A composite material, its preparation and use

Abstract

This invention relates to the field of novel functional technologies for environmental nanomaterials, and discloses a composite material, its preparation method, and its applications. The composite material comprises ordered mesoporous alumina with amino groups modified on its surface, and perfluorooctyl sulfonyl fluoride grafted through the amino groups. The composite material of this invention utilizes the amino and hyperbranched perfluorooctyl functional groups enriched on the matrix surface to adsorb and anchor perfluorooctyl sulfonate ions in foam extinguishing agents and fire-fighting wastewater; and flexibly controls the solution pH value to protonate the amino functional groups, providing targeting sites for the adsorption of perfluorooctyl sulfonate anions.

Description

Technical Field

[0001] This invention relates to the field of new functional technologies for environmental nanomaterials, specifically to a composite material, its preparation method, and its applications. Background Technology

[0002] Perfluorooctane sulfonate (PFOS) and perfluorooctane sulfonic acid (PFOA) are widely used in foam fire extinguishing agents due to their high surface activity, high chemical stability, and high thermal stability. However, because PFOS and PFOA are difficult to degrade, they pose serious ecological hazards and environmental pollution problems. Experiments have shown that PFOS does not decompose after boiling in concentrated sulfuric acid for 1 hour and remains stable in various anaerobic and aerobic biodegradation experiments. Furthermore, it exhibits bioaccumulation, entering the human body through the respiratory tract and drinking water, and is difficult to excrete, eventually accumulating in the blood and organs such as the liver, kidneys, and brain. The concentration of PFOS gradually increases with the increase of trophic level in the food chain. Even if the concentration of PFOS in aquatic animals is only in the trace range (ng / g), it can be amplified through the food chain and accumulate in the human body, harming human health. Currently, PFOS has been detected in water bodies, organisms, humans, and food. Therefore, countries around the world have successively introduced corresponding laws and regulations to restrict its production and use. In 2009, the United Nations Environment Programme (EPA) adopted the Stockholm Convention on Persistent Organic Pollutants, which included nine categories of substances, including perfluorooctane sulfonate (PFOS) and perfluorooctane sulfonyl fluoride (PFOSF), in the list of persistent organic pollutants.

[0003] Both the "Integrated Wastewater Discharge Standard" (GB8978-1996) and the "Pollutant Discharge Standard for Urban Wastewater Treatment Plants" (GB18918-2002) clearly stipulate that the maximum allowable discharge concentration of fluoride-containing wastewater into municipal pipe networks is 10 mg / L, and the effluent standard for urban wastewater treatment plants is also 10 mg / L. This means that current national standards only require a fluoride concentration of 10 mg / L for water discharged into bodies of water. Therefore, upgrading fluoride treatment standards will be a common challenge facing the wastewater treatment industry. The treatment of fluoride-containing fire-fighting water to meet relevant standards has become a popular research area.

[0004] Domestic and international methods for treating fluoride-containing wastewater include chemical precipitation, adsorption, electrochemical methods, reverse osmosis, ion exchange, and biological treatment technologies. Emerging technologies include photodegradation, supercritical elemental iron reduction degradation, and ultrasonic degradation; however, these technologies have stringent reaction conditions, making practical application difficult. Adsorption, which utilizes solid materials with special structures to adsorb perfluorinated compounds from wastewater, is a wastewater treatment method with significant potential for widespread application. Adsorption offers advantages such as low cost, ease of operation, high efficiency, minimal or no secondary pollution, and a wide availability of adsorbent materials, gradually becoming a primary and relatively mature method for fluoride removal. In adsorption fluoride removal, fluoride-containing wastewater is passed through an adsorption device or mixed and impregnated with an adsorbent. The principle of fluoride removal is the exchange of fluoride ions with fluoride-loving groups or other ions on the adsorbent, resulting in a decrease in the fluoride concentration in the water. After fluoride absorption, the adsorbent can be regenerated through acid washing, and the fluoride removal effect remains good even after acid washing. Commonly used solid adsorbents include iron-based adsorbents, aluminum-based adsorbents, rare earth adsorbents, and bioadsorbents. Different adsorbents have different specific surface areas, resulting in different adsorption capacities. A good adsorbent should have a large adsorption capacity and a fast adsorption rate, reaching adsorption equilibrium quickly.

[0005] The commonly used aluminum-based adsorbent is activated alumina, with an adsorption capacity of 0.8–2.0 mg / g. Activated alumina offers low reagent and operating costs for fluoride removal. Therefore, it is the most widely used and effective method for fluoride removal. The structure of activated alumina determines its excellent adsorption function. The second layer of activated alumina contains twice as many oxygen ions as the first layer, and these oxygen ions are bonded to aluminum ions. This results in exposed aluminum ions on the surface, allowing it to adsorb fluoride. - It combines and achieves the purpose of defluorination.

[0006] Because foam extinguishing agents and fire-fighting wastewater contain a lot of organic matter, they can interfere with the adsorption of PFOS and PFOA. Furthermore, the interaction between activated carbon or alumina and perfluorinated compounds is too weak, resulting in limited adsorption efficiency. In addition, traditional Al2O3, due to its amorphous channels, small specific surface area, and small pore volume, has a low saturation adsorption capacity for perfluorinated compounds. Therefore, it is essential to develop adsorbents with high affinity and rapid removal of PFOS and PFOA from fire-fighting water. Summary of the Invention

[0007] The purpose of this invention is to overcome the problem that existing defluorination adsorbents have poor adsorption capacity for PFOS and PFOA in fire-fighting water, and to provide a composite material, its preparation method and application.

[0008] To achieve the above objectives, a first aspect of the present invention provides a composite material comprising ordered mesoporous alumina with an amino group modified on its surface, and perfluorooctyl sulfonyl fluoride grafted through the amino group.

[0009] Preferably, the composite material has a mesopore size range of 6-13 nm, an average pore size of 8-9.8 nm, and a pore volume of 0.7-1 cm³. 3 / g, specific surface area is 230-320m² 2 / g.

[0010] A second aspect of the present invention provides a method for preparing a composite material, the method comprising the following steps:

[0011] (1) Ordered mesoporous alumina is subjected to amination pretreatment to obtain ordered mesoporous alumina with amino surface modification.

[0012] (2) The ordered mesoporous alumina with amino-modified surface is reacted with perfluorooctyl sulfonyl fluoride.

[0013] Preferably, in step (1), the method for preparing the ordered mesoporous alumina includes:

[0014] (a) Mix aluminum salt with template agent and then stir to obtain a mixture;

[0015] (b) Add a pH adjuster to the mixture to adjust the pH of the system to ≥9, and then stir to obtain a gel mixture;

[0016] (c) The gel mixture is sequentially filtered, washed, dried and calcined to obtain ordered mesoporous alumina.

[0017] Preferably, in step (a), the aluminum salt is selected from one or more of AlCl3·6H2O, Al(NO3)3, NaAlO2 and aluminum sulfate.

[0018] Preferably, the aluminum salt is AlCl3·6H2O.

[0019] Preferably, in step (a), the template agent is selected from one or more of polyethylene glycol, polyvinyl alcohol, and polypropylene alcohol.

[0020] Preferably, the template agent is polyethylene glycol.

[0021] Preferably, in step (a), the weight ratio of the aluminum salt to the template agent is 1:0.5-2.

[0022] Preferably, the stirring conditions include: a speed of 200-500 rpm and a time of 20-40 min.

[0023] Preferably, in step (b), the pH adjuster is selected from one or more of ammonia, ammonium carbonate, and sodium hydroxide.

[0024] Preferably, the pH adjuster is ammonia.

[0025] Preferably, in step (b), the pH of the system is adjusted to 9-9.5.

[0026] Preferably, in step (b), the stirring conditions include: a speed of 500-800 rpm, a temperature of 40-70°C, and a time of 10-18 h.

[0027] Preferably, in step (c), the drying conditions include a temperature of 40-80°C and a time of 10-24 hours.

[0028] Preferably, the calcination conditions include: a temperature of 500-600℃ and a time of 4-6 hours.

[0029] Preferably, in step (1), the specific process of pre-treating the ordered mesoporous alumina with amination includes:

[0030] S1: Mix ordered mesoporous alumina with toluene, then sonicate, then heat to 100-120℃, and then add 3-aminopropyltriethoxysilane for reflux reaction;

[0031] S2: Centrifuge the material obtained after the reflux reaction in step S1, and wash and dry the resulting solid.

[0032] Preferably, in step S1, the ultrasound duration is 5-10 minutes.

[0033] Preferably, in step S1, the solid-liquid ratio of the ordered mesoporous alumina to toluene is 1g:40-80mL.

[0034] Preferably, the solid-liquid ratio of the ordered mesoporous alumina to the 3-aminopropyltriethoxysilane is 1g:0.4-0.8mL.

[0035] Preferably, the reflux reaction conditions include: a temperature of 100-120°C and a time of 16-24 hours.

[0036] Preferably, in step (2), the specific process of reacting the amino-modified ordered mesoporous alumina with perfluorooctyl sulfonyl fluoride includes:

[0037] (I) Mix perfluorooctyl sulfonyl fluoride, chloroform and isopropyl ether to obtain a perfluorooctyl sulfonyl fluoride solution;

[0038] (II) Under stirring conditions, ordered mesoporous alumina with amino-modified surface is mixed with isopropyl ether, and then perfluorooctyl sulfonyl fluoride solution is added dropwise to obtain a mixed solution;

[0039] (III) React the mixture, then centrifuge it, and dry the resulting solid.

[0040] Preferably, in step (I), the volume ratio of the perfluorooctyl sulfonyl fluoride, chloroform and isopropyl ether is 0.6:1.8-2.2:0.9-1.1.

[0041] Preferably, in step (II), the stirring temperature is 0-10℃ and the stirring speed is 800-1200rpm.

[0042] Preferably, the solid-liquid ratio of the amino-modified ordered mesoporous alumina to isopropyl ether is 1g:4-6mL.

[0043] Preferably, the solid-liquid ratio of the amino-modified ordered mesoporous alumina to perfluorooctyl sulfonyl fluoride is 1 g: 0.4-2 mL.

[0044] Preferably, in step (III), the reaction conditions include a temperature of 50-70°C and a time of 0.5-1 h.

[0045] A third aspect of the present invention provides the application of the above-described composite material or the composite material prepared by the above-described preparation method in the adsorption of perfluorooctane sulfonate and perfluorooctane sulfonic acid.

[0046] This invention employs a template method to prepare ordered mesoporous alumina, followed by high-temperature calcination to produce the ordered mesoporous alumina material. Then, considering the weak interaction between pure alumina and perfluorinated compounds, the alumina is functionalized by grafting 3-aminopropyltriethoxysilane onto the surface of the mesoporous alumina. The enriched amino functional groups on the surface are used to adsorb and anchor perfluorooctylsulfonyl fluoride, ultimately yielding a hyperbranched functionalized alumina material rich in perfluorooctylsulfonyl fluoride groups. Utilizing the fluorophilic interaction mechanism between perfluoroalkyl chains and the interaction between partially protonated amines and PFOS / PFOA, PFOS and PFOA in fire-fighting wastewater can be removed. Attached Figure Description

[0047] Figure 1 The N2 adsorption-desorption curve of the composite material obtained in Example 1 is shown.

[0048] Figure 2 This is a pore size distribution diagram of the composite material obtained in Example 1. Detailed Implementation

[0049] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0050] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0051] In one aspect, the present invention provides a composite material comprising ordered mesoporous alumina with an amino group modified on its surface, and perfluorooctyl sulfonyl fluoride grafted through the amino group.

[0052] In a preferred embodiment of the present invention, the mesopore size distribution of the composite material is in the range of 6-13 nm, the average pore size is 8-9.8 nm, and the pore volume is 0.7-1 cm³. 3 / g, specific surface area is 230-320m² 2 / g.

[0053] In specific embodiments, the average pore size of the composite material can be 8nm, 8.5nm, 8.7nm, 9nm, 9.2nm, 9.5nm, 9.7nm, or 9.8nm.

[0054] In a specific embodiment, the pore volume of the composite material can be 0.7 cm. 3 / g, 0.8cm 3 / g, 0.9cm 3 / g or 1cm 3 / g.

[0055] In a specific embodiment, the specific surface area of ​​the composite material can be 230 m². 2 / g、250m 2 / g、270m 2 / g、300m 2 / g or 320m 2 / g.

[0056] A second aspect of the present invention provides a method for preparing a composite material, the method comprising the following steps:

[0057] (1) Ordered mesoporous alumina is subjected to amination pretreatment to obtain ordered mesoporous alumina with amino surface modification.

[0058] (2) The ordered mesoporous alumina with amino-modified surface is reacted with perfluorooctyl sulfonyl fluoride.

[0059] In a preferred embodiment of the present invention, in step (1), the method for preparing the ordered mesoporous alumina includes:

[0060] (a) Mix aluminum salt with template agent and then stir to obtain a mixture;

[0061] (b) Add a pH adjuster to the mixture to adjust the pH of the system to ≥9, and then stir to obtain a gel mixture;

[0062] (c) The gel mixture is sequentially filtered, washed, dried and calcined to obtain ordered mesoporous alumina.

[0063] In a preferred embodiment of the present invention, in step (a), the aluminum salt is selected from one or more of AlCl3·6H2O, Al(NO3)3, NaAlO2 and aluminum sulfate, and is more preferably AlCl3·6H2O.

[0064] In step (a) of the present invention, in a preferred case, the aluminum salt is first mixed with water to obtain an aluminum salt solution, and then mixed with the template agent. At this time, the solid-liquid ratio of the aluminum salt to water is 1g:15-40mL, specifically 1g:15mL, 1g:30mL, 1g:35mL or 1g:40mL.

[0065] In a preferred embodiment of the present invention, in step (a), the template agent is selected from one or more of polyethylene glycol, polyvinyl alcohol and polypropylene alcohol, and more preferably polyethylene glycol.

[0066] In a preferred embodiment of the present invention, in step (a), the weight ratio of the aluminum salt to the template agent is 1:0.5-2, specifically 1:0.5, 1:0.7, 1:1, 1:1.2, 1:1.5, 1:1.7 or 1:2.

[0067] In a preferred embodiment of the present invention, in step (a), the stirring conditions include: a speed of 200-500 rpm and a time of 20-40 min.

[0068] In a specific implementation, in step (a), the stirring speed can be 200 rpm, 250 rpm, 300 rpm, 350 rpm, 400 rpm, 450 rpm or 500 rpm, and the stirring time can be 20 min, 22 min, 25 min, 27 min, 30 min, 32 min, 35 min, 37 min or 40 min.

[0069] In a preferred embodiment of the present invention, in step (b), the pH adjuster is selected from one or more of ammonia, ammonium carbonate and sodium hydroxide, and is more preferably ammonia.

[0070] In a preferred embodiment of the present invention, in step (b), the pH value of the system is adjusted to 9-9.5, specifically to 9, 9.1, 9.2, 9.3, 9.4 or 9.5.

[0071] In a preferred embodiment of the present invention, in step (b), the stirring conditions include: a speed of 500-800 rpm, a temperature of 40-70°C, and a time of 10-18 h.

[0072] In a specific implementation, in step (b), the stirring speed can be 500 rpm, 550 rpm, 600 rpm, 650 rpm, 700 rpm, 750 rpm, or 800 rpm, the stirring temperature can be 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, or 70℃, and the stirring time can be 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, or 18h.

[0073] In a preferred embodiment of the present invention, in step (c), the drying conditions include a temperature of 40-80°C and a time of 10-24 hours.

[0074] In a specific embodiment of the present invention, in step (c), the drying temperature can be 40°C, 50°C, 60°C, 70°C or 80°C, and the drying time can be 10h, 13h, 15h, 17h, 20h or 24h.

[0075] In a preferred embodiment of the present invention, in step (c), the calcination conditions include: a temperature of 500-600°C and a time of 4-6 hours.

[0076] In step (c) of the present invention, after the drying operation is completed, the temperature is raised to 500-600°C at a heating rate of 1-2°C / min for calcination.

[0077] In a specific embodiment of the present invention, in step (c), the calcination temperature can be 500°C, 520°C, 540°C, 550°C, 560°C, 580°C or 600°C, and the calcination time can be 4h, 4.5h, 5h, 5.5h or 6h.

[0078] In a preferred embodiment of the present invention, the specific process of pre-treating ordered mesoporous alumina by amination in step (1) includes:

[0079] S1: Mix ordered mesoporous alumina with toluene, then sonicate, then heat to 100-120℃, and then add 3-aminopropyltriethoxysilane for reflux reaction;

[0080] S2: Centrifuge the material obtained after the reflux reaction in step S1, and wash and dry the resulting solid.

[0081] In a preferred embodiment, the ultrasound duration in step S1 is 5-10 minutes, specifically 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, or 10 minutes.

[0082] In a preferred embodiment, in step S1, the solid-liquid ratio of the ordered mesoporous alumina to toluene is 1g:40-80mL, specifically 1g:40mL, 1g:50mL, 1g:60mL, 1g:70mL, or 1g:80mL.

[0083] In a preferred embodiment, in step S1, the solid-liquid ratio of the ordered mesoporous alumina to the 3-aminopropyltriethoxysilane is 1g:0.4-0.8mL, specifically 1g:0.4mL, 1g:0.5mL, 1g:0.6mL, 1g:0.7mL, or 1g:0.8mL.

[0084] In step S1 of this invention, the conditions for the reflux reaction include: a temperature of 100-120°C and a time of 16-24 hours.

[0085] In a specific implementation, the temperature of the reflux reaction can be 100°C, 105°C, 110°C, 115°C or 120°C, and the temperature and time of the reflux reaction can be 16h, 18h, 20h, 22h or 24h.

[0086] In step S2 of the present invention, the centrifugation conditions include: a rotation speed of 5500-6500 rpm and a time of 15-30 min.

[0087] In one specific embodiment, in step S2, the centrifugation speed is 6000 rpm and the centrifugation time is 20 min.

[0088] In one specific embodiment of the present invention, ethanol is used for washing in step S2.

[0089] In a preferred embodiment of the present invention, the specific process of reacting the amino-modified ordered mesoporous alumina with perfluorooctyl sulfonyl fluoride in step (2) includes:

[0090] (I) Mix perfluorooctyl sulfonyl fluoride, chloroform and isopropyl ether to obtain a perfluorooctyl sulfonyl fluoride solution;

[0091] (II) Under stirring conditions, ordered mesoporous alumina with amino-modified surface is mixed with isopropyl ether, and then perfluorooctyl sulfonyl fluoride solution is added dropwise to obtain a mixed solution;

[0092] (III) React the mixture, then centrifuge it, and dry the resulting solid.

[0093] In a preferred embodiment of the present invention, in step (I), the volume ratio of the amounts of perfluorooctyl sulfonyl fluoride, chloroform and isopropyl ether is 0.6:1.8-2.2:0.9-1.1.

[0094] In a specific implementation, in step (I), the volume ratio of the perfluorooctyl sulfonyl fluoride to the chloroform can be 0.6:1.8, 0.6:1.9, 0.6:2, 0.6:2.1, or 0.6:2.2, and the volume ratio of the perfluorooctyl sulfonyl fluoride to the isopropyl ether can be 0.6:0.9, 0.6:1, or 0.6:1.1.

[0095] In a preferred embodiment of the present invention, in step (II), the stirring temperature is 0-10℃ and the stirring speed is 800-1200rpm.

[0096] In a specific implementation, in step (II), the stirring temperature can be 0℃, 2℃, 5℃, 7℃ or 10℃, and the stirring speed can be 800rpm, 900rpm, 1000rpm, 1100rpm or 1200rpm.

[0097] In a preferred embodiment of step (II), the solid-liquid ratio of the amino-modified ordered mesoporous alumina to isopropyl ether is 1g:4-6mL, specifically 1g:4mL, 1g:5mL or 1g:6mL.

[0098] In a preferred embodiment of the present invention, the solid-liquid ratio of the amino-modified ordered mesoporous alumina to perfluorooctyl sulfonyl fluoride is 1g:0.4-2mL, specifically 1g:0.4mL, 1g:0.5mL, 1g:0.6mL, 1g:0.7mL, 1g:0.8mL, 1g:0.9mL, 1g:1mL, 1g:1.1mL, 1g:1.2mL, 1g:1.3mL, 1g:1.4mL, 1g:1.5mL, 1g:1.6mL, 1g:1.7mL, 1g:1.8mL, 1g:1.9mL, or 1g:2mL.

[0099] In a preferred embodiment of the present invention, in step (II), in order to enable the perfluorooctyl sulfonyl fluoride to react fully with the aminated ordered mesoporous alumina, the perfluorooctyl sulfonyl fluoride solution needs to be added dropwise slowly, and the dropping rate needs to be controlled.

[0100] Therefore, in a preferred embodiment, in step (II), the dropping rate is 3-10 drops / min, and the volume of each drop of perfluorooctyl sulfonyl fluoride solution is 90-120 μL.

[0101] In a specific implementation, in step (II), the dripping rate can be 3 drops / min, 4 drops / min, 5 drops / min, 6 drops / min, 7 drops / min, 8 drops / min, 9 drops / min or 10 drops / min, and the volume of each drop of perfluorooctyl sulfonyl fluoride solution can be 90 μL, 95 μL, 100 μL, 105 μL, 110 μL, 115 μL or 120 μL.

[0102] In a preferred embodiment of the present invention, in step (III), the reaction conditions include: a temperature of 50-70°C and a time of 0.5-1h.

[0103] In the specific implementation of step (III), the reaction temperature can be 50°C, 55°C, 60°C, 65°C or 70°C, and the reaction time can be 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1h.

[0104] In step (III) of the present invention, the centrifugation conditions include: a rotation speed of 5500-6500 rpm and a time of 15-30 min.

[0105] In one specific embodiment, in step (III), the centrifugation speed is 6000 rpm and the centrifugation time is 20 min.

[0106] A third aspect of the present invention provides the application of the above-described composite material or the composite material prepared by the above-described preparation method in the adsorption of perfluorooctyl sulfonate and perfluorooctyl sulfonic acid.

[0107] This method prepares ordered mesoporous alumina using a template method. First, a template agent with a specific structure is selected. Then, chemically active reactants are added, and a precursor is generated through a physicochemical process. The template agent is then removed by washing and calcination, resulting in ordered mesoporous alumina with a defined pore structure and size. This method effectively controls the pore structure of the product. Ordered mesoporous alumina possesses advantages such as good mechanical stability, specific surface area, and pore structure, ease of control, low cost, and abundant crystal forms. Furthermore, the ordered mesoporous alumina is functionalized by grafting amino groups onto its surface. The surface-enriched amino functional groups are then used to adsorb and anchor perfluorooctyl sulfonyl fluoride, resulting in a hyperbranched functionalized alumina material rich in perfluorooctyl sulfonyl fluoride groups.

[0108] This invention utilizes ordered mesoporous alumina materials with large pore size and high specific surface area as a matrix, and grafts hyperbranched perfluorooctyl sulfonyl fluoride onto its surface (the amount of functionalized alumina targeting groups can be controlled by changing the amount of 3-aminopropyltriethoxysilane and perfluorooctyl sulfonyl fluoride added). The amino and hyperbranched perfluorooctyl functional groups enriched on the matrix surface are used to adsorb and anchor perfluorooctane sulfonate in foam extinguishing agents and fire-fighting wastewater. The pH value of the solution is flexibly controlled to protonate the amino functional groups, providing target sites for the adsorption of perfluorooctane sulfonate.

[0109] The present invention will be described in detail below through embodiments, but the scope of protection of the present invention is not limited thereto.

[0110] Example 1

[0111] (1) Weigh 5.4g of aluminum salt (AlCl3·6H2O) and dissolve it in 97.0mL of deionized water. Place the solution in a constant temperature water bath at 40℃ and stir evenly on a magnetic stirrer to obtain an aluminum salt solution. Then weigh 6.0g of template agent (polyethylene glycol PEG-20000). The weight ratio of aluminum salt to template agent is 1:1.11. Slowly add the template agent to the aluminum salt solution and mix. Then continue stirring (stirring conditions include: speed of 300rpm and time of 30min) to obtain a transparent mixture.

[0112] (2) Slowly add pH adjuster (ammonia) to the transparent mixture to adjust the pH value of the system to 9.0, and then continue stirring (stirring conditions include: stirring speed of 600 rpm, temperature of 60℃, and time of 12h) to obtain a gel mixture;

[0113] (3) The gel mixture was filtered, the solid obtained was washed with water and then transferred to an oven to dry at 80°C for 18 hours. Then, in a muffle furnace, the temperature was increased to 550°C at a heating rate of 1°C / min and calcined at 550°C for 6 hours to obtain ordered mesoporous alumina B1.

[0114] (4) Dissolve 1g of ordered mesoporous alumina obtained in step (3) in 60mL of toluene, then sonicate for 10min, then heat the oil bath to 110℃, then add 0.6mL of 3-aminopropyltriethoxysilane, and continue to reflux at the temperature (110℃) for 18h.

[0115] (5) After the reflux reaction is completed, the material obtained is centrifuged (centrifugation speed is 6000 rpm, centrifugation time is 20 min), the obtained solid is washed with ethanol and then dried to obtain ordered mesoporous alumina B2 with amino surface modification.

[0116] (6) Mix 0.6 mL of perfluorooctyl sulfonyl fluoride with a mixed solution of 2 mL of chloroform and 1 mL of isopropyl ether to obtain a perfluorooctyl sulfonyl fluoride solution;

[0117] (7) Under stirring conditions (temperature 0℃, speed 1000rpm), 1g of ordered mesoporous alumina with amino surface modified is dissolved in 5mL of isopropyl ether and mixed evenly. Then, under stirring conditions (temperature 0℃, speed 1000rpm), perfluorooctane sulfonyl fluoride solution is slowly added dropwise (the addition rate is 5 drops / min, and the volume of each drop of perfluorooctane sulfonyl fluoride solution is 100μL). After the addition is completed, a mixture is obtained.

[0118] (8) The mixture was stirred at 500 rpm at 60°C for 0.5 h, then centrifuged (centrifugation speed was 6000 rpm, centrifugation time was 20 min), and the resulting solid was dried to obtain composite material A1.

[0119] Example 2

[0120] (1) Weigh 5.4g of aluminum salt (AlCl3·6H2O) and dissolve it in 97.0mL of deionized water. Place the solution in a constant temperature water bath at 40℃ and stir evenly on a magnetic stirrer to obtain an aluminum salt solution. Then weigh 6.0g of template agent (polyethylene glycol PEG-20000). The weight ratio of aluminum salt to template agent is 1:1.11. Slowly add the template agent to the aluminum salt solution and mix. Then continue stirring (stirring conditions include: speed of 300rpm and time of 30min) to obtain a transparent mixture.

[0121] (2) Slowly add pH adjuster (ammonia) to the transparent mixture to adjust the pH value of the system to 9.0, and then continue stirring (stirring conditions include: stirring speed of 600 rpm, temperature of 60℃, and time of 12h) to obtain a gel mixture;

[0122] (3) The gel mixture was filtered, the solid obtained was washed with water and then transferred to an oven to dry at 80°C for 18 hours. Then, in a muffle furnace, the temperature was increased to 550°C at a heating rate of 1°C / min and calcined at 550°C for 6 hours to obtain ordered mesoporous alumina.

[0123] (4) Dissolve 1g of ordered mesoporous alumina obtained in step (3) in 60mL of toluene, then sonicate for 10min, then heat the oil bath to 110℃, then add 0.4mL of 3-aminopropyltriethoxysilane, and continue to reflux at the temperature (110℃) for 18h.

[0124] (5) After the reflux reaction is completed, the material obtained is centrifuged (centrifugation speed is 6000 rpm, centrifugation time is 20 min), the obtained solid is washed with ethanol and then dried to obtain ordered mesoporous alumina with amino surface modification.

[0125] (6) Mix 0.6 mL of perfluorooctyl sulfonyl fluoride with a mixed solution of 2 mL of chloroform and 1 mL of isopropyl ether to obtain a perfluorooctyl sulfonyl fluoride solution;

[0126] (7) Under stirring conditions (temperature 0℃, speed 1000rpm), 1g of ordered mesoporous alumina with amino surface modified is dissolved in 5mL of isopropyl ether and mixed evenly. Then, under stirring conditions (temperature 0℃, speed 1000rpm), perfluorooctane sulfonyl fluoride solution is slowly added dropwise (the addition rate is 5 drops / min, and the volume of each drop of perfluorooctane sulfonyl fluoride solution is 100μL). After the addition is completed, a mixture is obtained.

[0127] (8) The mixture was stirred at 500 rpm at 60°C for 0.5 h, then centrifuged (centrifugation speed was 6000 rpm, centrifugation time was 20 min), and the resulting solid was dried to obtain composite material A2.

[0128] Example 3

[0129] (1) Weigh 5.4g of aluminum salt (AlCl3·6H2O) and dissolve it in 97.0mL of deionized water. Place the solution in a constant temperature water bath at 40℃ and stir evenly on a magnetic stirrer to obtain an aluminum salt solution. Then weigh 6.0g of template agent (polyethylene glycol PEG-20000). The weight ratio of aluminum salt to template agent is 1:1.11. Slowly add the template agent to the aluminum salt solution and mix. Then continue stirring (stirring conditions include: speed of 300rpm and time of 30min) to obtain a transparent mixture.

[0130] (2) Slowly add pH adjuster (ammonia) to the transparent mixture to adjust the pH value of the system to 9.0, and then continue stirring (stirring conditions include: stirring speed of 600 rpm, temperature of 60℃, and time of 12h) to obtain a gel mixture;

[0131] (3) The gel mixture was filtered, the solid obtained was washed with water and then transferred to an oven to dry at 80°C for 18 hours. Then, in a muffle furnace, the temperature was increased to 550°C at a heating rate of 1°C / min and calcined at 550°C for 6 hours to obtain ordered mesoporous alumina.

[0132] (4) Dissolve 1g of ordered mesoporous alumina obtained in step (3) in 60mL of toluene, then sonicate for 10min, then heat the oil bath to 110℃, then add 0.8mL of 3-aminopropyltriethoxysilane, and continue to reflux at the temperature (110℃) for 18h.

[0133] (5) After the reflux reaction is completed, the material obtained is centrifuged (centrifugation speed is 6000 rpm, centrifugation time is 20 min), the obtained solid is washed with ethanol and then dried to obtain ordered mesoporous alumina with amino surface modification.

[0134] (6) Mix 0.8 mL of perfluorooctyl sulfonyl fluoride with a mixed solution of 2.7 mL of chloroform and 1.4 mL of isopropyl ether until homogeneous (the volume ratio of perfluorooctyl sulfonyl fluoride, chloroform and isopropyl ether is 0.6:2.025:1.05) to obtain a perfluorooctyl sulfonyl fluoride solution.

[0135] (7) Under stirring conditions (temperature 0℃, speed 1000rpm), 1g of ordered mesoporous alumina with amino surface modified is dissolved in 5mL of isopropyl ether and mixed evenly. Then, under stirring conditions (temperature 0℃, speed 1000rpm), perfluorooctane sulfonyl fluoride solution is slowly added dropwise (the addition rate is 5 drops / min, and the volume of each drop of perfluorooctane sulfonyl fluoride solution is 100μL). After the addition is completed, a mixture is obtained.

[0136] (8) The mixture was stirred at 500 rpm at 60°C for 0.5 h, then centrifuged (centrifugation speed was 6000 rpm, centrifugation time was 20 min), and the resulting solid was dried to obtain composite material A3.

[0137] Example 4

[0138] (1) Weigh 5.4g of aluminum salt (AlCl3·6H2O) and dissolve it in 97.0mL of deionized water. Place the solution in a constant temperature water bath at 40℃ and stir evenly on a magnetic stirrer to obtain an aluminum salt solution. Then weigh 6.0g of template agent (polyethylene glycol PEG-20000). The weight ratio of aluminum salt to template agent is 1:1.11. Slowly add the template agent to the aluminum salt solution and mix. Then continue stirring (stirring conditions include: speed of 300rpm and time of 30min) to obtain a transparent mixture.

[0139] (2) Slowly add pH adjuster (ammonia) to the transparent mixture to adjust the pH value of the system to 9.0, and then continue stirring (stirring conditions include: stirring speed of 600 rpm, temperature of 60℃, and time of 12h) to obtain a gel mixture;

[0140] (3) The gel mixture was filtered, the solid obtained was washed with water and then transferred to an oven to dry at 80°C for 18 hours. Then, in a muffle furnace, the temperature was increased to 550°C at a heating rate of 1°C / min and calcined at 550°C for 6 hours to obtain ordered mesoporous alumina.

[0141] (4) Dissolve 1g of ordered mesoporous alumina obtained in step (3) in 60mL of toluene, then sonicate for 10min, then heat the oil bath to 110℃, then add 0.6mL of 3-aminopropyltriethoxysilane, and continue to reflux at this temperature for 18h.

[0142] (5) After the reflux reaction is completed, the material obtained is centrifuged (centrifugation speed is 6000 rpm, centrifugation time is 20 min), the obtained solid is washed with ethanol and then dried to obtain ordered mesoporous alumina with amino surface modification.

[0143] (6) Mix 1.2 mL of perfluorooctyl sulfonyl fluoride with a mixed solution of 4 mL of chloroform and 2 mL of isopropyl ether to obtain a perfluorooctyl sulfonyl fluoride solution;

[0144] (7) Under stirring conditions (temperature 0℃, speed 1000rpm), 1g of ordered mesoporous alumina with amino surface modified is dissolved in 5mL of isopropyl ether and mixed evenly. Then, under stirring conditions (temperature 0℃, speed 1000rpm), perfluorooctane sulfonyl fluoride solution is slowly added dropwise (the addition rate is 5 drops / min, and the volume of each drop of perfluorooctane sulfonyl fluoride solution is 100μL). After the addition is completed, a mixture is obtained.

[0145] (8) The mixture was stirred at 500 rpm for 0.5 h at 60 °C, and then centrifuged (centrifugation speed was 6000 rpm and centrifugation time was 20 min). The resulting solid was dried to obtain composite material A4.

[0146] Example 5

[0147] (1) Weigh 5.4g of aluminum salt (AlCl3·6H2O) and dissolve it in 97.0mL of deionized water. Place the solution in a constant temperature water bath at 40℃ and stir evenly on a magnetic stirrer to obtain an aluminum salt solution. Then weigh 6.0g of template agent (polyethylene glycol PEG-20000). The weight ratio of aluminum salt to template agent is 1:1.11. Slowly add the template agent to the aluminum salt solution and mix. Then continue stirring (stirring conditions include: speed of 300rpm and time of 30min) to obtain a transparent mixture.

[0148] (2) Slowly add pH adjuster (ammonia) to the transparent mixture to adjust the pH value of the system to 9.0, and then continue stirring (stirring conditions include: stirring speed of 600 rpm, temperature of 60℃, and time of 12h) to obtain a gel mixture;

[0149] (3) The gel mixture was filtered, the solid obtained was washed with water and then transferred to an oven to dry at 80°C for 18 hours. Then, in a muffle furnace, the temperature was increased to 550°C at a heating rate of 1°C / min and calcined at 550°C for 6 hours to obtain ordered mesoporous alumina.

[0150] (4) Dissolve 1g of ordered mesoporous alumina obtained in step (3) in 60mL of toluene, then sonicate for 10min, then heat the oil bath to 110℃, then add 0.6mL of 3-aminopropyltriethoxysilane, and continue to reflux at the temperature (110℃) for 18h.

[0151] (5) After the reflux reaction is completed, the material obtained is centrifuged (centrifugation speed is 6000 rpm, centrifugation time is 20 min), the obtained solid is washed with ethanol and then dried to obtain ordered mesoporous alumina with amino surface modification.

[0152] (6) Mix 1.0 mL of perfluorooctyl sulfonyl fluoride with 3.3 mL of chloroform and 1.7 mL of isopropyl ether until homogeneous (the volume ratio of perfluorooctyl sulfonyl fluoride, chloroform and isopropyl ether is 0.6:1.98:1.02) to obtain a perfluorooctyl sulfonyl fluoride solution.

[0153] (7) Under stirring conditions (temperature 0℃, speed 1000rpm), 1g of ordered mesoporous alumina with amino surface modified is dissolved in 5mL of isopropyl ether and mixed evenly. Then, under stirring conditions (temperature 0℃, speed 1000rpm), perfluorooctane sulfonyl fluoride solution is slowly added dropwise (the addition rate is 5 drops / min, and the volume of each drop of perfluorooctane sulfonyl fluoride solution is 100μL). After the addition is completed, a mixture is obtained.

[0154] (8) The mixture was stirred at 500 rpm at 60°C for 0.5 h, then centrifuged (centrifugation speed was 6000 rpm, centrifugation time was 20 min), and the resulting solid was dried to obtain composite material A5.

[0155] Example 6

[0156] (1) Weigh 5.4g of aluminum salt (AlCl3·6H2O) and dissolve it in 97.0mL of deionized water. Place the solution in a constant temperature water bath at 40℃ and stir evenly on a magnetic stirrer to obtain an aluminum salt solution. Then weigh 6.0g of template agent (polyethylene glycol PEG-20000). The weight ratio of aluminum salt to template agent is 1:1.11. Slowly add the template agent to the aluminum salt solution and mix. Then continue stirring (stirring conditions include: speed of 300rpm and time of 30min) to obtain a transparent mixture.

[0157] (2) Slowly add pH adjuster (ammonia) to the transparent mixture to adjust the pH value of the system to 9.0, and then continue stirring (stirring conditions include: stirring speed of 600 rpm, temperature of 50℃, and time of 12 h) to obtain a gel mixture;

[0158] (3) The gel mixture was filtered, the solid obtained was washed with water and then transferred to an oven to dry at 80°C for 18 hours. Then, in a muffle furnace, the temperature was increased to 550°C at a heating rate of 1°C / min and calcined at 550°C for 6 hours to obtain ordered mesoporous alumina.

[0159] (4) Dissolve 1g of ordered mesoporous alumina obtained in step (3) in 60mL of toluene, then sonicate for 10min, then heat the oil bath to 110℃, then add 0.6mL of 3-aminopropyltriethoxysilane, and continue to reflux at the temperature (110℃) for 18h.

[0160] (5) After the reflux reaction is completed, the material obtained is centrifuged (centrifugation speed is 6000 rpm, centrifugation time is 20 min), the obtained solid is washed with ethanol and then dried to obtain ordered mesoporous alumina with amino surface modification.

[0161] (6) Mix 0.6 mL of perfluorooctyl sulfonyl fluoride with a mixed solution of 2 mL of chloroform and 1 mL of isopropyl ether to obtain a perfluorooctyl sulfonyl fluoride solution;

[0162] (7) Under stirring conditions (temperature 0℃, speed 1000rpm), 1g of ordered mesoporous alumina with amino surface modified is dissolved in 5mL of isopropyl ether and mixed evenly. Then, under stirring conditions (temperature 0℃, speed 1000rpm), perfluorooctane sulfonyl fluoride solution is slowly added dropwise (the addition rate is 5 drops / min, and the volume of each drop of perfluorooctane sulfonyl fluoride solution is 100μL). After the addition is completed, a mixture is obtained.

[0163] (8) The mixture was stirred at 500 rpm at 60°C for 0.5 h, then centrifuged (centrifugation speed was 6000 rpm, centrifugation time was 20 min), and the resulting solid was dried to obtain composite material A6.

[0164] Example 7

[0165] (1) Weigh 5.4g of aluminum salt (AlCl3·6H2O) and dissolve it in 97.0mL of deionized water. Place the solution in a constant temperature water bath at 40℃ and stir evenly on a magnetic stirrer to obtain an aluminum salt solution. Then weigh 6.0g of template agent (polyethylene glycol PEG-20000). The weight ratio of aluminum salt to template agent is 1:1.11. Slowly add the template agent to the aluminum salt solution and mix. Then continue stirring (stirring conditions include: speed of 300rpm and time of 30min) to obtain a transparent mixture.

[0166] (2) Slowly add pH adjuster (ammonia) to the transparent mixture to adjust the pH value of the system to 9.0, and then continue stirring (stirring conditions include: stirring speed of 600 rpm, temperature of 70℃, and time of 12h) to obtain a gel mixture;

[0167] (3) The gel mixture was filtered, the solid obtained was washed with water and then transferred to an oven to dry at 80°C for 18 hours. Then, in a muffle furnace, the temperature was increased to 550°C at a heating rate of 1°C / min and calcined at 550°C for 6 hours to obtain ordered mesoporous alumina.

[0168] (4) Dissolve 1g of ordered mesoporous alumina obtained in step (3) in 60mL of toluene, then sonicate for 10min, then heat the oil bath to 110℃, then add 0.6mL of 3-aminopropyltriethoxysilane, and continue to reflux at the temperature (110℃) for 18h.

[0169] (5) After the reflux reaction is completed, the material obtained is centrifuged (centrifugation speed is 6000 rpm, centrifugation time is 20 min), the obtained solid is washed with ethanol and then dried to obtain ordered mesoporous alumina with amino surface modification.

[0170] (6) Mix 0.6 mL of perfluorooctyl sulfonyl fluoride with a mixed solution of 2 mL of chloroform and 1 mL of isopropyl ether to obtain a perfluorooctyl sulfonyl fluoride solution;

[0171] (7) Under stirring conditions (temperature 0℃, speed 1000rpm), 1g of ordered mesoporous alumina with amino surface modified is dissolved in 5mL of isopropyl ether and mixed evenly. Then, under stirring conditions (temperature 0℃, speed 1000rpm), perfluorooctane sulfonyl fluoride solution is slowly added dropwise (the addition rate is 5 drops / min, and the volume of each drop of perfluorooctane sulfonyl fluoride solution is 100μL). After the addition is completed, a mixture is obtained.

[0172] (8) The mixture was stirred at 500 rpm at 60°C for 0.5 h, then centrifuged (centrifugation speed was 6000 rpm, centrifugation time was 20 min), and the resulting solid was dried to obtain composite material A7.

[0173] Example 8

[0174] (1) Weigh 5.4g of aluminum salt (AlCl3·6H2O) and dissolve it in 97.0mL of deionized water. Place the solution in a constant temperature water bath at 40℃ and stir evenly on a magnetic stirrer to obtain an aluminum salt solution. Then weigh 9.72g of template agent (polyethylene glycol PEG-20000). The weight ratio of aluminum salt to template agent is 1:1.80. Slowly add the template agent to the aluminum salt solution and mix. Then continue stirring (stirring conditions include: speed of 300rpm and time of 30min) to obtain a transparent mixture.

[0175] (2) Slowly add pH adjuster (ammonia) to the transparent mixture to adjust the pH value of the system to 9.0, and then continue stirring (stirring conditions include: stirring speed of 600 rpm, temperature of 60℃, and time of 12h) to obtain a gel mixture;

[0176] (3) The gel mixture was filtered, the solid obtained was washed with water and then transferred to an oven to dry at 80°C for 18 hours. Then, in a muffle furnace, the temperature was increased to 550°C at a heating rate of 1°C / min and calcined at 550°C for 6 hours to obtain ordered mesoporous alumina.

[0177] (4) Dissolve 1g of ordered mesoporous alumina obtained in step (3) in 60mL of toluene, then sonicate for 10min, then heat the oil bath to 110℃, then add 0.6mL of 3-aminopropyltriethoxysilane, and continue to reflux at the temperature (110℃) for 18h.

[0178] (5) After the reflux reaction is completed, the material obtained is centrifuged (centrifugation speed is 6000 rpm, centrifugation time is 20 min), the obtained solid is washed with ethanol and then dried to obtain ordered mesoporous alumina with amino surface modification.

[0179] (6) Mix 0.6 mL of perfluorooctyl sulfonyl fluoride with a mixed solution of 2 mL of chloroform and 1 mL of isopropyl ether to obtain a perfluorooctyl sulfonyl fluoride solution;

[0180] (7) Under stirring conditions (temperature 0℃, speed 1000rpm), 1g of ordered mesoporous alumina with amino surface modified is dissolved in 5mL of isopropyl ether and mixed evenly. Then, under stirring conditions (temperature 0℃, speed 1000rpm), perfluorooctane sulfonyl fluoride solution is slowly added dropwise (the addition rate is 5 drops / min, and the volume of each drop of perfluorooctane sulfonyl fluoride solution is 100μL). After the addition is completed, a mixture is obtained.

[0181] (8) The mixture was stirred at 500 rpm at 60°C for 0.5 h, then centrifuged (centrifugation speed was 6000 rpm, centrifugation time was 20 min), and the resulting solid was dried to obtain composite material A8.

[0182] Example 9

[0183] (1) Weigh 5.4g of aluminum salt (AlCl3·6H2O) and dissolve it in 97.0mL of deionized water. Place the solution in a constant temperature water bath at 40℃ and stir evenly on a magnetic stirrer to obtain an aluminum salt solution. Then weigh 3.24g of template agent (polyethylene glycol PEG-20000). The weight ratio of aluminum salt to template agent is 1:0.6. Slowly add the template agent to the aluminum salt solution and mix. Then continue stirring (stirring conditions include: speed of 300rpm and time of 30min) to obtain a transparent mixture.

[0184] (2) Slowly add pH adjuster (ammonia) to the transparent mixture to adjust the pH value of the system to 9.0, and then continue stirring (stirring conditions include: stirring speed of 600 rpm, temperature of 60℃, and time of 12h) to obtain a gel mixture;

[0185] (3) The gel mixture was filtered, the solid obtained was washed with water and then transferred to an oven to dry at 80°C for 18 hours. Then, in a muffle furnace, the temperature was increased to 550°C at a heating rate of 1°C / min and calcined at 550°C for 6 hours to obtain ordered mesoporous alumina.

[0186] (4) Dissolve 1g of ordered mesoporous alumina obtained in step (3) in 60mL of toluene, then sonicate for 10min, then heat the oil bath to 110℃, then add 0.6mL of 3-aminopropyltriethoxysilane, and continue to reflux at the temperature (110℃) for 18h.

[0187] (5) After the reflux reaction is completed, the material obtained is centrifuged (centrifugation speed is 6000 rpm, centrifugation time is 20 min), the obtained solid is washed with ethanol and then dried to obtain ordered mesoporous alumina with amino surface modification.

[0188] (6) Mix 0.6 mL of perfluorooctyl sulfonyl fluoride with a mixed solution of 2 mL of chloroform and 1 mL of isopropyl ether to obtain a perfluorooctyl sulfonyl fluoride solution;

[0189] (7) Under stirring conditions (temperature 0℃, speed 1000rpm), 1g of ordered mesoporous alumina with amino surface modified is dissolved in 5mL of isopropyl ether and mixed evenly. Then, under stirring conditions (temperature 0℃, speed 1000rpm), perfluorooctane sulfonyl fluoride solution is slowly added dropwise (the addition rate is 5 drops / min, and the volume of each drop of perfluorooctane sulfonyl fluoride solution is 100μL). After the addition is completed, a mixture is obtained.

[0190] (8) The mixture was stirred at 500 rpm at 60°C for 0.5 h, then centrifuged (centrifugation speed was 6000 rpm, centrifugation time was 20 min), and the resulting solid was dried to obtain composite material A9.

[0191] Example 10

[0192] (1) Weigh 5.4g of aluminum salt (AlCl3·6H2O) and dissolve it in 97.0mL of deionized water. Place the solution in a constant temperature water bath at 40℃ and stir evenly on a magnetic stirrer to obtain an aluminum salt solution. Then weigh 5.2g of template agent (polyethylene glycol PEG-20000). The weight ratio of aluminum salt to template agent is 1:0.96. Slowly add the template agent to the aluminum salt solution and mix. Then continue stirring (stirring conditions include: speed of 300rpm and time of 30min) to obtain a transparent mixture.

[0193] (2) Slowly add pH adjuster (ammonia) to the transparent mixture to adjust the pH value of the system to 9.0, and then continue stirring (stirring conditions include: stirring speed of 600 rpm, temperature of 40℃, and time of 12h) to obtain a gel mixture;

[0194] (3) The gel mixture was filtered, the solid obtained was washed with water and then transferred to an oven to dry at 80°C for 18 hours. Then, in a muffle furnace, the temperature was increased to 550°C at a heating rate of 1°C / min and calcined at 550°C for 6 hours to obtain ordered mesoporous alumina.

[0195] (4) Dissolve 1g of ordered mesoporous alumina obtained in step (3) in 60mL of toluene, then sonicate for 10min, then heat the oil bath to 110℃, then add 0.6mL of 3-aminopropyltriethoxysilane, and continue to reflux at the temperature (110℃) for 18h.

[0196] (5) After the reflux reaction is completed, the material obtained is centrifuged (centrifugation speed is 6000 rpm, centrifugation time is 20 min), the obtained solid is washed with ethanol and then dried to obtain ordered mesoporous alumina with amino surface modification.

[0197] (6) Mix 0.6 mL of perfluorooctyl sulfonyl fluoride with a mixed solution of 2 mL of chloroform and 1 mL of isopropyl ether to obtain a perfluorooctyl sulfonyl fluoride solution;

[0198] (7) Under stirring conditions (temperature 0℃, speed 1000rpm), 1g of ordered mesoporous alumina with amino surface modified is dissolved in 5mL of isopropyl ether and mixed evenly. Then, under stirring conditions (temperature 0℃, speed 1000rpm), perfluorooctane sulfonyl fluoride solution is slowly added dropwise (the addition rate is 5 drops / min, and the volume of each drop of perfluorooctane sulfonyl fluoride solution is 100μL). After the addition is completed, a mixture is obtained.

[0199] (8) The mixture was stirred at 500 rpm at 60°C for 0.5 h, then centrifuged (centrifugation speed was 6000 rpm, centrifugation time was 20 min), and the resulting solid was dried to obtain composite material A10.

[0200] Comparative Example 1

[0201] The method of Example 1 was followed, except that 3-aminopropyltriethoxysilane was not added in this comparative example, i.e., no amino pretreatment was performed. The specific operation is as follows:

[0202] (1) Weigh 5.4g of aluminum salt (AlCl3·6H2O) and dissolve it in 97.0mL of deionized water. Place the solution in a constant temperature water bath at 40℃ and stir evenly on a magnetic stirrer to obtain an aluminum salt solution. Then weigh 6.0g of template agent (polyethylene glycol PEG-20000). The weight ratio of aluminum salt to template agent is 1:1.11. Slowly add the template agent to the aluminum salt solution and mix. Then continue stirring (stirring conditions include: speed of 300rpm and time of 30min) to obtain a transparent mixture.

[0203] (2) Slowly add pH adjuster (ammonia) to the transparent mixture to adjust the pH value of the system to 9.0, and then continue stirring (stirring conditions include: stirring speed of 600 rpm, temperature of 60℃, and time of 12h) to obtain a gel mixture;

[0204] (3) The gel mixture was filtered, the solid obtained was washed with water and then transferred to an oven to dry at 80°C for 18 hours. Then, in a muffle furnace, the temperature was increased to 550°C at a heating rate of 1°C / min and calcined at 550°C for 6 hours to obtain ordered mesoporous alumina.

[0205] (4) Mix 0.6 mL of perfluorooctyl sulfonyl fluoride with a mixed solution of 2 mL of chloroform and 1 mL of isopropyl ether to obtain a perfluorooctyl sulfonyl fluoride solution;

[0206] (5) Under stirring conditions (temperature 0℃, speed 1000rpm), 1g of ordered mesoporous alumina was dissolved in 5mL of isopropyl ether and mixed evenly. Then, under stirring conditions (temperature 0℃, speed 1000rpm), perfluorooctane sulfonyl fluoride solution was slowly added dropwise (the addition rate was 5 drops / min, and the volume of each drop of perfluorooctane sulfonyl fluoride solution was 100μL). After the addition was completed, a mixture was obtained.

[0207] (6) The mixture was stirred at 500 rpm at 60°C for 0.5 h, then centrifuged (centrifugation speed was 6000 rpm, centrifugation time was 20 min), and the resulting solid was dried to obtain composite material D1.

[0208] Test Example 1

[0209] The specific surface area, pore volume, and pore size distribution of Al were determined using a BET adsorption analyzer. The results are as follows: Figure 1 and Figure 2 As shown. Figure 1 The N2 adsorption-desorption curves of composite material A1 show that the composite material exhibits an H4 type hysteresis loop in the relative pressure range of P / P0 = 0.6-1.0, and the isotherm belongs to the type IV adsorption equilibrium curve, indicating that the synthesized material has a mesoporous structure. Figure 2 The BJH pore size distribution diagram of composite material A1 shows that the mesopores in composite material A1 have a narrow pore size distribution, concentrated in the range of 8–11 nm, with an average pore size of 9.6 nm and a pore volume of 0.74 cm³. 3 / g, specific surface area 250m² 2 / g.

[0210] Test Example 2

[0211] The adsorption performance of perfluorooctane sulfonate (potassium) solution by A1-A10, B1, B2, and D1 was determined using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS). The test method was as follows: a 40 mg / L perfluorooctane sulfonate (potassium) solution was prepared, and 20 mg of A1-A10, B1, B2, and D1 were added respectively. The mixture was magnetically stirred and incubated in a 25°C water bath, with the pH adjusted to acidic. Timing was started at the addition of A1-A10, B1, B2, and D1, and samples were taken at 1, 2, 3, 4, 5, and 6 hours. The residual concentration of perfluorooctane sulfonate (potassium) in the solution was analyzed by HPLC-MS, and the removal efficiency of perfluorooctane sulfonate was calculated. The results are shown in Table 1.

[0212] Table 1

[0213]

[0214]

[0215] As shown in Table 1, after 6 hours of reaction, the PFOS removal rates of Examples 1-10 were 98.1%, 96.4%, 98.4%, 98.3%, 98.2%, 98.5%, 95.1%, 91.5%, 85.5%, and 96.5%, respectively. That is, the residual PFOS amounts after the reaction were 0.76 mg / L, 1.44 mg / L, 0.64 mg / L, 0.68 mg / L, 0.72 mg / L, 0.60 mg / L, 1.96 mg / L, 3.40 mg / L, 5.80 mg / L, and 1.40 mg / L, respectively. The PFOS removal rates of B1, B2, and D1 were 55.3%, 70.8%, and 59.4%, respectively, meaning that the residual PFOS amounts after the reaction were 17.88 mg / L, 11.68 mg / L, and 16.24 mg / L, respectively, which were far lower than the removal rates of the composite materials prepared in the examples.

[0216] Test Example 3

[0217] The adsorption performance of A1, A3, A6, B1, B2, and D1 on a mixed aqueous solution of perfluorooctane sulfonate (potassium) and alkyl glycoside was determined using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS). The test method was as follows: a mixed solution of perfluorooctane sulfonate (potassium) and alkyl glycoside (concentration of perfluorooctane sulfonate was 40 mg / L, and concentration of alkyl glycoside was 100 mg / L) was prepared. 20 mg of each of A1, A3, A6, B1, B2, and D1 were added, and the mixture was magnetically stirred and incubated in a 25°C water bath. The pH of the system was adjusted to acidic. Timing was started from the addition of A1, A3, A6, B1, B2, and D1. Samples were taken after 6 hours, and the residual concentration of perfluorooctane sulfonate in the solution was analyzed by HPLC-MS. The removal efficiency of perfluorooctane sulfonate was calculated, and the results are shown in Table 2.

[0218] Table 2

[0219]

[0220] As shown in Table 2, after 6 hours of reaction, the PFOS removal rates for Examples 1, 3, and 6 were 96.2%, 96.8%, and 97.0%, respectively, while the PFOS removal rates for B1, B2, and D1 were 44.1%, 58.9%, and 50.5%, respectively. Compared to the solution without alkyl glycosides, the addition of alkyl glycosides had little effect on the PFOS adsorption efficiency of the composite material.

[0221] Test Example 4

[0222] The adsorption performance of A1, A3, A6, B1, B2, and D1 on a mixed aqueous solution of perfluorooctane sulfonate (potassium) and sodium dodecyl sulfate was determined using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS). The test method was as follows: A mixed solution of perfluorooctane sulfonate (potassium) and sodium dodecyl sulfate (concentration of potassium perfluorooctane sulfonate was 40 mg / L, and concentration of sodium dodecyl sulfate was 100 mg / L) was prepared. 20 mg of each of A1, A3, A6, B1, B2, and D1 were added, and the mixture was magnetically stirred and incubated in a 25°C water bath. The pH of the system was adjusted to acidic. Timing was started from the addition of A1, A3, A6, B1, B2, and D1. Samples were taken after 6 hours, and the residual concentration of potassium perfluorooctane sulfonate in the solution was analyzed by HPLC-MS. The removal efficiency of potassium perfluorooctane sulfonate was calculated, and the results are shown in Table 3.

[0223] Table 3

[0224]

[0225] As shown in Table 3, after 6 hours of reaction, the PFOS removal rates of Examples 1, 3, and 6 were 80.1%, 82.4%, and 83.6%, respectively, while the PFOS removal rates of B1, B2, and D1 were 28.5%, 32.8%, and 35.6%, respectively, which were far lower than the removal rates of the composite materials prepared in the examples. Compared to the solution without sodium dodecyl sulfate, the adsorption rate of the composite material for PFOS decreased slightly after the addition of sodium dodecyl sulfate, but it still maintained a high adsorption rate.

[0226] Based on the experimental results of Test Example 3 and Test Example 4, it can be seen that the PFOS adsorption effect of the composite material of this application is not affected by anionic surfactants and nonionic surfactants.

[0227] Test Example 5

[0228] The adsorption properties of A1, A3, A6, B1, B2, and D1 on aqueous film-forming foam (AFCF) mixtures containing perfluorooctane sulfonate were determined using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS). The test method was as follows: AFCF agent (purchased from Jiangsu Jiangya Fire Protection Technology Co., Ltd.) and water were mixed at a weight ratio of 6:94 to prepare an AFCF mixture; a certain amount of perfluorooctane sulfonate was added to the AFCF mixture to obtain a mixture with a perfluorooctane sulfonate (potassium) concentration of 40 mg / L; then 20 mg of each of A1, A3, A6, B1, B2, and D1 were added, the mixture was magnetically stirred, and the system was in a 25°C water bath. The pH of the system was adjusted to acidic. Timing was started when A1, A3, A6, B1, B2 and D1 were added. Samples were taken after 6 hours of experimentation, and the residual concentration of perfluorooctane sulfonate (potassium) in the solution was analyzed by HPLC-MS. The removal efficiency of perfluorooctane sulfonate was calculated, and the results are shown in Table 4.

[0229] Table 4

[0230]

[0231] As shown in Table 4, after 6 hours of reaction, the PFOS removal rates of Examples 1, 3, and 6 were 96.0%, 96.4%, and 96.5%, respectively, while the PFOS removal rates of B1, B2, and D1 were 41.1%, 55.8%, and 49.5%, respectively. This indicates that the composite material can efficiently remove PFOS from fire-fighting water and has strong anti-interference ability.

[0232] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing a composite material for adsorbing perfluorooctane sulfonate and perfluorooctane sulfonic acid from fire-fighting wastewater, characterized in that, The preparation method includes the following steps: (1) Ordered mesoporous alumina is subjected to amination pretreatment to obtain ordered mesoporous alumina with amino surface modification; (2) The ordered mesoporous alumina with amino-modified surface is reacted with perfluorooctyl sulfonyl fluoride; In step (1), the specific process of amination pretreatment of ordered mesoporous alumina includes: S1: Mix ordered mesoporous alumina with toluene, then sonicate, then heat to 100-120℃, and then add 3-aminopropyltriethoxysilane for reflux reaction; S2: Centrifuge the material obtained after the reflux reaction in step S1, and wash and dry the resulting solid. The solid-liquid ratio of the ordered mesoporous alumina to the 3-aminopropyltriethoxysilane is 1 g: 0.4-0.8 mL; The solid-liquid ratio of the ordered mesoporous alumina with amino-modified surface to perfluorooctyl sulfonyl fluoride is 1 g: 0.4-2 mL; In step (1), the method for preparing the ordered mesoporous alumina includes: (a) Mix aluminum salt with template agent and then stir to obtain a mixture; (b) Add a pH adjuster to the mixture to adjust the pH of the system to 9-9.5, and then stir to obtain a gel mixture; (c) The gel mixture is sequentially filtered, washed, dried and calcined to obtain ordered mesoporous alumina; The weight ratio of the aluminum salt to the template agent is 1:1-2; the aluminum salt is selected from one or two of AlCl3•6H2O and Al(NO3)3; and the template agent is polyethylene glycol. The composite material has a mesopore size range of 6-13 nm, an average pore size of 8-9.8 nm, and a pore volume of 0.7-1 cm³. 3 / g, specific surface area is 230-320 m² 2 / g.

2. The preparation method according to claim 1, characterized in that, In step (a), the stirring conditions include a speed of 200-500 rpm and a time of 20-40 min.

3. The preparation method according to claim 1, characterized in that, In step (b), the pH adjuster is selected from one or more of ammonia, ammonium carbonate, and sodium hydroxide.

4. The preparation method according to claim 3, characterized in that, The pH adjuster is ammonia.

5. The preparation method according to claim 1, characterized in that, In step (b), the stirring conditions include: a speed of 500-800 rpm, a temperature of 40-70°C, and a time of 10-18 h.

6. The preparation method according to claim 1, characterized in that, In step (c), the drying conditions include a temperature of 40-80°C and a time of 10-24 hours.

7. The preparation method according to claim 6, characterized in that, The roasting conditions include a temperature of 500-600℃ and a time of 4-6 hours.

8. The preparation method according to claim 1, characterized in that, In step S1, the ultrasound duration is 5-10 minutes.

9. The preparation method according to claim 1 or 8, characterized in that, In step S1, the solid-liquid ratio of the ordered mesoporous alumina to toluene is 1g:40-80mL.

10. The preparation method according to claim 9, characterized in that, The reflux reaction conditions include: a temperature of 100-120℃ and a time of 16-24h.

11. The preparation method according to claim 1, characterized in that, In step (2), the specific process of reacting the amino-modified ordered mesoporous alumina with perfluorooctyl sulfonyl fluoride includes: (I) Mix perfluorooctyl sulfonyl fluoride, chloroform and isopropyl ether to obtain a perfluorooctyl sulfonyl fluoride solution; (II) Under stirring conditions, ordered mesoporous alumina with amino-modified surface is mixed with isopropyl ether, and then perfluorooctyl sulfonyl fluoride solution is added dropwise to obtain a mixed solution; (III) React the mixture, then centrifuge it, and dry the resulting solid.

12. The preparation method according to claim 11, characterized in that, In step (I), the volume ratio of the perfluorooctyl sulfonyl fluoride, chloroform and isopropyl ether is 0.6:1.8-2.2:0.9-1.

1.

13. The preparation method according to claim 11, characterized in that, In step (II), the stirring temperature is 0-10℃ and the stirring speed is 800-1200rpm.

14. The preparation method according to claim 13, characterized in that, The solid-liquid ratio of the amino-modified ordered mesoporous alumina to isopropyl ether is 1 g: 4-6 mL.

15. The preparation method according to claim 11, characterized in that, In step (III), the reaction conditions include a temperature of 50-70°C and a time of 0.5-1h.

16. The application of the composite material prepared by the preparation method according to any one of claims 1-15 in the adsorption of perfluorooctane sulfonate and perfluorooctane sulfonic acid in fire-fighting wastewater.

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