WO2020211186A1 - 一种亲水疏油海绵及其制备方法和应用 - Google Patents

一种亲水疏油海绵及其制备方法和应用 Download PDF

Info

Publication number
WO2020211186A1
WO2020211186A1 PCT/CN2019/091613 CN2019091613W WO2020211186A1 WO 2020211186 A1 WO2020211186 A1 WO 2020211186A1 CN 2019091613 W CN2019091613 W CN 2019091613W WO 2020211186 A1 WO2020211186 A1 WO 2020211186A1
Authority
WO
WIPO (PCT)
Prior art keywords
sponge
solution
nano
hydrophilic
silica
Prior art date
Application number
PCT/CN2019/091613
Other languages
English (en)
French (fr)
Inventor
何富安
何文旭
林博
李德豪
黎增田
陈婉怡
Original Assignee
广东石油化工学院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 广东石油化工学院 filed Critical 广东石油化工学院
Priority to US17/044,225 priority Critical patent/US11964220B2/en
Publication of WO2020211186A1 publication Critical patent/WO2020211186A1/zh

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/08—Thickening liquid suspensions by filtration
    • B01D17/10—Thickening liquid suspensions by filtration with stationary filtering elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C08J9/42—Impregnation with macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/038—Use of an inorganic compound to impregnate, bind or coat a foam, e.g. waterglass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08J2361/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08J2361/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • the invention relates to the technical field of functional material preparation, in particular to a hydrophilic and oleophobic sponge, and a preparation method and application thereof.
  • the purpose of the present invention is to provide a method for preparing a hydrophilic and oleophobic sponge.
  • the hydrophilic and oleophobic sponge prepared by the preparation method provided by the invention has good oil-water separation ability, thereby realizing high-efficiency filtration and separation of the oil-water mixture.
  • the present invention provides a preparation method of hydrophilic and oleophobic sponge, including the following steps:
  • the nanoparticle suspension is mixed with the modifier solution to obtain a modified solution;
  • the nanoparticle suspension includes a nano-iron tetroxide suspension with silica on the surface and/or an ethanol suspension of nano-silica;
  • the modifier solution is chitosan acetic acid aqueous solution and polyvinyl alcohol aqueous solution;
  • the sponge After the sponge is immersed in the modification solution, it is mixed with the glutaraldehyde aqueous solution for cross-linking reaction to obtain a hydrophilic and oleophobic sponge.
  • the volume ratio of the chitosan acetic acid aqueous solution and the polyvinyl alcohol aqueous solution is 1:2-15:1
  • the mass concentration of the chitosan acetic acid aqueous solution is 0.19% to 4.80%
  • the polyvinyl alcohol aqueous solution The mass concentration is 0.33% ⁇ 10.72%.
  • the nano ferroferric oxide suspension with silica coated on the surface is prepared by a preparation method including the following steps:
  • the tetraethoxysilane solution is mixed with the hydrophilic ferroferric oxide suspension, and the hydrolysis condensation reaction is performed to obtain the nano ferroferric oxide suspension with silica on the surface.
  • the ethanol suspension of nano-silica is prepared by a preparation method comprising the following steps:
  • the nano-silica particles are mixed with absolute ethanol to obtain an ethanol suspension of nano-silica.
  • the mass ratio of the nano ferroferric oxide particles in the silica-coated nano ferroferric oxide suspension to the modifier in the modifier solution is 0.5:2.7 ⁇ 1.5:0.5;
  • the mass ratio of the nano-silica particles in the ethanol suspension of nano-silica to the modifier in the modifier solution is 0.5:2.7 ⁇ 1.5:0.5.
  • the sponge includes melamine resin sponge and/or polyurethane sponge.
  • the mass ratio of the modifier in the modifier solution to the glutaraldehyde in the glutaraldehyde aqueous solution is 2.7 ⁇ 1.5:0.020 ⁇ 0.10.
  • the crosslinking reaction time is 10 to 14 hours.
  • the present invention also provides a hydrophilic and oleophobic sponge prepared by the preparation method described in the above technical solution, the hydrophilic and oleophobic sponge includes a sponge base and nanoparticles and modifiers loaded on the surface of the sponge base, and The nano particles include nano ferroferric oxide and/or nano silicon dioxide coated with silica on the surface, and the modifier is chitosan and polyvinyl alcohol.
  • the present invention also provides the application of the hydrophilic and oleophobic sponge described in the above technical scheme in the field of oil-water separation treatment of oil-water mixtures.
  • the present invention provides a method for preparing a hydrophilic and oleophobic sponge, which includes the following steps: mixing a nanoparticle suspension with a modifier solution to obtain a modified solution; the nanoparticle suspension includes a nanoparticle encapsulated with silica on the surface.
  • the nanoparticle suspension and the modifier solution are mixed and loaded on the surface of the sponge.
  • the hydrophilicity of the material is improved, and both polyvinyl alcohol and chitosan have affinity.
  • the data of the examples show that the hydrophilic and oleophobic sponge prepared by the preparation method provided by the present invention has an underwater contact angle of 150 degrees to 157 degrees with respect to methylene chloride, showing good hydrophilic and oleophobic ability, and can be simply passed through The gravity drive effectively separates the heavier water layer from the oil-water mixture of light oils such as lubricating oil, engine oil, pump oil, crude oil, gasoline, sunflower oil, etc.
  • Figure 1 is a diagram of the underwater contact angle of the hydrophilic and oleophobic sponges prepared in Examples 1-12 to methylene chloride;
  • Figure 2 is a water-oil separation effect diagram of the hydrophilic and oleophobic sponges prepared in Examples 1 to 6;
  • Figure 3 is a scanning electron microscope image of the hydrophilic and oleophobic sponge prepared in Example 7 under different magnification conditions, where a is a scanning electron microscope image of the hydrophilic and oleophobic sponge under 100 times conditions, and b is a hydrophilic and oleophobic sponge The scanning electron micrograph under the 500 times condition, c is the scanning electron microscope picture of the hydrophilic and oleophobic sponge under 3000 times, and d is the scanning electron microscope picture of the hydrophilic and oleophobic sponge under 10000 times.
  • the present invention provides a preparation method of hydrophilic and oleophobic sponge, including the following steps:
  • the nanoparticle suspension is mixed with the modifier solution to obtain a modified solution;
  • the nanoparticle suspension includes a nano-iron tetroxide suspension with silica on the surface and/or an ethanol suspension of nano-silica;
  • the modifier solution is chitosan acetic acid aqueous solution and polyvinyl alcohol aqueous solution;
  • the sponge After the sponge is immersed in the modification solution, it is mixed with the glutaraldehyde aqueous solution for cross-linking reaction to obtain a hydrophilic and oleophobic sponge.
  • the nanoparticle suspension is mixed with the modifier solution to obtain a modified solution;
  • the nanoparticle suspension includes a nano-iron tetroxide suspension with silica on the surface and/or an ethanol suspension of nano-silica;
  • the modifier solution is chitosan acetic acid aqueous solution and polyvinyl alcohol aqueous solution.
  • the silica-coated nano ferroferric oxide suspension is preferably prepared by a preparation method including the following steps:
  • the tetraethoxysilane solution is mixed with the hydrophilic ferroferric oxide suspension, and the hydrolysis condensation reaction is performed to obtain the nano ferroferric oxide suspension with silica on the surface.
  • the soluble + trivalent iron salt is preferably FeCl 3 ⁇ 6H 2 O
  • the soluble + divalent iron salt is preferably FeCl 2 ⁇ 4H 2 O
  • the alkaline solution is preferably a sodium hydroxide solution
  • the mass concentration of the sodium hydroxide solution is preferably 0.09% to 0.16%.
  • the specific sources of FeCl 3 ⁇ 6H 2 O, FeCl 2 ⁇ 4H 2 O and sodium hydroxide are not particularly limited, and commercial products well known in the art can be used.
  • the present invention preferably dissolves the soluble+trivalent iron salt and the soluble+divalent iron salt in water to obtain an aqueous solution of soluble+trivalent iron salt and soluble+divalent iron salt.
  • the dosage ratio of the soluble + trivalent iron salt, soluble + divalent iron salt and water is preferably 1.2984 ⁇ 3.246g:0.4776 ⁇ 1.194g:12 ⁇ 30mL, and more preferably 1.623g:0.597g: 30mL.
  • the temperature at which the soluble+trivalent iron salt and the soluble+divalent iron salt are dissolved in water is preferably 40-60°C.
  • the dissolution method and time are not particularly limited, and a conventional dissolution method in the field can be used, specifically, stirring for 20-30 minutes.
  • the present invention has no special limitation on the stirring rate, as long as the soluble+trivalent iron salt and the soluble+divalent iron salt can be dissolved in water.
  • the mass ratio of the soluble + trivalent iron salt, alkaline solution and trisodium citrate is preferably 1.2984 ⁇ 3.246:20.8 ⁇ 52:0.125 ⁇ 0.4, and more preferably 1.623:26:0.125.
  • the mixing sequence of the alkaline solution and trisodium citrate is not particularly limited, and any mixing sequence can be adopted.
  • the mixing method of the alkaline solution and trisodium citrate is not particularly limited, and the conventional mixing method in this field may be used.
  • the temperature of the co-precipitation reaction is preferably 80 to 90° C.
  • the time of the co-precipitation reaction is preferably 1 to 2 h.
  • the present invention preferably cools the co-precipitation reaction product to room temperature and performs magnetic separation, and washes it with deionized water for 5-6 times, and then adds deionized water to obtain a hydrophilic ferroferric oxide suspension.
  • the dosage ratio of the soluble + trivalent iron salt to deionized water is preferably 1.2984-3.246g: 40-100 mL, and more preferably 1.2984-3.246g: 50 mL.
  • the present invention preferably mixes the hydrophilic ferroferric oxide suspension with ammonia water at room temperature and under the protection of nitrogen, and then adds tetraethoxysilane for hydrolysis and condensation reaction to obtain Nano ferroferric oxide coated with silicon dioxide.
  • the amount ratio of ferroferric oxide to ammonia in the hydrophilic ferric oxide suspension is preferably 1 ⁇ 3g: 3 ⁇ 8mL, more preferably 1 ⁇ 3g: 3.2 ⁇ 4mL, The concentration of ammonia is preferably 25% by weight.
  • the present invention does not specifically limit the specific source of the ammonia water, and commercially available products well known in the art can be used.
  • the mixing method and time of the ammonia water and the hydrophilic ferroferric oxide suspension are not particularly limited, and a conventional mixing method in the field may be used, for example, stirring for 5 minutes.
  • the amount ratio of triiron tetroxide to tetraethoxysilane in the hydrophilic triiron tetroxide suspension is preferably 0.5 ⁇ 1.5g: 0.25 ⁇ 1mL, more preferably 0.5 ⁇ 1.5g: 0.25 ⁇ 0.5mL.
  • the modification reaction time is preferably 10 to 14 hours, more preferably 12 hours, and the temperature of the modification reaction is preferably room temperature.
  • the present invention preferably magnetically separates the modified reaction product and washes it with deionized water for 5 to 6 times, and then adds deionized water to obtain a nano ferroferric oxide suspension with silica on the surface.
  • the dosage ratio of nano ferroferric oxide to deionized water in the modified reaction product is preferably 0.5 to 1.5 g: 30 to 90 mL, and more preferably 0.5 to 1.5 g: 45 mL.
  • the ethanol suspension of nano-silica is preferably prepared by a preparation method including the following steps:
  • the nano-silica particles are mixed with absolute ethanol to obtain an ethanol suspension of nano-silica.
  • tetraethyl silicate and ammonia water are sequentially added in anhydrous ethanol in a nitrogen atmosphere to carry out hydrolysis and condensation reaction, followed by washing and drying to obtain nano silica particles.
  • the volume ratio of the absolute ethanol, tetraethyl silicate and ammonia is preferably 100:10:10.
  • the concentration of the ammonia water is preferably 25 wt%.
  • the specific sources of the absolute ethanol, tetraethyl silicate and ammonia are not particularly limited, and commercially available products well known in the art can be used.
  • the mixing is preferably carried out in a 250 mL flat bottom flask.
  • the present invention does not specifically limit the mixing method, as long as the conventional mixing method in the field is adopted, specifically, after the mouth of the flat-bottomed flask is stoppered with a glass stopper, the mixture is magnetically stirred for 1 hour.
  • the time of the hydrolysis condensation reaction is preferably 12h, and the temperature of the hydrolysis condensation reaction is preferably 20-40°C.
  • the present invention preferably performs washing with deionized water and centrifugal separation 4 to 5 times for the hydrolysis condensation reaction product in sequence. After the centrifugal separation is completed, in the present invention, it is preferred that the obtained washing is washed with ethanol and then separated into solid and liquid to obtain a solid.
  • the present invention After obtaining the solid, it is preferable in the present invention to dry the obtained solid.
  • the present invention does not specifically limit the specific drying method, as long as the conventional drying method in the art is adopted.
  • the drying temperature is preferably 60° C.
  • the drying time is preferably 12 hours.
  • the nano silica particles are mixed with absolute ethanol to obtain an ethanol suspension of nano silica particles.
  • the nano-silica particles are mixed with the absolute ethanol solution under stirring conditions to obtain an ethanol suspension solution of nano-silica.
  • the dosage ratio of the nano silica particles to the absolute ethanol solution is preferably 0.4 ⁇ 1.5g:20 ⁇ 75mL.
  • the stirring time is preferably 2h.
  • the dosage ratio of the chitosan to the acetic acid solution is preferably 0.3 to 1.5 g: 30 to 150 mL, and more preferably 0.35 to 0.6 g: 35 to 60 mL.
  • the mass concentration of the acetic acid solution is preferably 1 to 2 wt%. The present invention does not specifically limit the specific sources of the chitosan and acetic acid solution, and commercially available products well known in the art can be used.
  • the dosage ratio of the polyvinyl alcohol to the deionized water is preferably 0.2 ⁇ 1.2g: 10 ⁇ 60mL, more preferably 0.32 ⁇ 0.6g:9.6 ⁇ 18mL.
  • the present invention does not specifically limit the specific source of the polyvinyl alcohol, and commercially available products well known in the art can be used.
  • the present invention does not have special restrictions on the mixing method, as long as the conventional mixing method in the field can be used, such as stirring.
  • the stirring time is preferably 2h, and the stirring temperature is preferably 45-50°C.
  • the mixing of the nanoparticle suspension and the modification solution is preferably carried out in a round bottom flask.
  • the mixing sequence of the nanoparticle suspension and the modification solution is preferably to first mix the nanoparticle suspension with the chitosan acetic acid aqueous solution, and then mix with the polyvinyl alcohol aqueous solution.
  • the nano ferroferric oxide particles in the silica-coated nano ferroferric oxide suspension when the silica-coated nano ferroferric oxide suspension and the modified solution are mixed, the nano ferroferric oxide particles in the silica-coated nano ferroferric oxide suspension
  • the mass ratio of the modifier to the modifier in the modifier solution is preferably 0.5:2.7 ⁇ 1.5:0.5; when the ethanol suspension of nano silica and the modification solution are mixed, the ethanol suspension of nano silica
  • the mass ratio of the nano silica particles in the modifier solution to the modifier in the modifier solution is preferably 0.5:2.7 ⁇ 1.5:0.5; when the surface is coated with silica nano-ferric oxide suspension, nano-silica
  • the mass ratio of the nano ferroferric oxide particles and nano dioxide particles in the suspension mixture to the modifier in the modifier solution is preferably 0.5:2.7 ⁇ 1.5: 0.5.
  • the volume ratio of the chitosan acetic acid aqueous solution and the polyvinyl alcohol aqueous solution is preferably 1:2-15:1, and the concentration of the chitosan acetic acid aqueous solution is preferably 0.19% to 4.80%.
  • the concentration of the aqueous vinyl alcohol solution is preferably 0.33% to 10.72%.
  • the present invention does not have any special restrictions on the mixing mode, as long as the conventional mixing mode in the field is adopted, specifically, stirring.
  • the present invention immerses the sponge in the modified solution and mixes it with the glutaraldehyde aqueous solution for cross-linking reaction to obtain a hydrophilic and oleophobic sponge.
  • the sponge is preferably a melamine resin sponge and/or a polyurethane sponge; the volume of the sponge is preferably 3cm ⁇ 2cm ⁇ 0.5cm ⁇ 4cm ⁇ 3cm ⁇ 1cm.
  • the present invention does not specifically limit the specific source of the sponge, and commercially available products well known in the art can be used.
  • preferably 4-6 sponges are immersed in the modified nanoparticle suspension.
  • the mass concentration of the glutaraldehyde aqueous solution is preferably 25%-50%, and more preferably 50%.
  • the mass ratio of the modifier in the modifier solution to the glutaraldehyde in the glutaraldehyde aqueous solution is preferably 2.7 ⁇ 1.5:0.020 ⁇ 0.10, more preferably 2.7 ⁇ 1.5:0.05 ⁇ 0.075.
  • the present invention does not have any special restrictions on the mixing method, as long as the conventional mixing method in the field is used, for example, stirring; the stirring time is preferably 10-20 min.
  • the present invention has no special limitation on the speed of the stirring.
  • the stirring speed well known to those skilled in the art may be used.
  • the time of the crosslinking reaction is preferably 10 to 14 hours, and more preferably 12 hours.
  • the present invention preferably drying the crosslinking reaction product to obtain a hydrophilic and oleophobic sponge.
  • the drying is preferably performed under vacuum conditions; the drying temperature is preferably 50-60° C., and the drying time is preferably 20-24 hours.
  • the present invention also provides a hydrophilic and oleophobic sponge prepared by the preparation method described in the above technical solution, the hydrophilic and oleophobic sponge includes a sponge base and nanoparticles and modifiers loaded on the surface of the sponge base, and The nano particles include nano ferroferric oxide and/or nano silicon dioxide coated with silica on the surface, and the modifier is chitosan and polyvinyl alcohol.
  • the present invention also provides the application of the hydrophilic and oleophobic sponge described in the above technical scheme in the field of oil-water separation treatment of oil-water mixtures.
  • the application preferably includes the following steps:
  • the hydrophilic and oleophobic sponge After the hydrophilic and oleophobic sponge is soaked and saturated in water, it is taken out and stuffed into the neck of the funnel. After the oil is poured, the water is poured in to achieve water and oil separation.
  • hydrophilic and oleophobic sponge provided by the present invention and its preparation method and application will be described in detail with reference to the examples, but they cannot be understood as limiting the protection scope of the present invention.
  • the underwater contact angle of the obtained modified sponge to methylene chloride was 157 degrees, as shown in Fig. 1.
  • Fig. 1 After soaking the modified sponge with water, plug it into the neck of the funnel. After adding lubricating oil and water sequentially, the mixture of water and lubricating oil can be effectively separated under the action of gravity. The separation process is shown in Figure 2. .
  • the underwater contact angle of the obtained modified sponge to methylene chloride was 154 degrees, as shown in Fig. 1. After soaking the resulting modified sponge with water, plug it into the neck of the funnel. After adding oil and water sequentially, the mixture of water and oil can be effectively separated under the action of gravity. The separation process is shown in Figure 2.
  • the underwater contact angle of the obtained modified sponge to methylene chloride was 154 degrees, as shown in Fig. 1.
  • Fig. 1 After soaking the obtained modified sponge with water, plug it into the neck of the funnel. After adding pump oil and water in sequence, the mixture of water and pump oil can be effectively separated under the action of gravity. The separation process is shown in Figure 2. .
  • the underwater contact angle of the obtained modified sponge to dichloromethane is 154 degrees.
  • the modified sponge is soaked in water and stuffed in the neck of the funnel. After adding crude oil and water sequentially, it can Under the action of gravity, the mixture of water and crude oil can be effectively separated. The separation process is shown in Figure 2.
  • the underwater contact angle of the modified sponge to methylene chloride was 156 degrees, as shown in Figure 1. After soaking the modified sponge with water, plug it into the neck of the funnel. After adding gasoline and water in sequence, the mixture of water and gasoline can be effectively separated under the action of gravity. The separation process is shown in Figure 2.
  • the underwater contact angle of the hydrophilic and oleophobic sponge to methylene chloride was 156 degrees, as shown in Figure 1. After soaking the obtained hydrophilic and oleophobic sponge with water, it is stuffed in the neck of the funnel. After adding sunflower oil and water in sequence, the mixture of water and sunflower oil can be effectively separated under the action of gravity. The separation process is as follows As shown in Figure 2.
  • FIG. 2 is a water-oil separation effect diagram of the hydrophilic and oleophobic sponges prepared in Examples 1 to 6. It can be seen from Figure 2 that the hydrophilic and oleophobic sponge prepared by the present invention has good hydrophilic and oleophobic capacity, and can simply drive an effective filter pump oil by gravity (the hydrophilic and oleophobic sponge prepared in Example 1 Oil sponge), filter engine oil (the hydrophilic and oleophobic sponge prepared in Example 2), filtered sunflower oil (the hydrophilic and oleophobic sponge prepared in Example 3), filtered gasoline (the hydrophilic and oleophobic sponge prepared in Example 4) Hydrophilic oleophobic sponge), filtered lubricating oil (hydrophilic oleophobic sponge prepared in Example 5), filtered crude oil (hydrophilic oleophobic sponge prepared in Example 6) and other light oils. The heavy water layer is effectively separated.
  • the hydrophilic and oleophobic sponge prepared by the present invention has
  • the SEM results of the hydrophilic and oleophobic sponge obtained are shown in Figure 3, where a is the SEM image of the hydrophilic and oleophobic sponge under 100 times the condition, and b is the SEM image of the hydrophilic and oleophobic sponge under 500 times the condition , C is the scanning electron microscope image of the hydrophilic and oleophobic sponge under 3000 times, and d is the scanning electron microscope image of the hydrophilic and oleophobic sponge under 10000 times.
  • the underwater contact angle to methylene chloride is 151 degrees.
  • Figure 1 It can be seen from Figure 3 that the nano silica particles are uniformly supported on the surface of the sponge skeleton.
  • the underwater contact angle of the obtained hydrophilic and oleophobic sponge to methylene chloride was 152 degrees, as shown in Figure 1 for details.
  • the underwater contact angle of the obtained hydrophilic and oleophobic sponge to methylene chloride was 150 degrees, as shown in Figure 1 for details.
  • the underwater contact angle of the obtained hydrophilic and oleophobic sponge to methylene chloride was 152 degrees, as shown in Figure 1 for details.
  • Figure 1 is a diagram showing the underwater contact angle of the hydrophilic and oleophobic sponge prepared in Examples 1-12 to methylene chloride. It can be seen from Figure 1 that the hydrophilic and oleophobic sponge prepared in the present invention has a positive effect on dichloromethane.
  • the underwater contact angle is 150 degrees to 157 degrees, showing good hydrophilic and oleophobic ability.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Cosmetics (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Silicon Compounds (AREA)

Abstract

一种亲水疏油海绵及其制备方法和应用，属于功能材料制备技术领域。通过将纳米粒子悬浮液与改性剂溶液混合，得到改性溶液；所述纳米粒子悬浮液包括表面包裹二氧化硅的纳米四氧化三铁悬浮液和/或纳米二氧化硅的乙醇悬浮液；所述改性剂溶液为壳聚糖醋酸水溶液和聚乙烯醇水溶液；将海绵浸入所述的改性溶液中后，与戊二醛水溶液混合进行交联反应，得到亲水疏油海绵，使海绵具有良好的油水分离性能，可单纯地通过重力驱动有效的从润滑油、机油、泵油、原油、汽油、葵花籽油等轻质油的油水混合物中分离出较重的水层。上述方法制备得到的亲水疏油海绵在油水分离中具有良好的应用前景。

Description

一种亲水疏油海绵及其制备方法和应用 技术领域
本发明涉及功能材料制备技术领域，尤其涉及一种亲水疏油海绵及其制备方法和应用。
 背景技术
目前，大量油污的不慎泄漏与任意排放已对人类的生存环境造与自身健康造成严重威胁。人们一直致力于寻求一种省时、省力、易操作、低成本的除油方法。近年的研究表明亲油疏水材料是一个较佳的选择。特别地，疏松多孔的亲油疏水海绵材料能在阻挡水渗透的同时对油污以及有机溶剂具有良好的吸附与透过能力，能够仅仅在重力作用下即可把较重的油层（有机溶剂层）与较轻的水层进行分离，从而节省大量的时间、人力、物力与成本。
但是，大多数油污的密度都低于水，水会沉于底部而油污却会浮于水面，且海绵的亲油属性也容易导致长时间使用后的有机污染物堵孔现象，因而降低了亲油疏水海绵的油水分离能力。
 技术问题
鉴于此，本发明的目的在于提供一种亲水疏油海绵的制备方法。本发明提供的制备方法制得的亲水疏油海绵具有良好的油水分离能力，从而实现油水混合物的高效过滤分离。
 技术解决方案
为了实现上述发明目的，本发明提供以下技术方案：
本发明提供了一种亲水疏油海绵的制备方法，包括以下步骤：
将纳米粒子悬浮液与改性剂溶液混合，得到改性溶液；所述纳米粒子悬浮液包括表面包裹二氧化硅的纳米四氧化三铁悬浮液和/或纳米二氧化硅的乙醇悬浮液；所述改性剂溶液为壳聚糖醋酸水溶液和聚乙烯醇水溶液；
将海绵浸入所述的改性溶液中后，与戊二醛水溶液混合进行交联反应，得到亲水疏油海绵。
优选地，所述壳聚糖醋酸水溶液和聚乙烯醇水溶液的体积比为1:2~15:1，所述壳聚糖醋酸水溶液的质量浓度为0.19%~4.80%，所述聚乙烯醇水溶液的质量浓度为0.33%~10.72%。
优选地，所述表面包裹二氧化硅的纳米四氧化三铁悬浮液由包括如下步骤的制备方法制得：
在氮气气氛中，在可溶性+3价铁盐和可溶性+2价铁盐的水溶液中，依次加入碱性溶液、柠檬酸三钠进行共沉淀反应，得到亲水性四氧化三铁悬浮液；
将四乙氧基硅烷溶液与所述亲水性四氧化三铁悬浮液混合，进行水解缩合反应，得到表面包裹二氧化硅的纳米四氧化三铁悬浮液。
优选地，所述纳米二氧化硅的乙醇悬浮液由包括如下步骤的制备方法制得：
将硅酸四乙酯、氨水依次加入无水乙醇中混合，进行水解缩合反应，依次经洗涤和干燥，得到纳米二氧化硅颗粒；
将所述纳米二氧化硅颗粒与无水乙醇混合，得到纳米二氧化硅的乙醇悬浮液。
优选地，所述表面包裹二氧化硅的纳米四氧化三铁悬浮液中的纳米四氧化三铁粒子与改性剂溶液中的改性剂的质量比为0.5:2.7~1.5:0.5；所述纳米二氧化硅的乙醇悬浮液中的纳米二氧化硅粒子与改性剂溶液中的改性剂的质量比为0.5:2.7~1.5:0.5。
优选地，所述海绵包括密胺树脂海绵和/或聚氨酯海绵。
优选地，所述改性剂溶液中改性剂与戊二醛水溶液中戊二醛的质量比为2.7~1.5：0.020~0.10。
优选地，所述交联反应时间为10~14h。
本发明还提供了上述技术方案所述的制备方法制得的亲水疏油海绵，所述亲水疏油海绵包括海绵基底和负载在所述海绵基底表面上的纳米粒子与改性剂，所述纳米粒子包括表面包裹二氧化硅的纳米四氧化三铁和/或纳米二氧化硅，所述改性剂为壳聚糖和聚乙烯醇。
本发明还提供了上述技术方案所述的亲水疏油海绵在油水混合物的油水分离处理领域中的应用。
本发明提供了一种亲水疏油海绵的制备方法，包括以下步骤：将纳米粒子悬浮液与改性剂溶液混合，得到改性溶液；所述纳米粒子悬浮液包括表面包裹二氧化硅的纳米四氧化三铁悬浮液和/或纳米二氧化硅的乙醇悬浮液；所述改性剂溶液为壳聚糖醋酸水溶液和聚乙烯醇水溶液；将海绵浸入所述的改性溶液中后，与戊二醛水溶液混合进行交联反应，得到亲水疏油海绵。在本发明中，将纳米粒子悬浮液与改性剂溶液混合后负载于海绵表面，通过增加海绵表面的微观粗糙度，改善材料的亲水性，并利用聚乙烯醇和壳聚糖中均具有亲水疏油的官能团的特性，与戊二醛水溶液混合，通过戊二醛水溶液与壳聚糖和聚乙烯醇发生交联反应，使海绵具有良好的水油分离性能。实施例的数据表明，本发明提供的制备方法制得的亲水疏油海绵对二氯甲烷的水下接触角为150度~157度，显示出良好的亲水疏油能力，可单纯地通过重力驱动有效的从润滑油、机油、泵油、原油、汽油、葵花籽油等轻质油的油水混合物中分离出较重的水层。
 有益效果
。
 附图说明
下面结合附图和具体实施方式对本发明作进一步详细的说明。
图1为实施例1~12制得的亲水疏油海绵对二氯甲烷的水下接触角图；
图2为实施例1~6制得的亲水疏油海绵的水油分离效果图；
图3为实施例7制得的亲水疏油海绵在不同放大倍数条件下的扫描电镜图，其中a为亲水疏油海绵在100倍条件下的扫描电镜图，b为亲水疏油海绵在500倍条件下的扫描电镜图，c为亲水疏油海绵在3000倍条件下的扫描电镜图，d为亲水疏油海绵在10000倍条件下的扫描电镜图。
 本发明的实施方式
本发明提供了一种亲水疏油海绵的制备方法，包括以下步骤：
将纳米粒子悬浮液与改性剂溶液混合，得到改性溶液；所述纳米粒子悬浮液包括表面包裹二氧化硅的纳米四氧化三铁悬浮液和/或纳米二氧化硅的乙醇悬浮液；所述改性剂溶液为壳聚糖醋酸水溶液和聚乙烯醇水溶液；
将海绵浸入所述的改性溶液中后，与戊二醛水溶液混合进行交联反应，得到亲水疏油海绵。
将纳米粒子悬浮液与改性剂溶液混合，得到改性溶液；所述纳米粒子悬浮液包括表面包裹二氧化硅的纳米四氧化三铁悬浮液和/或纳米二氧化硅的乙醇悬浮液；所述改性剂溶液为壳聚糖醋酸水溶液和聚乙烯醇水溶液。
在本发明中，所述表面包裹二氧化硅的纳米四氧化三铁悬浮液优选由包括如下步骤的制备方法制得：
在氮气气氛中，在可溶性+3价铁盐和可溶性+2价铁盐的水溶液中，依次加入碱性溶液、柠檬酸三钠进行共沉淀反应反应，得到亲水性四氧化三铁悬浮液；
将四乙氧基硅烷溶液与所述亲水性四氧化三铁悬浮液混合，进行水解缩合反应，得到表面包裹二氧化硅的纳米四氧化三铁悬浮液。
本发明在氮气气氛中，在可溶性+3价铁盐和可溶性+2价铁盐的水溶液中，依次加入碱性溶液、柠檬酸三钠进行共沉淀反应，得到亲水性四氧化三铁悬浮液。在本发明中，所述可溶性+3价铁盐优选为FeCl 3∙6H 2O，所述可溶性+2价铁盐优选为FeCl 2∙4H 2O。在本发明中，所述碱性溶液优选为氢氧化钠溶液，所述氢氧化钠溶液的质量浓度优选为0.09%~0.16%。本发明对所述FeCl 3∙6H 2O、FeCl 2∙4H 2O和氢氧化钠的具体来源没有特殊的限定，采用本领域所熟知的市售产品均可。
本发明优选将所述可溶性+3价铁盐和可溶性+2价铁盐溶于水中，得到可溶性+3价铁盐和可溶性+2价铁盐的水溶液。在本发明中，所述可溶性+3价铁盐、可溶性+2价铁盐和水的用量比优选为1.2984~3.246g:0.4776~1.194g:12~30mL，进一步优选为1.623g:0.597g:30mL。
在本发明中，所述可溶性+3价铁盐和可溶性+2价铁盐溶于水中的温度优选为40~60℃。本发明对所述溶解的方式和时间没有特殊限定，采用本领域常规的溶解方式即可，具体的如，搅拌20~30min。本发明对所述搅拌的速率没有特殊的限定，能够满足可溶性+3价铁盐和可溶性+2价铁盐溶于水中即可。
在本发明中，所述可溶性+3价铁盐、碱性溶液与柠檬酸三钠的质量比优选为1.2984~3.246:20.8~52:0.125~0.4，进一步优选为1.623:26:0.125。
本发明对所述碱性溶液与柠檬酸三钠的混合顺序没有特殊的限定，采用任意混合顺序均可。本发明对所述碱性溶液与柠檬酸三钠的混合方式没有特殊的限定，采用本领域常规混合方式即可。
在本发明中，所述共沉淀反应的温度优选为80~90℃，共沉淀反应的时间优选为1~2h。
共沉淀反应结束后，本发明优选将共沉淀反应产物自然冷却至室温后进行磁分离，并用去离子水洗涤5~6次，然后加入去离子水得到亲水性四氧化三铁悬浮液。在本发明中，所述可溶性+3价铁盐与去离子水的用量比优选为1.2984~3.246g:40~100mL，进一步优选为1.2984~3.246g:50mL。
得到亲水性四氧化三铁悬浮液后，本发明优选在室温、氮气保护下，将所述亲水性四氧化三铁悬浮液与氨水混合后加入四乙氧基硅烷进行水解缩合反应，得到表面包裹二氧化硅的纳米四氧化三铁。在本发明中，所述亲水性四氧化三铁悬浮液中的四氧化三铁与氨水的用量比优选为1~3g：3~8mL，进一步优选为1~3g：3.2~4mL，所述氨水的浓度优选为25wt%。本发明对所述氨水的具体来源没有特殊的限定，采用本领域所熟知的市售产品均可。本发明对所述氨水与亲水性四氧化三铁悬浮液的混合方式和时间没有特殊限定，采用本领域常规的混合方式即可，具体的如，搅拌5min。
在本发明中，所述亲水性四氧化三铁悬浮液中的四氧化三铁与四乙氧基硅烷的用量比优选为0.5~1.5g：0.25~1mL，进一步优选为0.5~1.5g：0.25~0.5mL。
在本发明中，所述改性反应时间优选为10~14h，进一步优选为12h，所述改性反应的温度优选为室温。
改性反应结束后，本发明优选将改性反应产物进行磁分离，并用去离子水洗涤5~6次，然后加入去离子水得到表面包裹二氧化硅的纳米四氧化三铁悬浮液。在本发明中，所述改性反应产物中的纳米四氧化三铁与去离子水的用量比优选为0.5~1.5g：30~90mL，进一步优选为0.5~1.5g：45mL。
在本发明中，所述纳米二氧化硅的乙醇悬浮液优选由包括如下步骤的制备方法制得：
将硅酸四乙酯、氨水依次加入无水乙醇中混合，进行水解缩合反应，依次经洗涤和干燥，得到纳米二氧化硅颗粒；
将所述纳米二氧化硅颗粒与无水乙醇混合，得到纳米二氧化硅的乙醇悬浮液。
本发明在氮气气氛中，在无水乙醇中，依次加入硅酸四乙酯和氨水进行水解缩合反应后，依次经洗涤和干燥，得到纳米二氧化硅颗粒。在本发明中，所述无水乙醇、硅酸四乙酯与氨水的体积比优选为100：10：10。在本发明中，所述氨水的浓度优选为25wt%。本发明对所述无水乙醇、硅酸四乙酯和氨水的具体来源没有特殊的限定，采用本领域所熟知的市售产品均可。
在本发明中，所述混合优选在250mL平底烧瓶中进行。本发明对所述混合的方式没有特殊的限定，采用本领域常规的混合方式即可，具体的如，用玻璃塞塞住平底烧瓶瓶口后，磁力搅拌1h。
在本发明中，所述水解缩合反应的时间优选为12h，所述水解缩合反应的温度优选为20~40℃。
得到水解缩合反应产物后，本发明优选将所述水解缩合反应产物依次进行去离子水洗涤和离心分离4~5次。离心分离完成后，本发明优选将所得洗涤物进行乙醇洗涤后固液分离，得到固体。
得到固体后，本发明优选将所得固体进行干燥。本发明对所述干燥的具体方式没有特殊限定，采用本领域常规干燥方式即可，具体的，所述干燥的温度优选为60℃，干燥的时间优选为12h。
得到干燥的纳米二氧化硅颗粒后，将所述纳米二氧化硅颗粒与无水乙醇混合，得到纳米二氧化硅的乙醇悬浮液。
本发明优选在搅拌条件下，将纳米二氧化硅颗粒与无水乙醇溶液混合，得到纳米二氧化硅的乙醇悬浮溶液。在本发明中，所述纳米二氧化硅颗粒与无水乙醇溶液的用量比优选为0.4~1.5g：20~75mL。
在本发明中，所述搅拌的时间优选为2h。
本发明优选将壳聚糖加入到醋酸溶液中，在室温下搅拌4h，得到壳聚糖醋酸水溶液。在本发明中，所述壳聚糖与醋酸溶液的用量比优选为0.3~1.5g：30~150mL，进一步优选为0.35~0.6g：35~60mL。在本发明中，所述醋酸溶液的质量浓度优选为1~2wt%。本发明对所述壳聚糖和醋酸溶液的具体来源没有特殊的限定，采用本领域所熟知的市售产品均可。
本发明优选将聚乙烯醇加入到去离子水中混合，得到聚乙烯醇水溶液。在本发明中，所述聚乙烯醇与去离子水的用量比优选为0.2~1.2g：10~60mL，进一步优选为0.32~0.6g：9.6~18mL。本发明对所述聚乙烯醇的具体来源没有特殊的限定，采用本领域所熟知的市售产品均可。本发明对所述的混合方式没有特殊的限定，采用本领域常规的混合方式即可，具体的如搅拌。在本发明中，所述搅拌的时间优选为2h，所述搅拌的温度优选为45~50℃。
在本发明中，所述纳米粒子悬浮液和改性溶液的混合优选在圆底烧瓶中进行。在本发明中，所述纳米粒子悬浮液和改性溶液的混合顺序优选为先将纳米粒子悬浮液与壳聚糖醋酸水溶液混合，再与聚乙烯醇水溶液混合。在本发明中，当表面包裹二氧化硅的纳米四氧化三铁悬浮液和改性溶液的混合时，所述表面包裹二氧化硅的纳米四氧化三铁悬浮液中的纳米四氧化三铁粒子与改性剂溶液中的改性剂的质量比优选为0.5:2.7~1.5:0.5；当纳米二氧化硅的乙醇悬浮液和改性溶液的混合时，所述纳米二氧化硅的乙醇悬浮液中的纳米二氧化硅粒子与改性剂溶液中的改性剂的质量比优选为0.5:2.7~1.5:0.5；当表面包裹二氧化硅的纳米四氧化三铁悬浮液、纳米二氧化硅的乙醇悬浮液和改性溶液的混合时，所述悬浮混合液中的纳米四氧化三铁粒子和纳米二氧化粒子与改性剂溶液中的改性剂的质量比优选为0.5:2.7~1.5:0.5。
在本发明中，所述壳聚糖醋酸水溶液和聚乙烯醇水溶液的体积比优选为1:2~15:1，所述壳聚糖醋酸水溶液的浓度优选为0.19%~4.80%，所述聚乙烯醇水溶液的浓度优选为0.33%~10.72%。本发明对所述混合的方式没有特殊限定，采用本领域常规混合方式即可，具体的如，搅拌。
得到改性溶液后，本发明将海绵浸入所述改性溶液中后与戊二醛水溶液混合进行交联反应，得到亲水疏油海绵。在本发明中，所述海绵优选为密胺树脂海绵和/或聚氨酯海绵；所述海绵的体积优选为3cm×2cm×0.5cm~4cm×3cm×1cm。本发明对所述海绵的具体来源没有特殊的限定，采用本领域所熟知的市售产品均可。在本发明中，优选将4~6块海绵浸入所述改性纳米粒子悬浮液中。
在本发明中，所述戊二醛水溶液的质量浓度优选为25%~50%，进一步优选为50%。
在本发明中，所述改性剂溶液中改性剂与戊二醛水溶液中戊二醛的质量比优选为2.7~1.5：0.020~0.10，进一步优选为2.7~1.5：0.05~0.075。
本发明对所述混合的方式没有特殊限定，采用本领域常规混合方式即可，具体的如，搅拌；所述搅拌时间优选为10~20min，本发明对所述搅拌的转速没有特殊的限定，采用本领域技术人员熟知的搅拌速度即可。
在本发明中，所述交联反应的时间优选为10~14h，进一步优选为12h。
交联反应完成后，本发明优选将交联反应产物进行干燥，得到亲水疏油海绵。在本发明中，所述干燥优选在真空条件下进行；所述干燥的温度优选为50~60℃，所述干燥的时间优选为20~24h。
本发明还提供了上述技术方案所述的制备方法制得的亲水疏油海绵，所述亲水疏油海绵包括海绵基底和负载在所述海绵基底表面上的纳米粒子与改性剂，所述纳米粒子包括表面包裹二氧化硅的纳米四氧化三铁和/或纳米二氧化硅，所述改性剂为壳聚糖和聚乙烯醇。
本发明还提供了上述技术方案所述的亲水疏油海绵在油水混合物的油水分离处理领域中的应用。
在本发明中，所述应用优选包括如下步骤：
将亲水疏油海绵放入水中浸泡饱和后，取出并塞入漏斗颈部，倒入油后，再倒入水，实现水油分离。
下面结合实施例对本发明提供的亲水疏油海绵及其制备方法和应用进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。
实施例 1
（1）将1.623g FeCl 3∙6H 2O与0.597g FeCl 2∙4H 2O溶于30mL去离子水中，在60℃，氮气保护下，搅拌30min；然后加入26g氢氧化钠水溶液（氢氧化钠1g、水25g），再加入柠檬酸三钠0.125g，温度升至80℃，搅拌反应1h；反应结束后待冷却至室温，得到亲水性四氧化三铁粒子后，进行磁分离并用去离子水洗涤6次，然后添加50mL的去离子水配成亲水性四氧化三铁粒子悬浮液；向上述悬浮液中加入4mL氨水（浓度为25wt%）后搅拌5min，再加入0.25mL四乙氧基硅烷，然后室温下氮气保护搅拌反应12h；反应结束得到表面包裹二氧化硅的四氧化三铁粒子进行磁分离并用去离子水洗涤6次，然后添加去离子水配成45mL表面包裹二氧化硅的四氧化三铁悬浮液。
(2)称取0.6g壳聚糖溶于浓度为1wt%醋酸溶液中，在室温下搅拌4h，得到60mL壳聚糖醋酸水溶液。
(3)称取0.6g聚乙烯醇并加入到去离子水中，在50℃下搅拌2h，得到18mL聚乙烯醇水溶液。
(4)将45mL表面包裹二氧化硅的四氧化三铁悬浮液与60mL壳聚糖醋酸水溶液加于圆底烧瓶中，搅拌3min，然后加入18mL聚乙烯醇水溶液，搅拌5min，再将6块密胺海绵（4cm×2.5cm×0.7cm）浸泡于上述混合溶液中，搅拌15min后，加入0.075mL戊二醛水溶液，搅拌12h，最后从混合溶液中取出海绵，并直接在60℃下真空干燥24h，得到亲水疏油海绵。
所得改性海绵对二氯甲烷的水下接触角为157度，具体如图1所示。将所得改性海绵用水浸泡后，塞于漏斗的颈部，在依次加入润滑油和水后，能在重力作用下能对水与润滑油的混合物进行有效分离，其分离过程如图2所示。
实施例 2
(1)同实施1例步骤1。
(2)称取0.4g壳聚糖溶于浓度为1wt%醋酸溶液中，在室温下搅拌4h，得到40mL壳聚糖醋酸水溶液。
(3)称取0.4g聚乙烯醇并加入到去离子水中，50℃下搅拌2h，得到12mL聚乙烯醇水溶液。
(4)将45mL表面包裹二氧化硅的四氧化三铁悬浮液与40mL壳聚糖醋酸水溶液加于圆底烧瓶中，搅拌3min，然后加入12mL聚乙烯醇水溶液，搅拌5min，再将6块密胺海绵（4cm×2.5cm×0.7cm）浸泡于上述混合溶液中，搅拌15min后，加入0.075mL戊二醛水溶液，搅拌12h，最后从混合溶液中取出海绵并直接在60℃下真空干燥24h，得到亲水疏油海绵。所得改性海绵对二氯甲烷的水下接触角为154度，具体如图1所示。将所得改性海绵用水浸泡后，塞于漏斗的颈部，在依次加入机油和水后，能在重力作用下能对水与机油的混合物进行有效分离，其分离过程如图2所示。
实施例 3
（1）同实施1例步骤（1）。
（2）同实施1例步骤（2）。
（3）称取0.72g聚乙烯醇并加入到去离子水中，在50℃下搅拌2h，得到21.6mL聚乙烯醇水溶液。
（4）将45mL表面包裹二氧化硅的四氧化三铁悬浮液与60mL壳聚糖醋酸水溶液加于圆底烧瓶中，搅拌3min，然后加入21.6mL聚乙烯醇水溶液，搅拌5min，再将6块密胺海绵（4cm×2.5cm×0.7cm）浸泡于上述混合溶液中，搅拌15min后，加入0.075mL戊二醛水溶液，搅拌12h，最后从混合溶液中取出海绵，并直接在60℃下真空干燥24h，得到亲水疏油海绵。
所得改性海绵对二氯甲烷的水下接触角为154度，具体如图1所示。将所得改性海绵用水浸泡后，塞于漏斗的颈部，在依次加入泵油和水后，能在重力作用下能对水与泵油的混合物进行有效分离，其分离过程如图2所示。
实施例 4
（1）同实施1例步骤（1）。
（2）同实施2例步骤（2）。
（3）称取0.48g聚乙烯醇并加入到去离子水中，在50℃下搅拌2h，得到14.4mL聚乙烯醇水溶液。
（4）将45mL表面包裹二氧化硅的四氧化三铁悬浮液与40mL壳聚糖醋酸水溶液加于圆底烧瓶中，搅拌3min，然后加入14.4mL聚乙烯醇水溶液，搅拌5min，再将6块密胺海绵（4cm×2.5cm×0.7cm）浸泡于上述混合溶液中，搅拌15min后，加入0.075mL戊二醛水溶液，搅拌12h，最后从混合溶液中取出海绵，并直接在60℃下真空干燥24h，得到亲水疏油海绵。
所得改性海绵对二氯甲烷的水下接触角为154度，具体如图1所示，将所得改性海绵用水浸泡后，塞于漏斗的颈部，在依次加入原油和水后，能在重力作用下能对水与原油的混合物进行有效分离，其分离过程如图2所示。
实施例 5
（1）同实施1例步骤（1）。
（2）同实施1例步骤（2）。
（3）称取0.48g聚乙烯醇并加入到去离子水中，在50℃下搅拌2h得到14.4mL聚乙烯醇水溶液。
（4）将45mL表面包裹二氧化硅的四氧化三铁悬浮液与60mL壳聚糖醋酸水溶液加于圆底烧瓶中，搅拌3min，然后加入14.4mL聚乙烯醇水溶液，搅拌5min，再将6块密胺海绵（4cm×2.5cm×0.7cm）浸泡于上述混合溶液中，搅拌15min后，加入0.075mL戊二醛水溶液，搅拌12h，最后从混合溶液中取出海绵，并直接在60℃下真空干燥24h，得到亲水疏油海绵。
得改性海绵对二氯甲烷的水下接触角为156度，具体如图1所示。将所得改性海绵用水浸泡后，塞于漏斗的颈部，在依次加入汽油和水后，能在重力作用下能对水与汽油的混合物进行有效分离，其分离过程如图2所示。
实施例 6
（1）同实施例1步骤（1）。
（2）同实施例2步骤（2）。
（3）称取0.32g聚乙烯醇并加入到去离子水中，在50℃下搅拌2h，得到9.6mL聚乙烯醇水溶液。
（4）将45mL表面包裹二氧化硅的四氧化三铁悬浮液与40mL壳聚糖醋酸水溶液加于圆底烧瓶中，搅拌3min，然后加入9.6mL聚乙烯醇水溶液，搅拌5min，再将6块密胺海绵（4cm×2.5cm×0.7cm）浸泡于上述混合溶液中，搅拌15min后，加入0.075mL戊二醛水溶液，搅拌12h，最后从混合溶液中取出海绵，并直接在60℃下真空干燥24h，得到亲水疏油海绵。
得亲水疏油海绵对二氯甲烷的水下接触角为156度，具体如图1所示。将所得亲水疏油海绵用水浸泡后，塞于漏斗的颈部，在依次加入葵花籽油和水后，能在重力作用下能对水与葵花籽油的混合物进行有效分离，其分离过程如图2所示。
图2为实施例1~6制得的亲水疏油海绵的水油分离效果图。从图2中可以看出，本发明制得的亲水疏油海绵具有出良好的亲水疏油能力，可单纯地通过重力驱动有效的过滤泵油（采用实施例1制得的亲水疏油海绵）、过滤机油（采用实施例2制得的亲水疏油海绵）、过滤葵花籽油（采用实施例3制得的亲水疏油海绵）、过滤汽油（采用实施例4制得的亲水疏油海绵）、过滤润滑油（采用实施例5制得的亲水疏油海绵）、过滤原油（采用实施例6制得的亲水疏油海绵）等轻质油，将油中较重的水层有效的分离出。
实施例 7
（1）量取100mL无水乙醇，在磁力搅拌下加入250mL平底烧瓶中，再分别量取10mL硅酸四乙酯和10mL氨水（浓度为25wt%），先后加入无水乙醇中，使用玻璃塞塞住平底烧瓶瓶口，持续搅拌1h后停止磁力搅拌。静置反应12h后得到白色二氧化硅悬浊液。后用蒸馏水多次洗涤，离心分离，最后一次用乙醇洗涤，最后在60℃下干燥。在搅拌情况下，将0.5g烘干的SiO 2粉末加入到无水乙醇中，在室温下搅拌2h，得到25mL纳米二氧化硅的乙醇悬浮液。
(2)称取0.4g壳聚糖溶于浓度为1wt%的醋酸溶液中，在室温下搅拌4h，得到40mL壳聚糖醋酸水溶液。
(3)称取0.2g聚乙烯醇并加入到去离子水中，50℃下搅拌2h得到10mL聚乙烯醇水溶液。
(4)将25mL纳米二氧化硅的乙醇悬浮液与40mL壳聚糖醋酸水溶液加于圆底烧瓶中，搅拌3min，然后加入10mL聚乙烯醇水溶液，搅拌5min，再将4块聚氨酯海绵（4cm×2.5cm×0.7cm）浸泡于上述混合溶液中，搅拌15min后，加入0.05mL戊二醛水溶液，搅拌12h，最后从混合溶液中取出海绵，并直接在60℃下真空干燥24h，得到亲水疏油海绵。
所得亲水疏油海绵的扫描电镜结果如图3所示，其中a为亲水疏油海绵在100倍条件下的扫描电镜图，b为亲水疏油海绵在500倍条件下的扫描电镜图，c为亲水疏油海绵在3000倍条件下的扫描电镜图，d为亲水疏油海绵在10000倍条件下的扫描电镜图，对二氯甲烷的水下接触角为151度，具体如图1所示。从图3中可看出，纳米二氧化硅颗粒均匀的负载于海绵骨架表面上。
实施例 8
（1）同实施例7步骤（1）。
（2）称取0.35g壳聚糖溶于浓度为1wt%的醋酸溶液中，在室温下搅拌4h，得到35mL壳聚糖醋酸水溶液。
（3）称取0.4g聚乙烯醇并加入到去离子水中，在50℃下搅拌2h，得到20mL聚乙烯醇水溶液。
（4）将25mL纳米二氧化硅的乙醇悬浮液与35mL壳聚糖醋酸水溶液加于圆底烧瓶中，搅拌3min，然后加入20mL聚乙烯醇水溶液，搅拌5min，再将4块聚氨酯海绵（4cm×2.5cm×0.7cm）浸泡于上述混合溶液中，搅拌15min后，加入0.05mL戊二醛水溶液，搅拌12h，最后从混合溶液中取出海绵，并直接在60℃下真空干燥24h，得到亲水疏油海绵。
所得亲水疏油海绵对二氯甲烷的水下接触角为152度，具体如图1所示。
实施例 9
（1）量取100mL无水乙醇，在磁力搅拌下加入250mL平底烧瓶中，再分别量取10mL硅酸四乙酯和10mL氨水（浓度为25wt%），先后加入无水乙醇中，使用玻璃塞塞住平底烧瓶瓶口，持续搅拌1h后停止磁力搅拌。静置反应12h后得到白色二氧化硅悬浊液。后用蒸馏水多次洗涤，离心分离，最后一次用乙醇洗涤，最后在60℃下干燥。在搅拌情况下，将0.4g烘干的SiO 2粉末加入到无水乙醇中，在室温下搅拌2h，得到20mL纳米二氧化硅的乙醇悬浮液。
（2）同实施例7步骤（2）。
（3）同实施例7步骤（3）。
（4）将20mL纳米二氧化硅的乙醇悬浮液与40mL壳聚糖醋酸水溶液加于圆底烧瓶中，搅拌3min，然后加入10mL聚乙烯醇水溶液，搅拌5min，再将4块聚氨酯海绵（4cm×2.5cm×0.7cm）浸泡于上述混合溶液中，搅拌15min后，加入0.05mL戊二醛水溶液，搅拌12h，最后从混合溶液中取出海绵并直接60℃下真空干燥24h得到亲水疏油海绵。
所得亲水疏油海绵对二氯甲烷的水下接触角为150度，具体如图1所示。
实施例 10
（1）将1.2984g FeCl 3·6H 2O与0.4776g FeCl 2·4H 2O溶于12mL去离子水中，在60℃，氮气保护的下，搅拌30min。然后加入20.8g氢氧化钠水溶液（氢氧化钠0.8g、水20g），再加入柠檬酸三钠0.128g，温度升至80℃搅拌反应1h。反应结束后待冷却至室温，对所得亲水性纳米四氧化三铁粒子进行磁分离，并用去离子水洗涤6次，然后加入40mL的去离子水配成悬浮液。向上述悬浮液中加入3.2mL氨水（浓度为25wt%）后，搅拌5min，再加入0.4mL四乙氧基硅烷，然后在室温，氮气保护下，搅拌，反应12h。反应结束后对所得表面包裹二氧化硅的四氧化三铁粒子进行磁分离，并用去离子水洗涤6次，然后加入去离子水，配成45mL的表面包裹二氧化硅的四氧化三铁悬浮液。
（2）量取100mL无水乙醇，在磁力搅拌下加入250mL平底烧瓶中，再分别量取10mL硅酸四乙酯和10mL氨水（浓度为25wt%），先后加入无水乙醇中，使用玻璃塞塞住平底烧瓶瓶口，持续搅拌1h后停止磁力搅拌。静置反应12h后得到白色二氧化硅悬浊液。后用蒸馏水多次洗涤，离心分离，最后一次用乙醇洗涤，最后在60℃下干燥。在搅拌情况下，将0.8g烘干的SiO 2粉末加入到无水乙醇中，室温下搅拌2h，得到40mL纳米二氧化硅的乙醇悬浮液。
（3）同实施例7步骤（2）。
（4）同实施例7步骤（3）。
（5）将45mL表面包裹二氧化硅的四氧化三铁悬浮液、40mL纳米二氧化硅的乙醇悬浮液与40mL壳聚糖醋酸水溶液加于圆底烧瓶中，搅拌3min，然后加入10mL聚乙烯醇水溶液，搅拌5min，再将4块聚氨酯海绵（4cm×2.5cm×0.7cm）浸泡于上述混合溶液中，搅拌15min后，加入0.05mL戊二醛水溶液，搅拌12h，最后从混合溶液中取出海绵，并直接在60℃下真空干燥24h，得到亲水疏油海绵。所得改性海绵对二氯甲烷的水下接触角为152度，具体如图1所示。
实施例 11
（1）同实施例10步骤（1）。
（2）同实施例10步骤（2）。
（3）称取0.3g壳聚糖溶于浓度为1wt%的醋酸溶液中，室温下搅拌4h得到30mL壳聚糖醋酸水溶液。
（4）同实施例7步骤（3）。
（5）将45mL表面包裹二氧化硅的四氧化三铁悬浮液、40mL纳米二氧化硅的乙醇悬浮液与30mL壳聚糖醋酸水溶液加于圆底烧瓶中，搅拌3min，然后加入10mL聚乙烯醇水溶液，搅拌5min，再将4块聚氨酯海绵（4cm×2.5cm×0.7cm）浸泡于上述混合溶液中，搅拌15min后，加入0.05mL戊二醛水溶液，搅拌12h，最后从混合溶液中取出海绵，并直接在60℃下真空干燥24h，得到亲水疏油海绵。所得改性海绵对二氯甲烷的水下接触角为152度，具体如图1所示。
实施例 12
（1）同实施例10步骤（1）。
（2）同实施例10步骤（2）。
（3）同实施例7步骤（2）。
（4）同实施例8步骤（3）。
（5）将45mL表面包裹二氧化硅的纳米四氧化三铁悬浮液、40mL纳米二氧化硅的乙醇悬浮液与40mL壳聚糖醋酸水溶液加于圆底烧瓶中，搅拌3min，然后加入20mL聚乙烯醇水溶液，搅拌5min，再将4块聚氨酯海绵（4cm×2.5cm×0.7cm）浸泡于上述混合溶液中，搅拌15min后，加入0.05mL戊二醛水溶液，搅拌12h，最后从混合溶液中取出海绵，并直接在60℃下真空干燥24h，得到亲水疏油海绵。
所得亲水疏油海绵对二氯甲烷的水下接触角为152度，具体如图1所示。
图1为实施例1~12制得的亲水疏油海绵对二氯甲烷的水下接触角图，从图1中可以看出，本发明制得的亲水疏油海绵对二氯甲烷的水下接触角为150度~157度，显示出良好的亲水疏油能力。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
 

Claims (10)

  1. 一种亲水疏油海绵的制备方法，其特征在于，包括如下步骤：
    将纳米粒子悬浮液与改性剂溶液混合，得到改性溶液；所述纳米粒子悬浮液包括表面包裹二氧化硅的纳米四氧化三铁悬浮液和/或纳米二氧化硅的乙醇悬浮液；所述改性剂溶液为壳聚糖醋酸水溶液和聚乙烯醇水溶液；
    将海绵浸入所述的改性溶液中后，与戊二醛水溶液混合进行交联反应，得到亲水疏油海绵。
  2. 根据权利要求1所述的制备方法，其特征在于，所述壳聚糖醋酸水溶液和聚乙烯醇水溶液的体积比为1:2~15:1，所述壳聚糖醋酸水溶液的质量浓度为0.19%~4.80%，所述聚乙烯醇水溶液的质量浓度为0.33%~10.72%。
  3. 根据权利要求1所述的制备方法，其特征在于，所述表面包裹二氧化硅的纳米四氧化三铁悬浮液由包括如下步骤的制备方法制得：
    在氮气气氛中，在可溶性+3价铁盐和可溶性+2价铁盐的水溶液中，依次加入碱性溶液、柠檬酸三钠进行共沉淀反应，得到亲水性四氧化三铁悬浮液；
    将四乙氧基硅烷溶液与所述亲水性四氧化三铁悬浮液混合，进行水解缩合反应，得到表面包裹二氧化硅的纳米四氧化三铁悬浮液。
  4. 根据权利要求1所述的制备方法，其特征在于，所述纳米二氧化硅的乙醇悬浮液由包括如下步骤的制备方法制得：
    将硅酸四乙酯、氨水依次加入无水乙醇中混合，进行水解缩合反应，依次经洗涤和干燥，得到纳米二氧化硅颗粒；
    将所述纳米二氧化硅颗粒与无水乙醇混合，得到纳米二氧化硅的乙醇悬浮液。
  5. 根据权利要求1所述的制备方法，其特征在于，所述表面包裹二氧化硅的纳米四氧化三铁悬浮液中的纳米四氧化三铁粒子与改性剂溶液中的改性剂的质量比为0.5:2.7~1.5:0.5；所述纳米二氧化硅的乙醇悬浮液中的纳米二氧化硅粒子与改性剂溶液中的改性剂的质量比为0.5:2.7~1.5:0.5。
  6. 根据权利要求1所述的制备方法，其特征在于，所述海绵包括密胺树脂海绵和/或聚氨酯海绵。
  7. 根据权利要求1所述的制备方法，其特征在于，所述改性剂溶液中改性剂与戊二醛水溶液中戊二醛的质量比为2.7~1.5：0.020~0.10。
  8. 根据权利要求1所述的制备方法，其特征在于，所述交联反应时间为10~14h。
  9. 权利要求1~8任一项所述的制备方法制得的亲水疏油海绵，其特征在于，所述亲水疏油海绵包括海绵基底和负载在所述海绵基底表面上的纳米粒子与改性剂，所述纳米粒子包括表面包裹二氧化硅的纳米四氧化三铁和/或纳米二氧化硅，所述改性剂为壳聚糖和聚乙烯醇。
  10. 权利要求9所述的亲水疏油海绵在油水混合物的油水分离处理领域中的应用。
PCT/CN2019/091613 2019-04-16 2019-06-18 一种亲水疏油海绵及其制备方法和应用 WO2020211186A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US17/044,225 US11964220B2 (en) 2019-04-16 2019-06-18 Hydrophilic/oleophobic sponge, preparation method and use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910303861.XA CN110028696B (zh) 2019-04-16 2019-04-16 一种亲水疏油海绵及其制备方法和应用
CN201910303861.X 2019-04-16

Publications (1)

Publication Number Publication Date
WO2020211186A1 true WO2020211186A1 (zh) 2020-10-22

Family

ID=67238609

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/091613 WO2020211186A1 (zh) 2019-04-16 2019-06-18 一种亲水疏油海绵及其制备方法和应用

Country Status (3)

Country Link
US (1) US11964220B2 (zh)
CN (1) CN110028696B (zh)
WO (1) WO2020211186A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114054001A (zh) * 2021-11-18 2022-02-18 军事科学院军事医学研究院环境医学与作业医学研究所 一种磁性纳米吸附剂及其制备方法和应用
CN114797177A (zh) * 2022-04-02 2022-07-29 孝感市光源电力集团有限责任公司 一种特高压电站事故变压器油应急处置方法及其设备

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110947363A (zh) * 2019-12-04 2020-04-03 四川农业大学 油水分离用磁驱动轻质碳海绵及其制备方法
CN113845117B (zh) * 2020-06-28 2023-05-26 中国石油天然气股份有限公司 一种油水两亲性二氧化硅纳米粒子及其制备方法
CN112354215A (zh) * 2020-09-18 2021-02-12 山东大学 一种用于油水分离的超大孔超双亲壳聚糖聚合物及油水分离方法
CN112390981B (zh) * 2020-11-17 2022-03-29 中国科学院长春应用化学研究所 一种韧性增强三聚氰胺甲醛-聚乙烯醇复合泡沫材料的制备方法
CN112553963B (zh) * 2020-12-02 2022-05-06 中国科学院长春应用化学研究所 一种硅藻土基滤纸、其制备方法及应用
CN113521881A (zh) * 2021-07-23 2021-10-22 江西离子型稀土工程技术研究有限公司 一种稀土冶炼含油废水处理用过滤布及其制备方法
CN114345306B (zh) * 2021-12-10 2023-08-08 吉林省电力科学研究院有限公司 一种亲水型带正电乳液分离材料的制备方法
CN114940777A (zh) * 2022-04-18 2022-08-26 中国石油大学(华东) 一种带正电荷的油水分离海绵的制备方法
CN117756459A (zh) * 2023-12-25 2024-03-26 万特福建筑构件有限公司 一种绿色环保混凝土及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5997146A (ja) * 1982-11-26 1984-06-04 Asahi Shinbunsha:Kk 感光性平版印刷版
CN105778158A (zh) * 2014-12-16 2016-07-20 中国科学院宁波材料技术与工程研究所 一种超亲水-超疏油纤维素海绵及其制备方法
CN107583470A (zh) * 2017-09-18 2018-01-16 上海大学 超亲水并且水下超疏油的油水分离膜及其制备方法
CN108101385A (zh) * 2017-12-28 2018-06-01 中科院广州化学有限公司 一种透明超疏水涂层及其制备方法和应用
CN109364888A (zh) * 2018-10-04 2019-02-22 南京航空航天大学溧水仿生产业研究院有限公司 仿生超疏水吸附海绵的制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5997146B2 (ja) * 2010-07-30 2016-09-28 エルジー イノテック カンパニー リミテッド タッチパネル
CN104874295B (zh) * 2015-05-04 2016-08-31 哈尔滨工业大学 一种超亲水自清洁多功能分等级油水分离材料的制备方法
CN108410005A (zh) * 2018-02-12 2018-08-17 杭州师范大学 一种磁性超疏水海绵材料的制备方法
CN109261127B (zh) * 2018-08-27 2021-08-24 浙江工业大学 一种无选择性疏油亲水材料及其制备方法和应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5997146A (ja) * 1982-11-26 1984-06-04 Asahi Shinbunsha:Kk 感光性平版印刷版
CN105778158A (zh) * 2014-12-16 2016-07-20 中国科学院宁波材料技术与工程研究所 一种超亲水-超疏油纤维素海绵及其制备方法
CN107583470A (zh) * 2017-09-18 2018-01-16 上海大学 超亲水并且水下超疏油的油水分离膜及其制备方法
CN108101385A (zh) * 2017-12-28 2018-06-01 中科院广州化学有限公司 一种透明超疏水涂层及其制备方法和应用
CN109364888A (zh) * 2018-10-04 2019-02-22 南京航空航天大学溧水仿生产业研究院有限公司 仿生超疏水吸附海绵的制备方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114054001A (zh) * 2021-11-18 2022-02-18 军事科学院军事医学研究院环境医学与作业医学研究所 一种磁性纳米吸附剂及其制备方法和应用
CN114797177A (zh) * 2022-04-02 2022-07-29 孝感市光源电力集团有限责任公司 一种特高压电站事故变压器油应急处置方法及其设备
CN114797177B (zh) * 2022-04-02 2023-08-08 孝感市光源电力集团有限责任公司 一种特高压电站事故变压器油应急处置方法及其设备

Also Published As

Publication number Publication date
CN110028696A (zh) 2019-07-19
US20210346823A1 (en) 2021-11-11
CN110028696B (zh) 2021-09-10
US11964220B2 (en) 2024-04-23

Similar Documents

Publication Publication Date Title
WO2020211186A1 (zh) 一种亲水疏油海绵及其制备方法和应用
WO2018049965A1 (zh) 一种以微乳液为前体快速制备气凝胶的方法
CN104998623B (zh) 一种复合磁性纳米颗粒吸附剂及其制备方法和应用
CN105969330B (zh) 一种石墨烯纳米材料的制备方法
CN105149011B (zh) 绿泥石介孔复合材料和负载型催化剂及其制备方法和应用以及环己酮甘油缩酮的制备方法
CN107790102A (zh) 一种三维褶皱球状MOFs@rGO吸油材料及制备方法
CN107790075B (zh) 一种核-壳-壳结构的磁性介孔SiO2纳米粒子的制备方法
CN109261138A (zh) 一种用于重金属离子吸附的超支化聚酰胺改性海藻酸钠微球及其制备方法
CN107961764A (zh) 一种羧甲基-β-环糊精功能化磁性介孔硅微球的制备方法
CN106179249A (zh) 一种凹凸棒纤维素复合吸附微球的制备方法
CN109133070A (zh) 一种以水玻璃为原料超快速常压制备疏水二氧化硅气凝胶的方法
CN105597708B (zh) 一种空气中pm2.5净化剂的制备方法
CN104623973B (zh) 一种改性石英砂及其改性方法
CN109092240A (zh) 一种多孔磁性羟基磷灰石微球的制备方法
CN105344325A (zh) 一种处理重金属污染水体的纳米铁/介孔硅复合材料的制备方法
CN106732221B (zh) 一种具有开口结构的两亲性Janus分级孔微囊的制备方法
CN109317061A (zh) 一种水合氧化铁壳聚糖负载氧化石墨烯气凝胶的制备方法
CN107913677A (zh) 一种纳米重金属废水离子吸附微球及其制备方法
CN110420502A (zh) 壳聚糖包覆的超亲水水下超疏油硬质颗粒滤料的制备方法
CN104289200B (zh) 一种磁性hacc/氧化多壁碳纳米管吸附剂的制备方法及应用
CN108295812A (zh) 一种用于选择性去除水中金属离子的氧化石墨烯复合膜及其制备方法、应用
CN109663572A (zh) 氨基和巯基双功能化介孔二氧化硅的制备方法及其在砷去除中的应用
CN116177822A (zh) 一种污水处理药剂及其制备方法
CN114405475B (zh) 一种吸附材料及其制备方法和应用
CN109956479A (zh) 一种中空微球及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19925176

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19925176

Country of ref document: EP

Kind code of ref document: A1