-4 or the superhydrophobic activated carbon material obtained by the preparation method according to any one of claims 5-8 in volatile organic compound adsorption.
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