CN110523297B - Graphene oxide composite nanofiltration membrane and preparation method thereof - Google Patents
Graphene oxide composite nanofiltration membrane and preparation method thereof Download PDFInfo
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- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
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Abstract
The invention provides a graphene oxide composite nanofiltration membrane and a preparation method thereof, wherein the method comprises the following steps: and (3) dropping the graphene oxide dispersion liquid prepared by the improved Hummers method on one side of the base film, uniformly coating the graphene oxide dispersion liquid by using a coating rod, drying and partially reducing to obtain the graphene oxide composite nanofiltration membrane. The method avoids the harsh requirements of the traditional nanofiltration membrane preparation process on conditions, overcomes the defect that the existing graphene oxide composite nanofiltration membrane preparation method is difficult to continuously produce in a large area, is simple and feasible, has strong adjustability, low production cost and no pollution, and therefore has important significance for the industrial application of the graphene oxide composite nanofiltration membrane. The graphene oxide composite nanofiltration membrane prepared by the method has the operating pressure of 3.0-5.0 bar and Na2SO4The solution concentration is 1.5g/L, and the water flux is 3.7-13.0 kg/(m)2H and bar) and the salt rejection rate is 39.1-91.8%.
Description
Technical Field
The invention belongs to the technical field of composite nanofiltration membranes, and particularly relates to a graphene oxide composite nanofiltration membrane and a preparation method thereof.
Background
Nanofiltration (NF) is a pressure-driven membrane separation process between ultrafiltration and reverse osmosis with the separation precision of 1-10 nm, and has wide application prospects in the industries of water treatment, food, petrochemical industry, biological medicine and the like. The preparation method of the nanofiltration membrane mainly comprises an L-S phase inversion method, a blending method, a charging method and an interfacial polymerization method, and at the present stage, the method for effectively preparing the nanofiltration membrane and large-scale application is the interfacial polymerization method and is prepared by compounding a polymer thin layer with separation performance on a porous substrate. In the process of interfacial polymerization, conditions such as concentration of reaction monomers, reaction time, reaction temperature, environmental humidity and the like need to be controlled strictly, so that the preparation difficulty of the nanofiltration membrane is greatly increased, and the nanofiltration membrane prepared by the interfacial polymerization method has the advantages of high flux, high rejection rate and the like, but due to membrane surface hydrophobicity, membrane surface roughness, interaction between a base membrane and a functional layer and the like, the nanofiltration membrane has defects in aspects such as pollution resistance and stability, and is poor in chlorine resistance, so that the membrane performance is greatly reduced, the service life of the composite nanofiltration membrane is also shortened, and the application and development of the composite nanofiltration membrane are severely restricted.
Graphene Oxide (GO) is a carbon material with excellent performance, has a structure similar to graphene, has a single-layer honeycomb hexagonal planar structure of graphene, contains rich oxygen-containing functional groups such as hydroxyl, carboxyl, epoxy, carbonyl and the like, has the characteristics of good hydrophilicity, thin lamella, high movement speed of water molecules among the lamella and the like, can realize interception of solutes by adjusting the interlayer spacing of GO, and shows excellent nanofiltration performance. Therefore, graphene oxide has become a hot material for preparing nanofiltration membranes. At present, the preparation method of the graphene oxide composite nanofiltration membrane mainly comprises a vacuum filtration method, a dip coating method, a spin coating method, a spraying method and a layer-by-layer self-assembly method. However, none of the preparation methods can continuously prepare the graphene oxide composite nanofiltration membrane in a large area, and the preparation methods have the disadvantages of complex process, high equipment investment cost and difficulty in realizing industrial application.
Disclosure of Invention
In view of this, the invention aims to provide a graphene oxide composite nanofiltration membrane and a preparation method thereof, wherein the method is simple and can realize large-area production.
The invention provides a preparation method of a graphene oxide composite nanofiltration membrane, which comprises the following steps:
and (3) dropping the graphene oxide dispersion liquid prepared by the improved Hummers method on one side of the base film, uniformly coating the dispersion liquid by using a coating rod, drying and partially reducing to obtain the graphene oxide composite nanofiltration membrane.
Preferably, the concentration of the graphene oxide dispersion liquid is 1-5.0 g/L.
Preferably, the base film is made of polycaprolactam, polyvinylidene fluoride, polysulfone, polyethersulfone, polyacrylonitrile, polypropylene, polyethylene, cellulose acetate, polyurethane, polyvinyl chloride or polyfuranol.
Preferably, the base membrane is selected from polycaprolactam membranes having an average pore size of 0.1 μm, polyvinylidene fluoride membranes having an average pore size of 0.1 μm, polycaprolactam membranes having an average pore size of 0.2 μm or polysulfone membranes having an average pore size of 0.2 μm.
Preferably, the uniform coating speed of the coating rod is 5-13 cm/s.
Preferably, the coating rod is a wire-wound coating rod; the size of the wire-wound coating rod is 0.2-1.2 mm.
Preferably, the drying mode is selected from natural airing, heating drying, vacuum drying or air flow blowing.
Preferably, the reduction is selected from the group consisting of ultraviolet reduction, high temperature reduction, hydrazine hydrate reduction or soda-boil reduction.
The invention provides a graphene oxide composite nanofiltration membrane prepared by the preparation method in the technical scheme.
The invention provides a preparation method of a graphene oxide composite nanofiltration membrane, which comprises the following steps: and (3) dropping the graphene oxide dispersion liquid prepared by the improved Hummers method on one side of the base film, uniformly coating the dispersion liquid by using a coating rod, drying and partially reducing to obtain the graphene oxide composite nanofiltration membrane. The method avoids the harsh requirements of the traditional nanofiltration membrane preparation process on conditions, overcomes the defect that the existing graphene oxide composite nanofiltration membrane preparation method is difficult to continuously produce in large area, is simple and feasible, and can be used for preparing the graphene oxide composite nanofiltration membraneThe method has the advantages of strong adjustability, low production cost and no pollution, and therefore, the method has important significance for the industrial application of the graphene oxide composite nanofiltration membrane. The experimental results show that: the graphene oxide composite nanofiltration membrane prepared by the method provided by the invention has the operating pressure of 3.0-5.0 bar and Na2SO4The solution concentration is 1.5g/L, and the water flux is 3.7-13.0 kg/(m)2H.bar), the salt cut-off rate is 39.1-91.8%.
Drawings
Fig. 1 is a surface electron microscope image of a base film used in example 1 of the present invention and a prepared graphene oxide composite nanofiltration membrane;
fig. 2 is a surface electron microscope image of the base film used in example 2 of the present invention and the prepared graphene oxide composite nanofiltration membrane;
fig. 3 is a surface electron microscope image of the base film used in example 3 of the present invention and the prepared graphene oxide composite nanofiltration membrane;
fig. 4 is a surface electron microscope image of the base film used in example 4 of the present invention and the prepared graphene oxide composite nanofiltration membrane;
fig. 5 is a surface electron microscope image of the base film used in example 5 of the present invention and the prepared graphene oxide composite nanofiltration membrane.
Detailed Description
The invention provides a preparation method of a graphene oxide composite nanofiltration membrane, which comprises the following steps:
and (3) dropping the graphene oxide dispersion liquid prepared by the improved Hummers method on one side of the base film, uniformly coating the graphene oxide dispersion liquid by using a coating rod, drying and partially reducing to obtain the graphene oxide composite nanofiltration membrane.
In the present invention, the preparation process of the graphene oxide prepared by the modified Hummers method preferably includes the following steps: firstly, ice-bath is carried out, concentrated sulfuric acid is added into a beaker, and a certain amount of KMnO is slowly added under magnetic stirring4Forming a dark green solution, and stirring for a certain time in an ice bath; slowly adding graphite, and stirring for a certain time at normal temperature; thirdly, transferring the wine red liquid into a water bath with a certain temperature, slowly stirring the mixture, and reacting the mixture for a certain time to form wine red liquid; fourthly, after the ice is cooled, a certain amount of ice is poured into the ice; fifthly, adding a certain amount of 30 percent after the ice is completely meltedHydrogen peroxide is fully stirred by a glass rod to become orange yellow dispersion liquid; sixthly, adding pure water for washing, naturally settling the flaky crystal, pouring out the supernatant after a definite boundary is formed, and then adding water for washing for multiple times until the solution is neutral, thus obtaining the required graphene oxide.
In the present invention, the volume of concentrated sulfuric acid and KMnO in step (i)4The mass ratio of (b) is preferably (50 to 200) mL: (2-18) g; in a specific embodiment, the addition amount of the concentrated sulfuric acid is 50-200 mL, and KMnO4The amount of (A) is 2 to 18 g. Stirring time in ice bath is 0.5-2 h.
In the invention, the mesh number of the graphite in the second step is 50-325 meshes; the graphite and KMnO4The mass ratio of (A) to (B) is preferably 1-4: 2-18; in a specific embodiment, the addition amount of the graphite is 1-4 g. In the second step, the stirring time is 0-2 h.
In the invention, the temperature of the water bath in the step III is 0-60 ℃, and the reaction time is 1-24 h.
In the invention, the mass ratio of ice to hydrogen peroxide in the step IV is preferably 100-500: 5-50; in a specific embodiment, the mass of ice in the step IV is 100-500 g; the amount of the hydrogen peroxide in the fifth step is 5-50 g.
In the invention, the concentration of the graphene oxide dispersion liquid is preferably 1.0-5.0 g/L. The invention realizes the preparation of the nanofiltration membrane by coating the low-concentration graphene oxide dispersion liquid. In specific embodiments, the concentration of the graphene oxide dispersion is 5.0g/L, 1.5g/L, or 1.0 g/L.
In the present invention, the base membrane is preferably selected from polycaprolactam, polyvinylidene fluoride, polysulfone, polyethersulfone, polyacrylonitrile, polypropylene, polyethylene, cellulose acetate, polyurethane, polyvinyl chloride, or polyfuranol, and more preferably from polycaprolactam membrane having an average pore diameter of 0.1. mu.m, polyvinylidene fluoride membrane having an average pore diameter of 0.1. mu.m, polycaprolactam membrane having an average pore diameter of 0.2. mu.m, or polysulfone membrane having an average pore diameter of 0.2. mu.m.
In the invention, the base film is preferably laid flat and fixed on a film coating machine; the flat laying and fixing mode is preferably to stick one end of the base film close to the coating rod on the coating machine by using a transparent adhesive tape.
In the invention, the uniform coating speed of the coating rod is 5-13 cm/s; in particular embodiments, the coating speed is 6cm/s, 8cm/s, 10cm/s, or 12 cm/s. The coating rod is preferably a wire-wound coating rod; the size of the wire-wound coating rod is 0.2-1.2 mm; in specific embodiments, the wire-wound coating rods have a size of 0.2mm, 0.3mm, 0.5mm, 0.8mm, or 1.0 mm.
The thickness of the graphene oxide coating can be adjusted according to the concentration of the graphene oxide dispersion liquid and the size of the coating rod, and the adjustability is strong.
In the invention, the drying mode is selected from natural airing, heating drying, vacuum drying or air flow blowing. The temperature for heating and drying is preferably 60 ℃ to 80 ℃, and more preferably 70 ℃.
In the invention, the reduction mode is selected from ultraviolet reduction, high-temperature reduction, hydrazine hydrate reduction or soda boiling reduction.
The invention provides a graphene oxide composite nanofiltration membrane prepared by the preparation method in the technical scheme. The graphene oxide composite nanofiltration membrane has the operating pressure of 3.0-5.0 bar and Na2SO4The solution concentration is 1.5g/L, and the water flux is 3.7-13.0 kg/(m)2H.bar), the salt cut-off rate is 39.1-91.8%.
The graphene oxide composite nanofiltration membrane comprises a base material and a graphene oxide layer compounded on the base material; the thickness of the base material is preferably 100-300 mu m; the thickness of the graphene oxide layer is preferably 50-200 μm.
In order to further illustrate the present invention, the graphene oxide composite nanofiltration membrane and the preparation method thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The graphene oxide prepared by the improved Hummers method in the technical scheme is prepared into 5.0g/L graphene oxide dispersion liquid, a polyvinylidene fluoride membrane with the average pore diameter of 0.1 mu m is flatly laid and fixed on a film coating machine, the GO dispersion liquid is dropped on one side of a base membrane, the GO dispersion liquid is uniformly coated on the surface of a flat-plate base membrane by a coating rod with the diameter of 0.3mm at the speed of 8cm/s, the flat-plate base membrane is naturally dried, and the dried membrane is subjected to high-temperature reduction to obtain the required graphene oxide composite nanofiltration membrane, wherein reference is made to fig. 1 which is a surface electron microscope image of the base membrane used in the embodiment 1 of the invention and the prepared graphene oxide composite nanofiltration membrane.
And (3) evaluating the water flux and the salt rejection rate of the prepared graphene oxide composite nanofiltration membrane by adopting a pressure filtration device. At an operating pressure of 4.0bar, Na2SO4The water flux of the membrane is 5.9 kg/(m) under the condition that the solution concentration is 1.5g/L2H.bar) with a salt cut-off of 74.6%.
Example 2:
graphene oxide prepared by an improved Hummers method is prepared into 1.5g/L graphene oxide dispersion liquid, a polycaprolactam film with the average pore diameter of 0.1 mu m is flatly laid and fixed on a film coating machine, the GO dispersion liquid is dropped on one side of a base film, the GO dispersion liquid is uniformly coated on the surface of a flat base film by a coating rod with the diameter of 0.2mm at the speed of 10cm/s, the flat base film is dried at 70 ℃, and the dried film is subjected to ultraviolet reduction to obtain the required graphene oxide composite nanofiltration film, wherein the reference to fig. 2 is a surface electron microscope image of the base film used in the embodiment 2 of the invention and the prepared graphene oxide composite nanofiltration film.
And (3) evaluating the water flux and the salt rejection rate of the prepared graphene oxide composite nanofiltration membrane by adopting a pressure filtration device. At an operating pressure of 4.0bar, Na2SO4The water flux of the membrane is 3.7 kg/(m) under the condition that the solution concentration is 1.5g/L2H.bar), the salt rejection rate can reach 91.8%.
Example 3:
graphene oxide prepared by an improved Hummers method is prepared into 5.0g/L graphene oxide dispersion liquid, a polycaprolactam film with the average pore diameter of 0.2 mu m is flatly laid and fixed on a film coating machine, the GO dispersion liquid is dripped on one side of a base film, the GO dispersion liquid is uniformly coated on the surface of a flat base film by a coating rod with the diameter of 0.5mm at the speed of 6cm/s, vacuum drying is carried out, and the dried film is subjected to ultraviolet reduction to obtain the required graphene oxide composite nanofiltration membrane, which is shown in figure 3, wherein figure 3 is a surface electron microscope image of the base film used in example 3 of the invention and the prepared graphene oxide composite nanofiltration membrane.
And (3) evaluating the water flux and the salt rejection rate of the prepared graphene oxide composite nanofiltration membrane by adopting a pressure filtration device. At an operating pressure of 3.0bar, Na2SO4The water flux of the membrane is 4.4 kg/(m) under the condition that the solution concentration is 1.5g/L2H.bar), the salt rejection can reach 86.5%.
Example 4:
graphene oxide prepared by an improved Hummers method is prepared into 1.5g/L graphene oxide dispersion liquid, a polysulfone membrane with the average pore diameter of 0.2 mu m is flatly laid and fixed on a coating machine, GO dispersion liquid is dropped on one edge of a base membrane, the GO dispersion liquid is uniformly coated on the surface of a flat base membrane by a coating rod with the diameter of 1.0mm at the speed of 10cm/s, the surface of the flat base membrane is naturally dried, and the dried membrane is subjected to high-temperature reduction to obtain the required graphene oxide composite nanofiltration membrane, wherein the reference figure 4 is a surface electron microscope image of the base membrane used in the embodiment 4 of the invention and the prepared graphene oxide composite nanofiltration membrane.
And (3) evaluating the water flux and the salt rejection rate of the prepared graphene oxide composite nanofiltration membrane by adopting a pressure filtering device. At an operating pressure of 5.0bar, Na2SO4The water flux of the membrane is 5.8 kg/(m) under the condition that the solution concentration is 1.5g/L2H.bar) the salt cut-off was 80.3%.
Example 5:
graphene oxide prepared by an improved Hummers method is prepared into 1.0g/L graphene oxide dispersion liquid, a polysulfone membrane with the average pore diameter of 0.2 mu m is flatly laid and fixed on a film coating machine, GO dispersion liquid is dropped on one side of a base membrane, the GO dispersion liquid is uniformly coated on the surface of a flat base membrane by a coating rod with the diameter of 0.8mm at the speed of 12cm/s, air flow blowing is carried out, and the dried membrane is subjected to high-temperature reduction, so that a required graphene oxide composite nanofiltration membrane can be obtained, and referring to fig. 5, fig. 5 is a surface electron microscope image of the base membrane used in the embodiment 5 of the invention and the prepared graphene oxide composite nanofiltration membrane.
And (3) evaluating the water flux and the salt rejection rate of the prepared graphene oxide composite nanofiltration membrane by adopting a pressure filtration device.At an operating pressure of 3.0bar, Na2SO4The water flux of the membrane is 13.0 kg/(m) under the condition that the solution concentration is 1.5g/L2H.bar) the salt cut-off was 39.1%.
The embodiment shows that the preparation method of the graphene oxide composite nanofiltration membrane provided by the invention comprises the following steps: and (3) dropping the graphene oxide dispersion liquid prepared by the improved Hummers method on one side of the base film, uniformly coating the dispersion liquid by using a coating rod, drying and partially reducing to obtain the graphene oxide composite nanofiltration membrane. The method avoids the harsh requirements of the traditional nanofiltration membrane preparation process on conditions, overcomes the defect that the existing graphene oxide composite nanofiltration membrane preparation method is difficult to continuously produce in a large area, is simple and feasible, has strong adjustability, low production cost and no pollution, and therefore has important significance for the industrial application of the graphene oxide composite nanofiltration membrane. The experimental results show that: the graphene oxide composite nanofiltration membrane prepared by the method provided by the invention has the operating pressure of 3.0-5.0 bar and Na2SO4The solution concentration is 1.5g/L, and the water flux is 3.7-13.0 kg/(m)2H and bar) and the salt rejection rate is 39.1-91.8%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (3)
1. A preparation method of a graphene oxide composite nanofiltration membrane comprises the following steps:
dropping the graphene oxide dispersion liquid prepared by the improved Hummers method on one side of a base film, uniformly coating the graphene oxide dispersion liquid by using a coating rod, drying, and partially reducing to obtain a graphene oxide composite nanofiltration membrane;
the concentration of the graphene oxide dispersion liquid is 1-5.0 g/L;
the basement membrane is selected from a polycaprolactam membrane with an average pore size of 0.1 μm, a polyvinylidene fluoride membrane with an average pore size of 0.1 μm, or a polycaprolactam membrane with an average pore size of 0.2 μm or a polysulfone membrane with an average pore size of 0.2 μm;
the uniform coating speed of the coating rod is 6-12 cm/s; the coating rod is a wire winding type coating rod; the size of the winding wire on the wire-winding type coating rod is 0.2-1.0 mm;
the drying mode is selected from natural airing, heating and drying, vacuum drying or air flow blowing;
the preparation process of the graphene oxide prepared by the improved Hummers method comprises the following steps: firstly, ice-bath is carried out, concentrated sulfuric acid is added into a beaker, and a certain amount of KMnO is slowly added under magnetic stirring4Forming a dark green solution, and stirring for a certain time in an ice bath; slowly adding graphite, and stirring for a certain time at normal temperature; thirdly, transferring the wine red liquid into a water bath with a certain temperature, slowly stirring the mixture, and reacting the mixture for a certain time to form wine red liquid; fourthly, after the ice is cooled, a certain amount of ice is poured into the ice; fifthly, adding a certain amount of 30% hydrogen peroxide when the ice is completely melted, and fully stirring the mixture by using a glass rod to obtain an orange-yellow dispersion liquid; sixthly, adding pure water for washing, naturally settling the flaky crystal, pouring out supernatant after a definite boundary is formed, and then adding water for washing for many times until the solution is neutral to obtain the required graphene oxide;
the graphene oxide composite nanofiltration membrane comprises a base membrane and a graphene oxide layer compounded on the base membrane; the thickness of the base film is 100-300 mu m; the thickness of the graphene oxide layer is 50-200 mu m.
2. The method of claim 1, wherein the reduction is performed by a method selected from the group consisting of UV reduction, high temperature reduction, hydrazine hydrate reduction, and soda-boil reduction.
3. A graphene oxide composite nanofiltration membrane prepared by the preparation method of any one of claims 1 to 2.
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