CN112076726A - Mesoporous molecular sieve loaded with ionic liquid and preparation method and application thereof - Google Patents

Mesoporous molecular sieve loaded with ionic liquid and preparation method and application thereof Download PDF

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Publication number
CN112076726A
CN112076726A CN201910506177.1A CN201910506177A CN112076726A CN 112076726 A CN112076726 A CN 112076726A CN 201910506177 A CN201910506177 A CN 201910506177A CN 112076726 A CN112076726 A CN 112076726A
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molecular sieve
mesoporous molecular
ionic liquid
cation
matrix
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Inventor
闫柯乐
林雨
肖安山
李莹
张红星
胡绪尧
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China Petroleum and Chemical Corp
Sinopec Qingdao Safety Engineering Institute
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China Petroleum and Chemical Corp
Sinopec Qingdao Safety Engineering Institute
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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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • 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
    • B01J20/16—Alumino-silicates
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention relates to the field of mesoporous molecular sieve surface modification, and discloses an ionic liquid loaded mesoporous molecular sieve, and a preparation method and application thereof. The mesoporous molecular sieve loaded with the ionic liquid comprises a mesoporous molecular sieve matrix and the ionic liquid loaded on the mesoporous molecular sieve matrix; wherein the surface of the mesoporous molecular sieve matrix is provided with a hydrophobic modification layer. The mesoporous molecular sieve loaded with the ionic liquid has the advantages of simple preparation method, large absorption capacity on volatile organic compounds and high efficiency.

Description

Mesoporous molecular sieve loaded with ionic liquid and preparation method and application thereof
Technical Field
The invention relates to the field of mesoporous molecular sieve surface modification, in particular to a mesoporous molecular sieve loaded with ionic liquid and a preparation method and application thereof.
Background
The ionic liquid is a salt composed of cations and anions and is liquid at a certain temperature. The composite material has the advantages of extremely low vapor pressure, high thermal stability, good solubility, designable structure and the like, and has good application prospect in the aspect of absorbing and treating VOCs. However, the ionic liquid has the disadvantages of high cost, large dosage, high viscosity, difficult separation after use and the like, so the ionic liquid has certain limitation in the aspect of industrial application. The method of loading the ionic liquid by the porous adsorption material can integrate the advantages of the ionic liquid and the porous adsorption material, so that the use amount of the ionic liquid can be greatly reduced, the cost is reduced, and the adsorption surface area is favorably enlarged, thereby promoting the reaction process. However, conventional porous materials such as activated carbon and the like have narrow channels and are difficult to effectively load ionic liquid, and mesoporous molecular sieves have incomparable advantages in terms of ionic liquid load type matrixes due to the advantages of large channels, large specific surface area, large pore volume, high hydrophobicity, surface inertness and the like.
The ionic liquid supporting method includes an immersion method, a chemical method, a sol-gel method, and the like. The impregnation method is simple to operate, generally, the ionic liquid is dripped into the macroporous carrier until the carrier is completely wet, and the ionic liquid which is not absorbed by the carrier is removed after the impregnation is carried out for a period of time, so that the method is simplest and has wider application; although the chemical loading method can avoid the loss of the ionic liquid, the chemical loading method is not widely used due to the defects of complicated steps, high cost, low loading rate and the like; the sol-gel method can be carried out at a lower temperature, the reaction process is easy to control, the chemical uniformity of the prepared material can reach the molecular level, and the sol-gel can not be widely applied because the sol-gel needs a longer time to complete. CN107651651A discloses a porous solid supported ionic liquid, which is composed of a porous solid carrier and an ionic liquid supported on the carrier, but the supported porous solid mainly aims at the adsorption treatment of acidic gases such as HCl, and the treatment effect of VOCs is not described. CN108114698A proposes a preparation method and application of a porous material loaded ionic liquid composite material gas collection, but the patent only simply loads ionic liquid on the porous material, but does not effectively modify the surface functional groups of the porous material, and the defects of small VOCs adsorption capacity, difficult regeneration and the like exist.
Disclosure of Invention
The invention aims to overcome the problems of small adsorption capacity, low efficiency, difficult regeneration and the like of a mesoporous molecular sieve for volatile organic compounds in the prior art, and provides an ionic liquid-loaded mesoporous molecular sieve, a preparation method and application thereof.
In order to achieve the above object, an aspect of the present invention provides an ionic liquid-supported mesoporous molecular sieve, characterized in that the mesoporous molecular sieve comprises a mesoporous molecular sieve matrix and an ionic liquid supported thereon; wherein the surface of the mesoporous molecular sieve matrix is provided with a hydrophobic modification layer.
Preferably, the particle diameter of the mesoporous molecular sieve matrix is 20-200 meshes, and the specific surface area is 100-1500m2Per g, pore volume of 0.25-1.8cm3(ii)/g, the average pore diameter is 2-20 nm.
Preferably, the particle diameter of the mesoporous molecular sieve matrix is 10-200 meshes, and the specific surface area is 100-500m2G, pore volume of 0.25-1.5cm3(ii)/g, the average pore diameter is 5-20 nm.
Preferably, the cation of the ionic liquid is one or more of 1-butyl-3-methylimidazole cation, 1-propyl-3-methylimidazole cation, 1-ethyl-3-methylimidazole cation, 1-hexyl-3-methylimidazole cation, 1-pentyl-3-methylimidazole cation, N-hexylpyridine cation, N-butylpyridine cation, N-octylpyridine cation and N-methylpyrrolidine cation.
Preferably, the anion of the ionic liquid is one or more of chloride, bromide, tetrafluoroborate and hexafluorophosphate.
Preferably, the loading of the ionic liquid is 1-40 wt% relative to the mesoporous molecular sieve matrix.
Preferably, the hydrophobic modification layer is a hydrophobic modifier layer.
Preferably, the hydrophobic modifier is one or more of 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane and 2-methoxy-propyltrimethoxysilane, preferably one or more of methyltriethoxysilane, phenyltriethoxysilane and 3-aminopropyltriethoxysilane.
Preferably, the hydrophobic modifier is used in an amount of 0.1 to 0.5 wt%, preferably 0.3 to 0.5 wt%, relative to the mesoporous molecular sieve matrix.
Preferably, the hydrophobically modified layer is a polymer layer.
Preferably, the polymer layer is polymerized from a first monomer and a second monomer; the first monomer is one or more of chloroethylene, acrylic acid, methyl acrylate, isobornyl methacrylate, n-butyl ethacrylate and hexadecyl ethacrylate; the second monomer is styrene and/or p-methylstyrene.
Preferably, the content of the first monomer is 50 to 100 wt%, preferably 70 to 100 wt%, and the content of the second monomer is 10 to 50 wt%, more preferably 30 to 50 wt%, with respect to the mesoporous molecular sieve matrix.
In a second aspect, the present invention provides a method for preparing a mesoporous molecular sieve loaded with an ionic liquid, the method comprising: the method comprises the step of contacting a mixed solution of an ionic liquid and a loaded organic solvent with a mesoporous molecular sieve matrix to obtain the mesoporous molecular sieve loaded with the ionic liquid, wherein the surface of the mesoporous molecular sieve matrix is provided with a hydrophobic modification layer.
Preferably, the particle diameter of the mesoporous molecular sieve matrix is 20-200 meshes, and the specific surface area is 100-1500m2Per g, pore volume of 0.25-1.8cm3(ii)/g, the average pore diameter is 2-20 nm.
Preferably, theThe particle diameter of the mesoporous molecular sieve matrix is 10-200 meshes, and the specific surface area is 100-2G, pore volume of 0.25-1.5cm3(ii)/g, the average pore diameter is 5-20 nm.
Preferably, the cation of the ionic liquid is one or more of 1-butyl-3-methylimidazole cation, 1-propyl-3-methylimidazole cation, 1-ethyl-3-methylimidazole cation, 1-hexyl-3-methylimidazole cation, 1-pentyl-3-methylimidazole cation, N-hexylpyridine cation, N-butylpyridine cation, N-octylpyridine cation and N-methylpyrrolidine cation.
Preferably, the anion of the ionic liquid is one or more of chloride, bromide, tetrafluoroborate and hexafluorophosphate.
Preferably, the organic solvent for supporting is one or more of methanol, ethanol, ethylene glycol and tetrahydrofuran, and preferably methanol.
Preferably, the weight ratio of the mixed solution of the ionic liquid and the organic solvent for supporting to the matrix of the mesoporous molecular sieve is (0.5-5): 1, preferably (1-4): 1, more preferably (1-2): 1.
preferably, the hydrophobic modification layer is formed of a hydrophobic modification agent.
Preferably, the hydrophobic modifier is one or more of 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane and 2-methoxy-propyltrimethoxysilane, preferably one or more of methyltriethoxysilane, phenyltriethoxysilane and 3-aminopropyltriethoxysilane.
Preferably, the hydrophobic modifier is used in an amount of 0.1 to 0.5 wt%, preferably 0.3 to 0.5 wt%, relative to the mesoporous molecular sieve matrix.
Preferably, the polymer layer is polymerized from a first monomer and a second monomer.
Preferably, the first monomer is used in an amount of 50 to 100 wt%, preferably 70 to 100 wt%, relative to the mesoporous molecular sieve matrix.
Preferably, the second monomer is used in an amount of 10 to 50 wt%, more preferably 30 to 50 wt%, relative to the mesoporous molecular sieve matrix.
In a third aspect, the invention provides an application of the ionic liquid supported mesoporous molecular sieve or the ionic liquid supported mesoporous molecular sieve obtained by the preparation method in adsorption of volatile organic compounds.
Through the technical scheme, the hydrophobic resin layer is formed on the surface of the mesoporous molecular sieve, and then the effective load of the ionic liquid is carried out, so that the capability of adsorbing and treating VOCs by the mesoporous molecular sieve is improved. The mesoporous molecular sieve loaded with the ionic liquid can effectively adsorb and treat volatile organic gases such as cyclohexane, toluene and the like to achieve the aim of rapid removal, has good adsorption speed and adsorption capacity, has the characteristics of high reaction rate, simple preparation, economy, environmental protection and the like, and has good application prospect.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the "particle diameter" is an average particle diameter.
The invention provides a mesoporous molecular sieve loaded with ionic liquid, which comprises a mesoporous molecular sieve matrix and the ionic liquid loaded on the mesoporous molecular sieve matrix; wherein the surface of the mesoporous molecular sieve matrix is provided with a hydrophobic modification layer.
According to the present invention, the mesoporous molecular sieve substrate may be an unmodified mesoporous molecular sieve, and the specific type thereof is not particularly limited, and may be, for example, an SBA type molecular sieve (SBA-15 type), an MCM type molecular sieve (MCM-41 type), or the like.
In order to further improve the adsorption performance of the mesoporous molecular sieve for loading the ionic liquid, the particle size of the mesoporous molecular sieve matrix is preferably 20-200 meshes by weightSurface area of 100-2Per g, pore volume of 0.25-1.8cm3(ii)/g, the average pore diameter is 2-20 nm. More preferably, the particle diameter of the mesoporous molecular sieve matrix is 10-200 meshes, and the specific surface area is 100-500m2G, pore volume of 0.25-1.5cm3(ii)/g, the average pore diameter is 5-20 nm.
According to a preferred embodiment of the present invention, the particle size of the mesoporous molecular sieve matrix is 100-200 mesh, preferably 150-180 mesh; the specific surface area is 800-2A/g of preferably 1000-2(ii)/g; the pore volume is 1.2-1.8cm3In g, preferably 1.2 to 1.5cm3(ii)/g; the average pore diameter is 2-10nm, preferably 3-5 nm.
According to another preferred embodiment of the present invention, the particle size of the mesoporous molecular sieve matrix is 20 to 100 mesh, more preferably 50 to 80 mesh; the specific surface area is 500-1000m2(ii)/g, more preferably 750-2(ii)/g; the pore volume is 0.6-1.5cm3Per g, more preferably 0.8 to 1.2cm3(ii)/g; the average pore diameter is 3 to 20nm, more preferably 8 to 12 nm.
According to the present invention, any ionic liquid capable of adsorbing volatile compounds may be used as the ionic liquid. Specifically, the cation of the ionic liquid is one or more of 1-butyl-3-methylimidazole cation, 1-propyl-3-methylimidazole cation, 1-ethyl-3-methylimidazole cation, 1-hexyl-3-methylimidazole cation, 1-pentyl-3-methylimidazole cation, N-hexylpyridine cation, N-butylpyridine cation, N-octylpyridine cation and N-methylpyrrolidine cation; preferably, the anion of the ionic liquid is one or more of chloride, bromide, tetrafluoroborate and hexafluorophosphate.
The specific ionic liquid can be one or more of 1-ethyl-3-methylimidazole methyl sulfate salt, 1-ethyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole bisulfate, 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 1-butyl-3-methylimidazole hexafluorophosphate, 1-ethyl-3-methylimidazole acetate, 1-ethyl-3-methylimidazole lactate and 1-ethyl-3-methylimidazole chloride salt; preferably one or more of 1-butyl-3-methylimidazole methyl sulfate and 1-butyl-3-methylimidazole hexafluorophosphate.
According to the present invention, preferably, the loading amount of the ionic liquid may be 1 to 40 wt% with respect to the mesoporous molecular sieve matrix.
According to a preferred embodiment of the present invention, the hydrophobic modification layer is a hydrophobic modifier layer.
The hydrophobic modifier can be any modifier which can be used for carrying out surface hydrophobic modification on the mesoporous molecular sieve, specifically can be one or more of 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane and 2-methoxy-propyltrimethoxysilane, and preferably is one or more of methyltriethoxysilane, phenyltriethoxysilane and 3-aminopropyltriethoxysilane. In order to further improve the adsorption performance of the mesoporous molecular sieve supporting the ionic liquid, the hydrophobic modifier is preferably used in an amount of 0.1 to 0.5 wt%, preferably 0.3 to 0.5 wt%, relative to the mesoporous molecular sieve matrix.
In addition, in order to obtain a better hydrophobic modification effect and improve the adsorption performance of the mesoporous molecular sieve carrying the ionic liquid, the hydrophobic modifier layer may preferably further contain a dispersant. The dispersant may be hydroxyethyl cellulose, CaCO3、MgCO3、NaCl、Na2CO3、NaHCO3、K2CO3、KHCO3、MgSO4Preferably hydroxyethyl cellulose, CaCO3、MgCO3、MgSO4One or more of (a). Preferably, the dispersant is used in an amount of 0.05 to 0.5 wt%, more preferably 0.1 to 0.3 wt%, relative to the mesoporous molecular sieve matrix.
According to another preferred embodiment of the invention, the hydrophobically modified layer is a polymer layer. Preferably, the polymer layer is polymerized from a first monomer and a second monomer; the first monomer is one or more of chloroethylene, acrylic acid, methyl acrylate, isobornyl methacrylate, n-butyl ethacrylate and hexadecyl ethacrylate; the second monomer is styrene and/or p-methylstyrene. Preferably, the content of the first monomer is 50 to 100 wt%, preferably 70 to 100 wt%, and the content of the second monomer is 10 to 50 wt%, more preferably 30 to 50 wt%, with respect to the mesoporous molecular sieve matrix. The polymerization conditions of the first monomer and the second monomer may be appropriately selected so that both are polymerized to obtain a polymer layer.
In a second aspect, the present invention provides a method for preparing a mesoporous molecular sieve loaded with an ionic liquid, the method comprising: the method comprises the step of contacting a mixed solution of an ionic liquid and a loaded organic solvent with a mesoporous molecular sieve matrix to obtain the mesoporous molecular sieve loaded with the ionic liquid, wherein the surface of the mesoporous molecular sieve matrix is provided with a hydrophobic modification layer.
The method of the present invention may be used for preparing the mesoporous molecular sieve loaded with the ionic liquid of the first aspect of the present invention, and the mesoporous molecular sieve matrix, the ionic liquid, the hydrophobic modification layer, and the like may be the same as those of the first aspect, and are not described herein again.
According to the present invention, the organic solvent for supporting is a polar organic solvent, such as alcohols, alkylene oxides, and the like, preferably, the organic solvent for supporting is one or more of methanol, ethanol, ethylene glycol, and tetrahydrofuran, preferably methanol.
In the invention, the ionic liquid and the organic solvent for loading are mixed, and then the obtained mixed solution is contacted with the surface hydrophobic mesoporous molecular sieve, so that the loading effect of the ionic liquid can be further improved, and the mesoporous molecular sieve loading the ionic liquid with better adsorption performance is prepared. The contacting may be carried out by an impregnation method, for example, an equivalent-volume impregnation method. Preferably, the mixed liquid of the ionic liquid and the organic solvent for supporting is dropped on the mesoporous molecular sieve matrix. Preferably, after the contacting, the heat treatment is carried out for 12-24h under the conditions of 150-250 ℃. The heat treatment is preferably performed under a sealed condition.
In order to further improve the adsorption performance of the mesoporous molecular sieve supporting the ionic liquid, the weight ratio of the organic solvent for supporting to the ionic liquid in the mixed liquid of the ionic liquid and the organic solvent for supporting is preferably (1-20): 1, preferably (1-10): 1, more preferably (3-5): 1.
according to the present invention, preferably, the weight ratio of the mixed liquid of the ionic liquid and the supporting organic solvent to the mesoporous molecular sieve matrix is (0.5-5): 1, preferably (1-4): 1, more preferably (1-2): 1.
according to a specific embodiment of the present invention, in the case where the hydrophobic modification layer is formed of a hydrophobic modification agent, the method of the present invention comprises:
(1) carrying out first contact on a mesoporous molecular sieve matrix, a first organic solvent, a hydrophobic modifier and a dispersant;
(2) separating a solid phase in the product obtained in the step (1) and carrying out first heat treatment to prepare a surface hydrophobic mesoporous molecular sieve;
(3) carrying out second contact on the mixed solution of the ionic liquid and the organic solvent for loading and the surface hydrophobic mesoporous molecular sieve;
(4) and (4) separating the solid phase in the product obtained in the step (3) and carrying out second heat treatment to obtain the mesoporous molecular sieve loaded with the ionic liquid.
According to the present invention, preferably, the mesoporous molecular sieve matrix is a SBA type molecular sieve (SBA-15 type). Preferably, the particle size of the mesoporous molecular sieve matrix is 20-100 meshes, more preferably 50-80 meshes; the specific surface area is 500-1000m2(ii)/g, more preferably 750-2(ii)/g; the pore volume is 0.6-1.5cm3Per g, more preferably 0.8 to 1.2cm3(ii)/g; the average pore diameter is 3 to 20nm, more preferably 8 to 12 nm.
In step (1), the hydrophobic modifier and the dispersant may be the same as those described above in the first aspect.
According to the present invention, in step (1), the first organic solvent may be a non-polar organic solvent, and may be, for example, paraffin, cycloparaffin, aromatic hydrocarbon and their halogenated compounds, ketones, sulfones, and the like, wherein one or more of n-hexane, cyclohexane, n-heptane, toluene, chloroform, acetone, and sulfolane is preferred, and one or more of cyclohexane, toluene, and sulfolane is more preferred.
In order to further improve the adsorption performance of the mesoporous molecular sieve supporting the ionic liquid, the hydrophobic modifier is preferably used in an amount of 0.1 to 0.5 wt%, more preferably 0.3 to 0.5 wt%, relative to the mesoporous molecular sieve matrix.
In addition, in order to obtain a better hydrophobic modification effect and thus improve the adsorption performance of the mesoporous molecular sieve loading the ionic liquid, the amount of the dispersant is preferably 0.05 to 0.5 wt%, more preferably 0.1 to 0.3 wt%, relative to the mesoporous molecular sieve matrix.
In order to further improve the adsorption performance of the mesoporous molecular sieve supporting the ionic liquid, the weight ratio of the first organic solvent to the mesoporous molecular sieve matrix is preferably (1.5-5): 1, more preferably (2-4): 1.
according to the present invention, in step (1), in order to obtain a better hydrophobic modification effect, preferably, the conditions of the first contacting include: the stirring time is 4 to 10 hours, more preferably 6 to 8 hours, and the temperature is 30 to 60 ℃, more preferably 40 to 48 ℃, and still more preferably 45 ℃.
According to the present invention, in the step (1), it is preferable that the mesoporous molecular sieve matrix is a dried mesoporous molecular sieve matrix. By drying, the effect of hydrophobic modification can be improved. Preferably, the drying conditions include: the heating temperature is 150-250 ℃, preferably 180-200 ℃, and the heating time is 12-24h, preferably 18-20 h. The drying is preferably carried out in a vacuum drying oven.
In the step (2) of the present invention, the solid phase in the product of the separation step (1) may be separated by any conventional solid-liquid separation method, for example, filtration, centrifugation, etc., as long as the effect of separating the solid phase mesoporous molecular sieve matrix from the product of the separation step (1) can be achieved. For the purpose of improving efficiency, it is preferable to perform suction filtration.
According to the present invention, in step (2), in order to further improve the adsorption performance of the ionic liquid-supporting mesoporous molecular sieve, preferably, the conditions of the first heat treatment include: the temperature is preferably 50-150 ℃, and more preferably 80-120 ℃; the time is preferably 8 to 24 hours, more preferably 10 to 12 hours.
In order to sufficiently remove the unreacted hydrophobic modifier and the dispersant, preferably, the step (2) further comprises: the solid phase in the product of step (1) is washed with a first organic solvent before said first heat treatment, the number of washes may be 2-10, preferably 3-6.
According to the present invention, in the step (3), any ionic liquid capable of adsorbing a volatile compound may be used as the ionic liquid. The ionic liquid is preferably one or more of 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, 1-butyl-3-methylimidazole hexafluorophosphate, 1-ethyl-3-methylimidazole acetate, 1-ethyl-3-methylimidazole lactate and 1-ethyl-3-methylimidazole chloride salt, and more preferably 1-butyl-3-methylimidazole hexafluorophosphate.
According to the present invention, in step (3), the organic solvent for supporting is a polar organic solvent, such as alcohols, alkylene oxides, and the like, wherein one or more of methanol, ethanol, ethylene glycol, and tetrahydrofuran is preferred, and methanol is more preferred.
In the invention, the ionic liquid and the organic solvent for loading are mixed, and then the obtained mixed solution is contacted with the surface hydrophobic mesoporous molecular sieve, so that the loading effect of the ionic liquid can be further improved, and the mesoporous molecular sieve loading the ionic liquid with better adsorption performance is prepared. In order to further improve the adsorption performance of the mesoporous molecular sieve supporting the ionic liquid, the weight ratio of the organic solvent for supporting to the ionic liquid in the mixed solution of the ionic liquid and the organic solvent for supporting is preferably (1-10): 1, more preferably (3-5): 1.
according to the present invention, in the step (3), it is preferable that the weight ratio of the mixed solution of the ionic liquid and the organic solvent for supporting to the surface hydrophobic mesoporous molecular sieve is (0.5 to 5): 1, more preferably (1-2): 1.
according to the present invention, in step (3), in order to obtain a better loading effect, it is preferable that the conditions of the second contact include: the stirring time is 5-15h, preferably 10-12 h; the temperature is 50 to 100 deg.C, more preferably 70 to 80 deg.C. Preferably, the conditions of the second heat treatment include: the temperature is 50-150 ℃, preferably 80-120 ℃, and more preferably 100-120 ℃; the time is 5 to 24 hours, preferably 10 to 12 hours;
preferably, step (4) further comprises: the mesoporous molecular sieve supporting the ionic liquid is washed with a supporting organic solvent before the second heat treatment, and the number of washing may be 2 to 10 times, preferably 3 to 6 times.
According to the present invention, in the step (4), the solid phase in the product of the separation step (3) can be separated by any conventional solid-liquid separation method, for example, filtration, centrifugation or the like, as long as the effect of separating the mesoporous molecular sieve matrix of the solid phase from the product of the separation step (3) can be achieved. For the purpose of improving efficiency, it is preferable to perform suction filtration.
According to another specific embodiment of the present invention, in the case where the polymer layer is polymerized from a first monomer and a second monomer, the preparation method of the present invention comprises:
(1) under the condition of a first polymerization reaction, carrying out a first polymerization reaction on a mesoporous molecular sieve matrix, a first monomer, a second organic solvent, an initiator and a cross-linking agent;
(2) adding a second monomer and a dispersant into the product obtained in the step (1), and carrying out a second polymerization reaction under the second polymerization reaction condition to obtain a surface hydrophobic mesoporous molecular sieve;
(3) the mixed liquid of ionic liquid and organic solvent for loading is contacted with the surface hydrophobic mesoporous molecular sieve;
(4) and (4) separating the solid phase in the product obtained in the step (3) and carrying out heat treatment to obtain the mesoporous molecular sieve loaded with the ionic liquid.
According to the present invention, in the step (1), the mesoporous molecular sieve substrate may be an unmodified mesoporous molecular sieve, and the specific type thereof is not particularly limited, and may be, for example, an MCM type molecular sieve (MCM-41 type).
In order to further improve the adsorption performance of the mesoporous molecular sieve loading the ionic liquid, the particle size of the mesoporous molecular sieve matrix is preferably 100-200 meshes, and preferably 150-180 meshes; the specific surface area is 800-2A/g of preferably 1000-2(ii)/g; the pore volume is 1.2-1.8cm3In g, preferably 1.2 to 1.5cm3(ii)/g; the average pore diameter is 2-10nm, preferably 3-5 nm.
According to the invention, in step (1), the first monomer is preferably one or more of vinyl chloride, acrylic acid, methyl acrylate, isobornyl methacrylate, n-butyl ethacrylate, and cetyl ethacrylate, and is more preferably acrylic acid and methyl acrylate.
According to the present invention, in step (1), preferably, the second organic solvent is one or more of tetrahydrofuran, ethanol, benzene, toluene, chloroform, acetone, sulfolane, more preferably acetone, chloroform.
According to the present invention, in step (1), the initiator and the crosslinking agent may be selected according to the requirements of the polymerization reaction. Preferably, the initiator is azobisisobutyronitrile and/or benzoyl peroxide, more preferably azobisisobutyronitrile. Preferably, the cross-linking agent is one or more of divinylbenzene, ethylene glycol diacrylate and diethylene glycol diacrylate, more preferably divinylbenzene.
In order to further improve the adsorption performance of the mesoporous molecular sieve supporting the ionic liquid, the first monomer is preferably used in an amount of 50 to 100 wt%, preferably 70 to 100 wt%, with respect to the mesoporous molecular sieve matrix.
And, in order to obtain better hydrophobic modification effect, preferably, the amount of the initiator is 0.01-0.5 wt%, preferably 0.1-0.2 wt%, relative to the mesoporous molecular sieve matrix; preferably, the cross-linking agent is used in an amount of 0.1 to 0.5 wt%, preferably 0.2 to 0.3 wt%, relative to the mesoporous molecular sieve matrix.
In order to further improve the adsorption performance of the mesoporous molecular sieve supporting the ionic liquid, the weight ratio of the second organic solvent to the matrix of the mesoporous molecular sieve is preferably (5-10): 1, more preferably (6-8): 1.
according to the present invention, in step (1), in order to obtain a better hydrophobic modification effect, preferably, the conditions of the first polymerization reaction include: the temperature is 50-100 deg.C, preferably 60-80 deg.C, more preferably 70 deg.C, and the time is 6-8h, more preferably 7 h.
According to the present invention, it is preferable that in the step (1), the mesoporous molecular sieve matrix is a dried mesoporous molecular sieve matrix. By drying, the effect of hydrophobic modification can be improved. Preferably, the drying conditions include: the temperature is 200-250 ℃, preferably 220-240 ℃ and the time is 12-18h, preferably 14-16 h. The drying is preferably carried out in a vacuum drying oven.
According to the present invention, in the step (2), hydrophobic modification of the mesoporous molecular sieve matrix is accomplished by further adding a second monomer and performing a second polymerization. Preferably, the second monomer is styrene and/or p-methylstyrene, preferably styrene. In order to further improve the adsorption performance of the mesoporous molecular sieve supporting the ionic liquid, the second monomer is preferably used in an amount of 10 to 50 wt%, more preferably 30 to 50 wt%, with respect to the mesoporous molecular sieve matrix.
According to the invention, in the step (2), preferably, the dispersant is talc, activated clay, bentonite, CaCO3、MgCO3、MgSO4More preferably activated clay or bentonite. Preferably, the dispersant is used in an amount of 0.1 to 0.3 wt%, more preferably 0.1 to 0.2 wt%, relative to the mesoporous molecular sieve matrix.
According to the present invention, in step (2), in order to obtain a better hydrophobic modification effect, preferably, the conditions of the second polymerization reaction include: the temperature is 50-100 deg.C, preferably 60-80 deg.C, and the time is 6-8 h.
In addition, the product of the second polymerization reaction is preferably subjected to solid-liquid separation to obtain a mesoporous molecular sieve with a hydrophobic surface. The solid-liquid separation is carried out by any conventional method, for example, filtration, centrifugation, etc., and suction filtration is preferable for improving efficiency.
According to the present invention, in the step (3), any ionic liquid capable of adsorbing a volatile compound may be used as the ionic liquid. The ionic liquid is preferably one or more of 1-ethyl-3-methylimidazole methyl sulfate salt, 1-ethyl-3-methylimidazole tetrafluoroborate and 1-ethyl-3-methylimidazole hydrogen sulfate; more preferably 1-butyl-3-methylimidazolium methyl sulfate.
According to the present invention, in step (3), the organic solvent for supporting is a polar organic solvent, such as alcohols, alkylene oxides, and the like, wherein one or more of methanol, ethanol, ethylene glycol, and tetrahydrofuran is preferred, and methanol is more preferred.
In the invention, the ionic liquid and the organic solvent for loading are mixed, and then the obtained mixed solution is contacted with the surface hydrophobic mesoporous molecular sieve, so that the loading effect of the ionic liquid can be further improved, and the mesoporous molecular sieve loading the ionic liquid with better adsorption performance is prepared. In order to further improve the adsorption performance of the mesoporous molecular sieve supporting the ionic liquid, the weight ratio of the organic solvent for supporting to the ionic liquid in the mixed liquid of the ionic liquid and the organic solvent for supporting is preferably (1-5): 1, more preferably (2-4): 1.
according to the present invention, in the step (3), it is preferable that the weight ratio of the mixed solution of the ionic liquid and the organic solvent for supporting to the surface hydrophobic mesoporous molecular sieve is (0.5 to 5): 1, more preferably (1-4): 1, more preferably (1-2): 1.
according to the present invention, in step (3), in order to obtain a better loading effect, preferably, the conditions of the contacting include: the stirring time is 10-18h, and more preferably 10-13 h; the temperature is 50 to 80 ℃ and more preferably 50 to 70 ℃.
In the present invention, the purpose of the heat treatment is to dry the ionic liquid-supporting mesoporous molecular sieve. Preferably, the conditions of the heat treatment include: the temperature is 50-150 ℃, and the temperature is more preferably 80-120 ℃; the time is 8-24h, more preferably 10-12 h. The heat treatment is preferably carried out in a vacuum drying oven.
Preferably, step (4) further comprises: before the heat treatment, the mesoporous molecular sieve carrying the ionic liquid is washed by a carrying organic solvent, and the washing frequency can be 2 to 10 times, and is preferably 3 to 6 times.
According to the present invention, in the step (4), the solid phase in the product of the separation step (3) can be separated by any conventional solid-liquid separation method, for example, filtration, centrifugation or the like, as long as the effect of separating the mesoporous molecular sieve matrix of the solid phase from the product of the separation step (3) can be achieved. For the purpose of improving efficiency, it is preferable to perform suction filtration.
In a third aspect, the present invention provides an application of the ionic liquid-supported mesoporous molecular sieve of the present invention or the ionic liquid-supported mesoporous molecular sieve obtained by the preparation method of the present invention in adsorption of volatile organic compounds. Specifically, the volatile organic compound is preferably a nonpolar volatile organic compound such as benzene, toluene, ethylbenzene, xylene, cyclohexane, n-pentane, or the like.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, a fixed bed adsorption column having an inner diameter of 10.0mm and a height of 150mm was used); the experimental test gas was a standard gas commercially available from midheaven standard technologies, ltd. The gas concentration was determined by gas chromatography.
Examples 1 to 9 and comparative examples 1 to 5 Using a mesoporous molecular sieve of SBA-15 type, having an average particle diameter of 50 mesh and a specific surface area of 580m, manufactured by Nanjing Xiapong nanomaterial science and technology Co., Ltd, as a mesoporous molecular sieve base2Per g, pore volume of 0.82cm3In terms of/g, the mean pore diameter is 4.3 nm.
In examples 10 to 19 and comparative examples 6 to 10, an MCM-41 mesoporous molecular sieve of Nanjing Xiapong nanomaterial science and technology Limited company, with an average particle size of 150 mesh and a specific surface area of 1220m, was used as a mesoporous molecular sieve substrate2G, pore volume of 1.2cm3In terms of/g, the mean pore diameter is 3.2 nm.
Example 1
The mesoporous molecular sieve substrate is modified to obtain the mesoporous molecular sieve loaded with the ionic liquid and capable of effectively adsorbing toluene gas, and the preparation steps are as follows:
(1) pretreatment of a mesoporous molecular sieve matrix: 200g of mesoporous molecular sieve matrix is dried for 18h at 180 ℃ for later use.
(2) 100g of dried mesoporous molecular sieve matrix, 400g of acetone, 0.2g of surface hydrophobic modifier methyl triethoxysilane and 0.3g of dispersant CaCO3Stirring uniformly and then stirring for reaction for 6 hours at the temperature of 45 ℃;
(3) carrying out suction filtration on the reaction product obtained in the step (2), washing the reaction product for 5 times by using acetone, and then drying the washed product at 100 ℃ for 12h to obtain a primarily modified surface hydrophobic mesoporous molecular sieve;
(4) uniformly mixing 20g of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate with 80g of methanol, slowly adding the mixture into a reactor filled with 100g of surface hydrophobic mesoporous molecular sieve, uniformly stirring, and then stirring and reacting for 12 hours at 75 ℃;
(5) and (4) carrying out suction filtration on the reaction product obtained in the step (4), washing the reaction product with methanol for 5 times, washing the reaction product with deionized water until the reaction product is neutral, and drying the washed product at 120 ℃ for 10 hours to obtain the final mesoporous molecular sieve 1 loaded with the ionic liquid.
Example 2
The mesoporous molecular sieve substrate is modified to obtain the mesoporous molecular sieve loaded with the ionic liquid and capable of effectively adsorbing toluene gas, and the preparation steps are as follows:
(1) pretreatment of a mesoporous molecular sieve matrix: 200g of mesoporous molecular sieve matrix is dried for 18h at 180 ℃ for later use.
(2) Weighing 100g of dried mesoporous molecular sieve matrix, 300g of cyclohexane, 0.3g of surface hydrophobic modifier phenyltriethoxysilane and 0.2g of dispersant CaCO3Fully stirring the mixture, and then stirring the mixture for reaction for 8 hours at the temperature of 60 ℃;
(3) carrying out suction filtration on the reaction product obtained in the step (2), washing the reaction product for 5 times by using cyclohexane, and drying the washed product at the temperature of 120 ℃ for 12 hours to obtain a primarily modified surface hydrophobic mesoporous molecular sieve;
(4) uniformly mixing 20g of ionic liquid 1-ethyl-3-methylimidazole acetate and 90g of methanol, slowly adding the mixture into a reactor filled with 100g of surface hydrophobic mesoporous molecular sieve, uniformly stirring, and then stirring and reacting for 10 hours at 80 ℃;
(5) and (4) carrying out suction filtration on the reaction product obtained in the step (4), washing the reaction product for 5 times by using methanol, then washing the reaction product to be neutral by using deionized water, and drying the washed product at the temperature of 120 ℃ for 5 hours to obtain the final mesoporous molecular sieve 2 loaded with the ionic liquid.
Example 3
The mesoporous molecular sieve substrate is modified to obtain the mesoporous molecular sieve loaded with the ionic liquid and capable of effectively adsorbing toluene gas, and the preparation steps are as follows:
(1) pretreatment of a mesoporous molecular sieve matrix: 200g of mesoporous molecular sieve matrix is dried for 20 hours at the temperature of 200 ℃ for standby.
(2) 100g of dried mesoporous molecular sieve matrix, 200g of acetone, 0.5g of surface hydrophobic modifier phenyltriethoxysilane and 0.1g of dispersant MgCO are weighed3Stirring uniformly and then stirring for reaction for 7 hours at the temperature of 40 ℃;
(3) carrying out suction filtration on the reaction product obtained in the step (2), washing the reaction product for 5 times by using acetone, and then drying the washed product at the temperature of 80 ℃ for 10 hours to obtain a primarily modified surface hydrophobic mesoporous molecular sieve;
(4) uniformly mixing 30g of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate with 90g of methanol, slowly adding the mixture into a reactor filled with 100g of surface hydrophobic mesoporous molecular sieve, uniformly stirring, and then stirring and reacting for 10 hours at 70 ℃;
(5) and (4) carrying out suction filtration on the reaction product obtained in the step (4), washing the reaction product with methanol for 5 times, washing the reaction product with deionized water until the reaction product is neutral, and drying the washed product at 80 ℃ for 12 hours to obtain the final mesoporous molecular sieve 3 loaded with the ionic liquid.
Example 4
According to the method of example 1, except that the amount of the hydrophobic modifier is 0.3g, the ionic liquid-supporting mesoporous molecular sieve 4 is obtained.
Example 5
According to the method of example 1, except that the amount of the ionic liquid was 20g and the amount of methanol was 100g, the ionic liquid-supporting mesoporous molecular sieve 5 was obtained.
Example 6
According to the method of example 1, except that the amount of the ionic liquid was 30g and the amount of methanol was 120g, the ionic liquid-supporting mesoporous molecular sieve 6 was obtained.
Example 7
According to the method of example 1, except that the drying is carried out at 50 ℃ for 12h in the step (3) and at 50 ℃ for 10h in the step (5), the mesoporous molecular sieve 7 supporting the ionic liquid is obtained.
Example 8
According to the method of example 1, except that the drying is carried out at 150 ℃ for 12h in the step (3) and at 150 ℃ for 10h in the step (5), the mesoporous molecular sieve 8 supporting the ionic liquid is obtained.
Example 9
A supported mesoporous molecular sieve was obtained according to the method of example 1 and was prepared in C7H8/N2The concentration of the mixed standard gas is 5.12g/m3And after the molecular sieve is penetrated, pouring the molecular sieve out of the fixed adsorption column, placing the molecular sieve in a tray, placing the tray in a vacuum drying oven, and performing vacuum drying at 80 ℃ for 60min to obtain the regenerated supported mesoporous molecular sieve 10.
Comparative example 1
Drying the mesoporous molecular sieve matrix at 80 ℃ for 18h to obtain the comparative mesoporous molecular sieve 1.
Comparative example 2
According to the process of example 1, except that no ionic liquid was supported, a comparative mesoporous molecular sieve 2 was obtained.
Comparative example 3
According to the method of example 1, except that no dispersant is added in the step (2), the mesoporous molecular sieve 3 for comparatively supporting the ionic liquid is obtained.
Comparative example 4
According to the method of example 1, except that methanol, which is the second organic solvent, is not used in the step (4), i.e., the ionic liquid is directly used for loading, the mesoporous molecular sieve 4 for comparatively loading the ionic liquid is obtained.
Comparative example 5
According to the method of example 1, except that the steps of supporting the ionic liquid in steps (4) and (5) were directly performed without performing the surface hydrophobic modification of the mesoporous molecular sieve matrix in steps (1) to (3), the mesoporous molecular sieve 5 supporting the ionic liquid was obtained as a comparative example.
Test example 1
0.25g of the ionic liquid-supporting mesoporous molecular sieve finally obtained in the examples and comparative examples was taken, and charged into a fixed bed adsorption column,then introducing C at 25 DEG C7H8/N2Mixed gas of C7H8The concentration is 5.12g/m3The flow rate of the mixed gas is 50mL/min, and the C content is controlled by the mesoporous molecular sieve pair loaded with the ionic liquid7H8/N2The adsorption treatment of the mixed gas, the experimental time required when the outlet concentration and the inlet concentration were equal was recorded, and the equilibrium adsorption amount of the ionic liquid-loaded mesoporous molecular sieve to toluene gas was obtained by integrating the dynamic breakthrough curve of the outlet concentration with the experimental time, and the results are shown in table 1.
Test example 2
Taking 0.25g of the ionic liquid-supported mesoporous molecular sieve finally obtained in the examples and the comparative examples, filling the molecular sieve into a fixed bed adsorption column, and then introducing C at 25 DEG C7H8/N2Mixed gas of C7H8The concentration is 8.38g/m3The flow rate of the mixed gas is 50mL/min, and the C content is controlled by the mesoporous molecular sieve pair loaded with the ionic liquid7H8/N2The adsorption treatment of the mixed gas, the experimental time (i.e. breakthrough time) required when the outlet concentration was equal to the inlet concentration was recorded, and the equilibrium adsorption amount of the ionic liquid-loaded mesoporous molecular sieve to toluene gas was obtained by integrating the dynamic breakthrough curve of the outlet concentration with the experimental time, and the results are shown in table 1.
Test example 3
Taking 0.25g of mesoporous molecular sieve loading ionic liquid finally obtained in the example, loading the molecular sieve into a fixed bed adsorption column, and then introducing C at the temperature of 25 DEG C7H8/N2Mixed gas of C7H8The concentration is 15.6g/m3The flow rate of the mixed gas is 50mL/min, and the C content is controlled by the mesoporous molecular sieve pair loaded with the ionic liquid7H8/N2The adsorption treatment of the mixed gas, the experimental time required when the outlet concentration and the inlet concentration were equal was recorded, and the equilibrium adsorption amount of the ionic liquid-loaded mesoporous molecular sieve to toluene gas was obtained by integrating the dynamic breakthrough curve of the outlet concentration with the experimental time, and the results are shown in table 1.
Test example 4
Taking 0.25g of mesoporous molecular sieve loading ionic liquid finally obtained in the example, loading the molecular sieve into a fixed bed adsorption column, and then introducing C at the temperature of 25 DEG C7H8/N2Mixed gas of C7H8The concentration is 21.3g/m3The flow rate of the mixed gas is 50mL/min, and the C content is controlled by the mesoporous molecular sieve pair loaded with the ionic liquid7H8/N2The adsorption treatment of the mixed gas, the experimental time required when the outlet concentration and the inlet concentration were equal was recorded, and the equilibrium adsorption amount of the ionic liquid-loaded mesoporous molecular sieve to toluene gas was obtained by integrating the dynamic breakthrough curve of the outlet concentration with the experimental time, and the results are shown in table 1.
TABLE 1
Figure BDA0002091892870000211
As can be seen from the results in table 1, the ionic liquid-supporting mesoporous molecular sieves of examples 1 to 9 obtained by the method of the present invention all have good adsorption performance for toluene, as compared with comparative examples 1 to 5.
Example 10
The mesoporous molecular sieve substrate is modified to obtain the mesoporous molecular sieve loaded with the ionic liquid and capable of effectively adsorbing cyclohexane gas, and the preparation steps are as follows:
(1) pretreatment of a mesoporous molecular sieve matrix: 200g of mesoporous molecular sieve matrix is dried for 18h at 180 ℃ for later use.
(2) Weighing 100g of dried mesoporous molecular sieve matrix, 400g of acetone, 600g of toluene, 70g of first monomer methyl acrylate, 0.1g of azobisisobutyronitrile and 0.2g of cross-linking agent divinylbenzene, fully stirring, and then stirring and reacting for 7 hours at the temperature of 70 ℃.
(3) Adding 30g of second monomer styrene and 0.2g of dispersant bentonite, stirring for reaction for 10 hours, and then carrying out suction filtration.
(4) And (3) uniformly mixing 20g of ionic liquid 1-butyl-3-methylimidazole methyl sulfate and 80g of methanol, slowly adding the mixture into a reactor containing 100g of the suction filtration product obtained in the step (3), uniformly stirring, and then stirring and reacting for 12 hours at 65 ℃.
(5) And (4) carrying out suction filtration on the reaction product in the step (4), washing the reaction product with methanol for 5 times, washing the reaction product with deionized water until the reaction product is neutral, and drying the washed product at 100 ℃ for 12 hours to obtain the final mesoporous molecular sieve loaded with the ionic liquid.
Example 11
The mesoporous molecular sieve substrate is modified to obtain the mesoporous molecular sieve loaded with the ionic liquid and capable of effectively adsorbing cyclohexane gas, and the preparation steps are as follows:
(1) pretreatment of a mesoporous molecular sieve matrix: 200g of mesoporous molecular sieve matrix is dried for 18h at 180 ℃ for later use.
(2) Weighing 100g of dried mesoporous molecular sieve matrix, 700g of chloroform, 80g of first monomer acrylic acid, 0.1g of azobisisobutyronitrile and 0.1g of cross-linking agent divinylbenzene, fully stirring, and stirring at 70 ℃ for reaction for 8 hours.
(3) Adding 30g of second monomer styrene and 0.2g of dispersant activated clay, stirring for reaction for 12 hours, and then carrying out suction filtration.
(4) And (3) uniformly mixing 20g of ionic liquid 1-butyl-3-methylimidazole methyl sulfate and 80g of ethanol, slowly adding the mixture into a reactor containing 100g of the suction filtration product obtained in the step (3), uniformly stirring, and then stirring and reacting for 12 hours at 70 ℃.
(5) And (4) carrying out suction filtration on the reaction product in the step (4), washing the reaction product with ethanol for 5 times, washing the reaction product with deionized water until the reaction product is neutral, and drying the washed product at 80 ℃ for 12 hours to obtain the final mesoporous molecular sieve loaded with the ionic liquid.
Example 12
The mesoporous molecular sieve substrate is modified to obtain the mesoporous molecular sieve loaded with the ionic liquid and capable of effectively adsorbing cyclohexane gas, and the preparation steps are as follows:
(1) pretreatment of a mesoporous molecular sieve matrix: 200g of mesoporous molecular sieve matrix is dried for 18h at 180 ℃ for later use.
(2) Weighing 100g of dried mesoporous molecular sieve matrix, 400g of acetone, 800g of toluene, 70g of first monomer methyl acrylate, 0.2g of azobisisobutyronitrile and 0.3g of cross-linking agent divinylbenzene, fully stirring, and stirring for reaction at 70 ℃ for 7 hours.
(3) Adding 50g of second monomer styrene and 0.1g of dispersant bentonite, stirring for reaction for 10 hours, and then carrying out suction filtration;
(4) and (3) uniformly mixing 40g of ionic liquid 1-butyl-3-methylimidazole methyl sulfate and 80g of methanol, slowly adding the mixture into a reactor containing 100g of the suction filtration product obtained in the step (3), uniformly stirring, and then stirring and reacting for 12 hours at 50 ℃.
(5) And (4) carrying out suction filtration on the reaction product in the step (4), washing the reaction product with methanol for 5 times, washing the reaction product with deionized water until the reaction product is neutral, and drying the washed product at 120 ℃ for 12 hours to obtain the final mesoporous molecular sieve loaded with the ionic liquid.
Example 13
According to the method of example 10, except that the amount of the first monomer used was 50g, an ionic liquid-supporting mesoporous molecular sieve was obtained.
Example 14
According to the method of example 10, except that the amount of the second monomer used was 10g, an ionic liquid-supporting mesoporous molecular sieve was obtained.
Example 15
According to the method of example 10, except that the amount of the ionic liquid was 20g and the amount of methanol was 100g, the mesoporous molecular sieve supporting the ionic liquid was obtained.
Example 16
According to the method of example 10, except that the amount of the ionic liquid was 30g and the amount of methanol was 120g, an ionic liquid-supporting mesoporous molecular sieve was obtained.
Example 17
According to the method of example 10, except that stirring reaction is carried out for 12h at 80 ℃ in the step (4), the mesoporous molecular sieve loaded with the ionic liquid is obtained.
Example 18
According to the method of example 10, except that, in the step (5), drying is carried out for 12h at 50 ℃, and the mesoporous molecular sieve for loading the ionic liquid is obtained.
Example 19
The method according to example 10 yields an ionic liquid loaded mesoporous molecular sieve, and in C6H12/N2The concentration of the mixed standard gas is 5.4g/m3And after the ion liquid is penetrated, pouring the molecular sieve out of the fixed adsorption column, placing the molecular sieve in a tray, placing the tray in a vacuum drying oven, and performing vacuum drying at 80 ℃ for 60min to obtain the regenerated mesoporous molecular sieve loaded with the ionic liquid.
Comparative example 6
Drying the mesoporous molecular sieve matrix at 80 ℃ for 18h to obtain the comparative mesoporous molecular sieve 6.
Comparative example 7
According to the method of example 10, except that no ionic liquid was supported, a comparative mesoporous molecular sieve 7 was obtained.
Comparative example 8
According to the method of example 10, except that no dispersant is added in the step (3), the mesoporous molecular sieve 8 for comparatively supporting an ionic liquid is obtained.
Comparative example 9
According to the method of example 10, except that the second organic solvent is not used in the step (4), i.e., the ionic liquid is directly used for supporting, the mesoporous molecular sieve 9 for comparatively supporting the ionic liquid is obtained.
Comparative example 10
According to the method of example 10, except that the steps of supporting the ionic liquid in steps (4) and (5) were directly performed without performing the surface hydrophobic modification of the mesoporous molecular sieve matrix in steps (1) to (3), the mesoporous molecular sieve 10 on which the ionic liquid was comparatively supported was obtained.
Test example 5
Taking 0.25g of the ionic liquid-supported mesoporous molecular sieve finally obtained in the examples and the comparative examples, filling the molecular sieve into a fixed bed adsorption column, and then introducing C at 25 DEG C6H12(cyclohexane, the same applies hereinafter)/N2Mixed gas of C6H12The concentration is 5.4g/m3The flow rate of the mixed gas is 50mL/min, and the C content is controlled by the mesoporous molecular sieve pair loaded with the ionic liquid6H12/N2The adsorption treatment of the mixed gas, the experimental time (namely the penetration time) required when the outlet concentration is equal to the inlet concentration is recorded, and the ion liquid loaded mesoporous molecular sieve pair C is obtained by integrating the dynamic penetration curve of the outlet concentration along with the experimental time6H12The results of the equilibrium adsorption amount of the gas are shown in Table 2.
Test example 6
Taking 0.25g of the ionic liquid-supported mesoporous molecular sieve finally obtained in the examples and the comparative examples, filling the molecular sieve into a fixed bed adsorption column, and then introducing C at 25 DEG C6H12/N2Mixed gas of C6H12The concentration is 9.2g/m3The flow rate of the mixed gas is 50mL/min, and the C content is controlled by the mesoporous molecular sieve pair loaded with the ionic liquid6H12/N2The adsorption treatment of the mixed gas, the experimental time required when the outlet concentration is equal to the inlet concentration is recorded, and the dynamic penetration curve of the outlet concentration along with the experimental time is integrated to obtain the mesoporous molecular sieve pair C of the loaded ionic liquid6H12The results of the equilibrium adsorption amount of the gas are shown in Table 2.
Test example 7
Taking 0.25g of mesoporous molecular sieve loading ionic liquid finally obtained in the example, loading the molecular sieve into a fixed bed adsorption column, and then introducing C at the temperature of 25 DEG C6H12/N2Mixed gas of C6H12The concentration is 16.3g/m3The flow rate of the mixed gas is 50mL/min, and the C content is controlled by the mesoporous molecular sieve pair loaded with the ionic liquid6H12/N2The adsorption treatment of the mixed gas, the experimental time required when the outlet concentration is equal to the inlet concentration is recorded, and the dynamic penetration curve of the outlet concentration along with the experimental time is integrated to obtain the mesoporous molecular sieve pair C of the loaded ionic liquid6H12The results of the equilibrium adsorption amount of the gas are shown in Table 2.
Test example 8
Taking 0.25g of mesoporous molecular sieve loading ionic liquid finally obtained in the example, loading the molecular sieve into a fixed bed adsorption column, and then introducing C at the temperature of 25 DEG C6H12/N2Mixed gas of C6H12The concentration is 21.2g/m3The flow rate of the mixed gas is 50mL/min, and the C content is controlled by the mesoporous molecular sieve pair loaded with the ionic liquid6H12/N2The adsorption treatment of the mixed gas, the experimental time required when the outlet concentration is equal to the inlet concentration is recorded, and the dynamic penetration curve of the outlet concentration along with the experimental time is integrated to obtain the mesoporous molecular sieve pair C of the loaded ionic liquid6H12The results of the equilibrium adsorption amount of the gas are shown in Table 2.
TABLE 2
Figure BDA0002091892870000271
As can be seen from the results in table 2, the ionic liquid-supporting mesoporous molecular sieves of examples 10 to 19 obtained by the method of the present invention all had good adsorption properties for VOCs, as compared with comparative examples 6 to 10.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (11)

1. The mesoporous molecular sieve is characterized by comprising a mesoporous molecular sieve matrix and ionic liquid loaded on the mesoporous molecular sieve matrix;
wherein the surface of the mesoporous molecular sieve matrix is provided with a hydrophobic modification layer.
2. The mesoporous molecular sieve as claimed in claim 1, wherein the mesoporous molecular sieve matrix has a particle size of 20-200 mesh and a specific surface area of 100-1500m2Per g, pore volume of 0.25-1.8cm3(ii)/g, average pore diameter is 2-20 nm;
preferably, the particle diameter of the mesoporous molecular sieve matrix is 10-200 meshes, and the specific surface area is 100-500m2G, pore volume of 0.25-1.5cm3(ii)/g, the average pore diameter is 5-20 nm.
3. The mesoporous molecular sieve of claim 1, wherein the cations of the ionic liquid are one or more of 1-butyl-3-methylimidazolium cation, 1-propyl-3-methylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-pentyl-3-methylimidazolium cation, N-hexylpyridinium cation, N-butylpyridinium cation, N-octylpyridinium cation, N-methylpyrrolidine cation;
preferably, the anion of the ionic liquid is one or more of chloride, bromide, tetrafluoroborate and hexafluorophosphate.
4. The mesoporous molecular sieve according to claim 3, wherein the ionic liquid is supported at a loading of 1 to 40 wt% with respect to the mesoporous molecular sieve matrix.
5. The mesoporous molecular sieve of any of claims 1-4, wherein the hydrophobic modification layer is a hydrophobic modifier layer;
preferably, the hydrophobic modifier is one or more of 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane and 2-methoxy-propyltrimethoxysilane, preferably one or more of methyltriethoxysilane, phenyltriethoxysilane and 3-aminopropyltriethoxysilane;
preferably, the hydrophobic modifier is used in an amount of 0.1 to 0.5 wt%, preferably 0.3 to 0.5 wt%, relative to the mesoporous molecular sieve matrix.
6. The mesoporous molecular sieve of any of claims 1-4, wherein the hydrophobically modified layer is a polymer layer;
preferably, the polymer layer is polymerized from a first monomer and a second monomer; the first monomer is one or more of chloroethylene, acrylic acid, methyl acrylate, isobornyl methacrylate, n-butyl ethacrylate and hexadecyl ethacrylate; the second monomer is styrene and/or p-methylstyrene;
preferably, the content of the first monomer is 50 to 100 wt%, preferably 70 to 100 wt%, and the content of the second monomer is 10 to 50 wt%, more preferably 30 to 50 wt%, with respect to the mesoporous molecular sieve matrix.
7. A preparation method of mesoporous molecular sieve loaded with ionic liquid is characterized by comprising the following steps: the mixed solution of the ionic liquid and the organic solvent for loading is contacted with the mesoporous molecular sieve matrix to obtain the mesoporous molecular sieve loading the ionic liquid,
wherein the surface of the mesoporous molecular sieve matrix is provided with a hydrophobic modification layer.
8. The preparation method as claimed in claim 7, wherein the mesoporous molecular sieve has a matrix with a particle size of 20-200 mesh and a specific surface area of 100-1500m2Per g, pore volume of 0.25-1.8cm3(ii)/g, average pore diameter is 2-20 nm;
preferably, the particle diameter of the mesoporous molecular sieve matrix is 10-200 meshes, and the specific surface area is 100-500m2G, pore volume of 0.25-1.5cm3(ii)/g, the average pore diameter is 5-20 nm;
preferably, the cation of the ionic liquid is one or more of 1-butyl-3-methylimidazole cation, 1-propyl-3-methylimidazole cation, 1-ethyl-3-methylimidazole cation, 1-hexyl-3-methylimidazole cation, 1-pentyl-3-methylimidazole cation, N-hexylpyridine cation, N-butylpyridine cation, N-octylpyridine cation and N-methylpyrrolidine cation;
preferably, the anion of the ionic liquid is one or more of chloride, bromide, tetrafluoroborate and hexafluorophosphate;
preferably, the organic solvent for loading is one or more of methanol, ethanol, ethylene glycol and tetrahydrofuran, preferably methanol;
preferably, the weight ratio of the mixed solution of the ionic liquid and the organic solvent for supporting to the matrix of the mesoporous molecular sieve is (0.5-5): 1, preferably (1-4): 1, more preferably (1-2): 1.
9. the production method according to claim 7, wherein the hydrophobic modification layer is formed of a hydrophobic modification agent;
preferably, the hydrophobic modifier is one or more of 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane and 2-methoxy-propyltrimethoxysilane, preferably one or more of methyltriethoxysilane, phenyltriethoxysilane and 3-aminopropyltriethoxysilane;
preferably, the hydrophobic modifier is used in an amount of 0.1 to 0.5 wt%, preferably 0.3 to 0.5 wt%, relative to the mesoporous molecular sieve matrix.
10. The production method according to claim 7, wherein the polymer layer is polymerized from a first monomer and a second monomer;
preferably, the first monomer is used in an amount of 50 to 100 wt%, preferably 70 to 100 wt%, relative to the mesoporous molecular sieve matrix;
preferably, the second monomer is used in an amount of 10 to 50 wt%, more preferably 30 to 50 wt%, relative to the mesoporous molecular sieve matrix.
11. Use of the ionic liquid-loaded mesoporous molecular sieve according to any one of claims 1 to 6 or the ionic liquid-loaded mesoporous molecular sieve obtained by the preparation method according to any one of claims 7 to 10 for the adsorption of volatile organic compounds.
CN201910506177.1A 2019-06-12 2019-06-12 Mesoporous molecular sieve loaded with ionic liquid and preparation method and application thereof Pending CN112076726A (en)

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CN113023679A (en) * 2021-04-27 2021-06-25 湖南万脉医疗科技有限公司 Oxygen generation device of medical high-temperature molecular sieve membrane adsorption tower and use method thereof
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