CN109821418B - Oriented carbon nanotube-based membrane, interfacial polymerization nanofiltration membrane using same and preparation method thereof - Google Patents
Oriented carbon nanotube-based membrane, interfacial polymerization nanofiltration membrane using same and preparation method thereof Download PDFInfo
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Abstract
The embodiment of the invention relates to the field of materials, in particular to an oriented carbon nanotube-based membrane, an interfacial polymerization nanofiltration membrane using the same and a preparation method thereof. The preparation method of the carbon nanotube base film with the high-voltage electric field orientation provided by the embodiment of the invention comprises the following steps: coating the casting solution containing the carbon nano tube on an insulating smooth substrate, putting the insulating smooth substrate into a high-voltage electric field device for acting, and putting the insulating smooth substrate into a water coagulation bath to remove the organic solvent to obtain the base film with the oriented carbon nano tube. The preparation method of the interface polymerization nanofiltration membrane provided by the embodiment of the invention comprises the following steps: the interfacial polymerization nanofiltration membrane is prepared by utilizing the base membrane with the oriented carbon nano tubes. The carbon nanotube base film with high-voltage electric field orientation has certain orientation and large water flux; the interfacial polymerization nanofiltration membrane prepared by the method can greatly improve the efficiency of water molecules passing through the base membrane, and ensure the selectivity while improving the permeability of the interfacial polymerization nanofiltration membrane.
Description
Technical Field
The invention relates to the field of materials, in particular to an oriented carbon nanotube-based membrane, an interfacial polymerization nanofiltration membrane using the same and a preparation method thereof.
Background
Due to increased environmental pollution and growing population, shortage of fresh water resources is attracting worldwide attention. The membrane separation technology is used as a water treatment method, and has the advantages of low energy consumption, moderate operation condition, environmental friendliness and the like. Ultrafiltration, nanofiltration and reverse osmosis membranes have been developed to reject different sized substances, with nanofiltration being an emerging pressure driven membrane process with excellent separation capability for divalent ions and low molecular weight organic matter.
The interfacial polymerization nanofiltration membrane based on the aromatic polyamide is widely used for water body purification and divalent salt removal due to high cost efficiency and quite simple operation, and in order to further improve the separation performance and the permeability and maintain good stability, the membrane needs to be modified so as to further explore the potential of the nanofiltration membrane. The modification method of the interfacial polymerization nanofiltration membrane mainly comprises two methods of membrane interfacial layer modification and base membrane modification. And the appearance of nano materials, such as carbon nano tubes, silicon dioxide, titanium dioxide, graphene oxide and the like, can be used as a better choice for the modified filler in the base film.
The high mechanical strength and excellent chemical stability of the carbon nanotubes themselves are extremely advantageous for the durability of the film. And the smooth and resistance-free inner wall of the membrane can be used as a fast channel of water molecules, so that the water molecules can pass through the membrane more quickly, and the permeability of the membrane is facilitated. However, the tendency of carbon nanotubes to form tangled agglomerates and their weak interfacial interactions with the polymer matrix make it difficult to disperse uniformly in the casting solution.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
Object of the Invention
In order to solve the above technical problems, carbon nanotubes have been modified by physical or chemical methods so that they form a homogeneous dispersion in a solvent, thereby improving the performance of the film. The invention aims to provide an oriented carbon nanotube-based membrane, an interfacial polymerization nanofiltration membrane using the same and a preparation method thereof. In the preparation method of the base membrane with the oriented carbon nano tubes, an external high-voltage electric field is applied to the casting solution containing the carbon nano tubes, so that the carbon nano tubes are polarized under the action of the high-voltage electric field, and the entanglement phenomenon is reduced; the two ends of the carbon nano tube induce charges opposite to the upper and lower conductive polar plates of the high-voltage electric field device, so that torque is generated to enable the carbon nano tube to be oriented along the direction of the electric field; therefore, the carbon nanotube base film with high-voltage electric field orientation prepared by the preparation method has certain orientation and large water flux. The interfacial polymerization nanofiltration membrane prepared by using the base membrane with the oriented carbon nanotubes greatly improves the efficiency of water molecules passing through the base membrane, and ensures the selectivity while improving the permeability of the interfacial polymerization nanofiltration membrane.
Solution scheme
In order to achieve the object of the present invention, an embodiment of the present invention provides a method for preparing a carbon nanotube-based film with a high-voltage electric field orientation, including the following steps: coating the casting solution containing the carbon nano tube on an insulating smooth substrate, putting the insulating smooth substrate into a high-voltage electric field device for acting, and putting the insulating smooth substrate into a water coagulation bath to obtain the base film with the oriented carbon nano tube. Wherein the insulating smooth substrate comprises a glass plate or the like.
The embodiment of the invention also provides a preparation method of the interfacial polymerization nanofiltration membrane, which comprises the following steps: the interfacial polymerization nanofiltration membrane is prepared by utilizing the base membrane with the oriented carbon nano tubes.
In one possible implementation manner, the preparation method of the carbon nanotube-based film with the high-voltage electric field orientation comprises the following steps of:
adding the carbon nano tube, the membrane additive and the membrane material into an organic solvent, performing ultrasonic dispersion, heating and stirring at 50-70 ℃ for 4-8h to form a uniform membrane casting solution, and performing vacuum defoaming on the membrane casting solution to obtain the membrane casting solution containing the carbon nano tube; alternatively, the mixture was heated and stirred at 60 ℃ for 6 h.
In one possible implementation mode of the preparation method of the carbon nanotube base film with the high-voltage electric field orientation, in the film casting solution, the mass of the carbon nanotube accounts for 0.2-2% of the total mass of the carbon nanotube, the film additive, the film material and the organic solvent; alternatively 0.5-1.5%, 0.5-1% or 1-1.5%.
In one possible implementation manner of the preparation method of the carbon nanotube-based film with the high-voltage electric field orientation, the mass ratio of the carbon nanotubes in the film casting solution to the film additive to the film material is as follows: (0.5-1.5): (0-2): (10-30).
In one possible implementation manner, the high-voltage electric field device comprises a power supply part, a conductive upper polar plate, a conductive lower polar plate, an insulating support column arranged between the conductive upper polar plate and the conductive lower polar plate, and an insulating net rack used for supporting an insulating smooth substrate coated with a casting solution; the insulating support columns are used for supporting the conductive upper polar plate and the conductive lower polar plate, and a cavity capable of accommodating the insulating smooth substrate coated with the casting solution is formed between the conductive upper polar plate and the conductive lower polar plate, and the height of the cavity is 10-30 cm; the insulating net frame is arranged in the cavity; the conductive upper polar plate and the conductive lower polar plate are connected with the power supply part through the conductive electrode. Wherein, the size of the insulating net rack is slightly larger than that of the insulating smooth substrate. When the power supply is switched on, a high-voltage electric field is generated between the conductive upper polar plate and the conductive lower polar plate.
In one possible implementation mode of the preparation method of the oriented carbon nanotube base film with the high-voltage electric field, the power supply part is a direct-current constant-voltage power supply, and the power supply working voltage of the high-voltage electric field device is less than or equal to 30000V; optionally, the working voltage is less than or equal to 20000V, and the working current is less than or equal to 0.02 mA; further alternatively, the operating voltage is 20000V, the operating current is 0.01mA, and the electric field strength ranges from 2000-.
In a possible implementation mode of the preparation method of the base film of the oriented carbon nanotube with the high-voltage electric field, the action time of the high-voltage electric field device is 0.5-5 min.
In one possible implementation mode, the carbon nanotube is a multi-walled carbon nanotube or a single-walled carbon nanotube, the outer diameter of the carbon nanotube is 10-20nm, the length of the carbon nanotube is 10-30 mu m, and the purity of the carbon nanotube is more than or equal to 98 wt%.
In one possible implementation manner of the preparation method of the carbon nanotube-based film with the high-voltage electric field orientation, the film additive comprises at least one of polyvinylpyrrolidone, methyl pyrrolidone, ethanol, lithium chloride and polyethylene glycol.
In a possible implementation manner, the membrane material comprises at least one of polysulfone, polyethersulfone, polyvinylidene fluoride and polyacrylonitrile.
In one possible implementation manner, the organic solvent comprises at least one of N-dimethylformamide, N-dimethylacetamide, methyl pyrrolidone, dimethyl sulfoxide, and hexamethylphosphoramide.
In a possible implementation manner of the preparation method of the oriented carbon nanotube base film with the high-voltage electric field, an ultrasonic dispersion machine performs ultrasonic dispersion for 1-2h, and the ultrasonic power is 100-200W.
In one possible implementation manner, the method for preparing the interfacial polymerization nanofiltration membrane by using the base membrane with the oriented carbon nanotubes comprises the following steps of: interfacial polymerization. The interfacial polymerization method is a commonly used method for preparing the interfacial polymerization nanofiltration membrane.
In one possible implementation manner, the interfacial polymerization method for preparing the nanofiltration membrane comprises the following steps:
respectively preparing an aqueous phase solution and an oil phase solution, and soaking the base membrane with the oriented carbon nano tubes in the prepared aqueous phase solution to obtain the base membrane with the surface covered with the aqueous phase solution; and placing a sealed reaction tank on the upper surface of the membrane, pouring the prepared oil phase solution into the reaction tank, reacting, and taking out the base membrane to obtain the interfacial polymerization nanofiltration membrane. Wherein, in the process, the interfacial polymerization reaction only occurs on the upper surface of the base film.
In a possible implementation manner, the method for preparing the interfacial polymerization nanofiltration membrane by using the base membrane with the oriented carbon nanotubes further comprises the following steps: putting the interfacial polymerization nanofiltration membrane into n-hexane to remove residual solution, then performing thermal curing in a vacuum oven, and putting into deionized water for storage; the heat curing temperature is 60-80 deg.C, optionally 70 deg.C.
In a possible implementation manner, the solute of the aqueous phase solution comprises at least one of m-phenylenediamine, piperazine, diethylenetriamine and triethylene tetramine, and the solvent is water; the solute concentration is 0.2-2 wt%.
In a possible implementation mode, the preparation method of the interfacial polymerization nanofiltration membrane is used for soaking in an aqueous phase solution for 1-10 min.
In a possible implementation manner, the solute of the oil phase solution comprises at least one of benzenedicarboxylic acid dichloride and trimesoyl chloride, and the solvent is n-hexane; the solute concentration is 0.02-0.2 wt%.
In a possible implementation mode, the preparation method of the interfacial polymerization nanofiltration membrane comprises the step of pouring the prepared oil phase solution into a reaction tank, and reacting for 0.5-2 min.
In a possible implementation mode of the preparation method of the interfacial polymerization nanofiltration membrane, the thermal curing time in a vacuum oven is 10-30 min.
In a possible implementation manner, the material of the sealed reaction tank comprises at least one of nylon 66, organic glass, polyether ether ketone or polycarbonate.
The embodiment of the invention also provides the carbon nanotube basement membrane with the high-voltage electric field orientation prepared by the preparation method of the carbon nanotube basement membrane with the high-voltage electric field orientation.
The embodiment of the invention also provides the interfacial polymerization nanofiltration membrane prepared by the preparation method of the interfacial polymerization nanofiltration membrane.
The embodiment of the invention also provides the application of the carbon nanotube base film with the high-voltage electric field orientation in water treatment.
The embodiment of the invention also provides application of the interfacial polymerization nanofiltration membrane in water treatment.
Advantageous effects
(1) According to the preparation method of the carbon nanotube base film with the high-voltage electric field orientation, provided by the embodiment of the invention, the carbon nanotube is polarized under the action of the high-voltage electric field by applying the external high-voltage electric field to the carbon nanotube casting film liquid, so that the entanglement phenomenon is reduced; the two ends of the carbon nano tube induce charges opposite to the upper and lower polar plates, so that torque is generated to enable the carbon nano tube to be oriented along the direction of the electric field; so that the prepared carbon nanotube-based membrane with high piezoelectric orientation has large water flux.
(2) According to the preparation method of the base membrane with the high-voltage electric field oriented carbon nanotubes, the used high-voltage electric field device is provided with the insulating net rack which can support the insulating smooth base plate coated with the casting solution, so that the casting solution is positioned at the position close to the upper polar plate in an electric field, and the carbon nanotubes can move towards the upper polar plate under the action of the electric field force, the probability that the carbon nanotubes appear on the upper surface of the membrane after the base membrane is formed is increased, the probability that the carbon nanotubes exist on the separation layer is increased when the carbon nanotubes appear on the upper surface of the membrane, the carbon nanotubes directly act on the carbon nanotubes of the separation layer, and the characteristic that the smooth inner wall of the carbon nanotubes is used as a water conveying.
(3) According to the preparation method of the interfacial polymerization nanofiltration membrane provided by the embodiment of the invention, the interfacial polymerization nanofiltration membrane is prepared by using the base membrane with the oriented carbon nanotubes, so that the efficiency of water molecules passing through the base membrane is greatly improved, the permeability of the interfacial polymerization nanofiltration membrane is improved, and the selectivity is ensured.
Drawings
One or more embodiments are illustrated by the corresponding figures in the drawings, which are not meant to be limiting. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
FIG. 1 is a schematic diagram of a manufacturing process for an embodiment of the present invention.
FIG. 2 is a cross-sectional view of the aligned carbon nanotube-based film M-1-DC obtained in example 1 of the present invention.
FIG. 3 is a sectional structural view of a non-oriented base film M-1 obtained in comparative example 1 of the present invention.
Fig. 4 is a result of water flux test of inventive experimental example on non/aligned carbon nanotube-based films prepared in example 1 and comparative example 1.
FIG. 5 shows water flux and Na of the interface polymerization nanofiltration membrane prepared in example 2 according to the experimental example of the present invention2SO4Retention test results.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some embodiments, materials, elements, methods, means, and the like that are well known to those skilled in the art are not described in detail in order to not unnecessarily obscure the present invention.
The multi-walled carbon nanotubes used in the following examples had an outer diameter of 20nm, a length of 20 μm, and a purity of 98 wt%;
the polyethersulfone is Ultrason E6020P, and has molecular weight of 58000 Da;
the polyvinylpyrrolidone has a type of K-30 and a molecular weight of 58000 Da.
The high voltage field apparatus used in the following examples:
the device comprises a power supply part, a conductive upper polar plate, a conductive lower polar plate and an insulating support column arranged between the conductive upper polar plate and the conductive lower polar plate; a cavity capable of accommodating the glass plate coated with the membrane casting solution is formed between the upper conductive polar plate and the lower conductive polar plate, and the height of the cavity is 10 cm;
the high-voltage electric field device also comprises a pair of conductive electrodes connected with the power supply part; the conductive electrode is respectively connected with the conductive upper polar plate and the conductive lower polar plate, and when a power supply is switched on, a high-voltage electric field can be generated between the conductive upper polar plate and the conductive lower polar plate;
the high-voltage electric field device is also provided with an insulating net rack which can support the glass plate coated with the casting film liquid, and the insulating net rack is slightly larger than the glass plate;
the power supply part is a direct-current constant-voltage power supply, the working voltage is 20000V, the working current is 0.01mA, and the electric field intensity range is 2000-2100V/cm;
the action time of the high-voltage electric field device is 1 min.
The preparation process of the present invention is schematically shown in FIG. 1, and will be understood by referring to the following specific examples.
Example 1
Respectively preparing non-oriented basement membranes M-0-DC and basement membranes M-0.5-DC, M-1-DC and M-1.5-DC with oriented carbon nanotubes, wherein the difference is that the contents of multi-wall carbon nanotubes are different:
(1) the preparation method of the non-oriented base film M-0-DC comprises the following steps:
0.5g of polyvinylpyrrolidone is dispersed in 41.5g N-N-dimethylacetamide, 8g of polyethersulfone is added into the solution under the stirring state, and the solution is heated and stirred for 6 hours at the temperature of 60 ℃ to form uniform casting solution. Removing bubbles from the casting solution in a vacuum environment, pouring the casting solution on a glass plate at room temperature, uniformly scraping the film on the glass plate by using a 150-micrometer film scraping knife, placing the glass plate in a high-voltage electric field device for 1min, transferring the glass plate into a water solidification bath (15 ℃, and no solvent is volatilized), allowing the film to automatically separate from the glass plate after 0-1min, soaking the glass plate in deionized water for 24h, and ensuring complete phase separation to obtain the non-oriented base film M-0-DC.
(2) The preparation method of the base membrane M-0.5-DC with the oriented carbon nano tube comprises the following steps: the difference of the preparation method of the M-0-DC membrane is only that: 0.25g of multi-walled carbon nanotubes and 0.5g of polyvinylpyrrolidone were dispersed in 41.25g N-N dimethylacetamide under ultrasonic conditions; the ultrasonic power is 100W, and the ultrasonic time is 30 min. "0.5" in M-0.5-DC means that the addition amount of the carbon nanotube (the addition amount of the carbon nanotube means the ratio of the mass of the carbon nanotube to the total mass of the carbon nanotube, the film additive, the film material and the organic solvent) is 0.5%, and the rest is analogized in turn.
(3) The preparation method of the base membrane M-1-DC with the oriented carbon nano tube comprises the following steps: the difference of the preparation method of the M-0.5-DC membrane is only that: 0.5g of multi-walled carbon nanotubes and 0.5g of polyvinylpyrrolidone were dispersed in 41g N-N dimethylacetamide under ultrasonic conditions. The cross-sectional structure of the prepared base film M-1-DC with oriented carbon nanotubes is shown in FIG. 2.
(4) The preparation method of the base membrane M-1.5-DC with the oriented carbon nano tube comprises the following steps: the difference of the preparation method of the M-0-DC membrane is only that: 0.75g of multi-walled carbon nanotubes and 0.5g of polyvinylpyrrolidone were dispersed in 40.75g of N-N dimethylacetamide under ultrasonic conditions.
Comparative example 1
Respectively preparing non-oriented base films M-0, M-0.5, M-1 and M-1.5 with different multi-wall carbon nano-tube contents and without high-voltage electric field treatment;
(1) the preparation method of the M-0 film comprises the following steps:
0.5g of polyvinylpyrrolidone is dispersed in 41.5g N-N-dimethylacetamide, 8g of polyethersulfone is added to the solution under stirring, and the mixture is heated and stirred at 60 ℃ for 6 hours to form a uniform casting solution. Removing bubbles from the casting solution in a vacuum environment, pouring the casting solution on a glass plate at room temperature, uniformly scraping the film on the glass plate by using a 150-micron film scraping knife, placing the glass plate in air for 1min, transferring the glass plate into a water solidification bath (15 ℃, and no solvent is volatilized), automatically separating the film from the glass plate after 0-1min, soaking the glass plate in deionized water for 24h, and ensuring complete phase separation to obtain the M-0 film.
(2) The preparation method of the M-0.5 film comprises the following steps: the difference with the preparation method of the M-0 film is that: 0.25g of multi-walled carbon nanotubes and 0.5g of polyvinylpyrrolidone were dispersed in 41.25g N-N dimethylacetamide under ultrasonic conditions.
(3) The preparation method of the M-1 film comprises the following steps: the difference with the preparation method of the M-0 film is that: 0.5g of multi-walled carbon nanotubes and 0.5g of polyvinylpyrrolidone were dispersed in 41g N-N dimethylacetamide under ultrasonic conditions. The cross-sectional structure of the resulting M-1 film is shown in FIG. 3.
(4) The preparation method of the M-1.5 film comprises the following steps: the difference with the preparation method of the M-0 film is that: 0.75g of multi-walled carbon nanotubes and 0.5g of polyvinylpyrrolidone were dispersed in 40.75g N-N dimethylacetamide under ultrasonic conditions.
Example 2
1. Preparing interface polymerization nanofiltration membranes M-0-DC/PA, M-0.5-DC/PA, M-1-DC/PA and M-1.5-DC/PA respectively by using the non/oriented carbon nanotube base membrane prepared in the example 1:
(1) the preparation method of the M-0-DC/PA interfacial polymerization nanofiltration membrane comprises the following steps:
dissolving 0.4g of piperazine in 20mL of water, and performing ultrasonic dispersion for 10min to obtain an aqueous phase solution; dissolving 0.04g of trimesoyl chloride in 20mL of normal hexane, and performing ultrasonic dispersion for 10min to prepare an oil phase solution;
soaking the M-0-DC obtained in the example 1 in the prepared aqueous phase solution for 5min to obtain a composite membrane with the surface covered with the aqueous phase solution, then placing a sealed reaction tank on the upper surface of the membrane, taking 2mL of the prepared oil phase solution, dripping into the reaction tank to enable interfacial polymerization reaction to only occur on the upper surface of the base membrane, and taking out the base membrane after the reaction is carried out for 1min to obtain an interfacial polymerization nanofiltration membrane; and (3) putting the interfacial polymerization nanofiltration membrane into n-hexane to remove residual solution, then performing heat curing in a vacuum oven at 70 ℃ for 30min to obtain the M-0-DC/PA interfacial polymerization nanofiltration membrane, and finally putting the membrane into deionized water for storage.
(2) The preparation method of the M-0.5-DC/PA interfacial polymerization nanofiltration membrane comprises the following steps: the difference of the preparation method is only that: and changing M-0-DC into M-0.5-DC.
(3) The preparation method of the M-1-DC/PA interfacial polymerization nanofiltration membrane comprises the following steps: the difference of the preparation method is only that: and changing M-0-DC into M-1-DC.
(4) The preparation method of the M-1.5-DC/PA interfacial polymerization nanofiltration membrane comprises the following steps: the difference of the preparation method is only that: the M-0-DC is changed into M-1.5-DC.
The preparation flow chart of the invention is shown in figure 1.
2. Respectively preparing interfacial polymerization nanofiltration membranes M-0/PA, M-0.5/PA, M-1/PA and M-1.5/PA by using the non-oriented base membrane prepared in the comparative example 1:
(1) the preparation method of the M-0/PA interfacial polymerization nanofiltration membrane comprises the following steps: the difference of the preparation method is only that: M-0-DC was replaced with M-0 prepared in comparative example 1.
(2) The preparation method of the M-0.5/PA interfacial polymerization nanofiltration membrane comprises the following steps: the difference of the preparation method is only that: M-0-DC was replaced with M-0.5 prepared in comparative example 1.
(3) The preparation method of the M-1/PA interfacial polymerization nanofiltration membrane comprises the following steps: the difference of the preparation method is only that: M-0-DC was replaced with M-1 prepared in comparative example 1.
(4) The preparation method of the M-1.5/PA interfacial polymerization nanofiltration membrane comprises the following steps: the difference of the preparation method is only that: M-0-DC was replaced with M-1.5 prepared in comparative example 1.
Test examples
1. The water flux test was performed on the non/aligned carbon nanotube-based films prepared in example 1 and comparative example 1:
the experimental results are shown in FIG. 4, and it can be seen from FIG. 4 that: the base film with the aligned carbon nanotubes has higher water flux than its corresponding non-aligned base film. Wherein, the water flux of the basal membrane with the oriented carbon nanotubes is changed along with the different addition of the carbon nanotubes, when the addition of the carbon nanotubes is 1 percent, the water flux of the basal membrane with the oriented carbon nanotubes (M-1-DC) is the largest, and the water flux is obviously superior to that of the corresponding basal membrane without the orientation (M-1); when the addition amount of the carbon nanotubes was increased to 1.5%, the water flux with the oriented carbon nanotube-based film (M-1.5-DC) was slightly superior to that of the corresponding non-oriented base film (M-1.5).
2. Water flux and Na were applied to the interfacially polymerized nanofiltration membrane prepared in example 22SO4Retention test of (2):
the results are shown in fig. 5, and it can be seen from fig. 5 that the water flux of the prepared interfacial polymerization nanofiltration membrane is in an increasing trend along with the increase of the content of the carbon nanotubes in the oriented carbon nanotube-based membrane; the water flux of the interface polymerization nanofiltration membrane prepared by the non-oriented base membrane is generally higher than that of the interface polymerization nanofiltration membrane prepared by the corresponding non-oriented base membrane, the difference shows a rising trend along with the increase of the content of the carbon nano tubes, and the difference is not obvious when the content of the carbon nano tubes is lower.
Meanwhile, Na of the interface polymerization nanofiltration membrane prepared by the oriented carbon nanotube base membrane2SO4The rejection rate of the nano-filtration membrane is generally higher than that of the interface polymerization nano-filtration membrane prepared by the corresponding non-oriented base membrane, and Na2SO4The retention rate of (A) is kept above 94%.
In addition, the water flux and Na of the interface polymerization nanofiltration membrane are further prepared by adding the base membrane obtained by the electric field treatment2SO4The retention rate of the nano-filtration membrane is higher than that of the corresponding interface polymeric nano-filtration membrane further prepared from the base membrane obtained without electric field treatment.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (5)
1. The preparation method of the interfacial polymerization nanofiltration membrane comprises the following steps: adding the carbon nano tube, the membrane additive and the membrane material into an organic solvent, performing ultrasonic dispersion, heating and stirring at 50-70 ℃ for 4-8h to form a uniform membrane casting solution, and performing vacuum defoaming on the membrane casting solution to obtain the membrane casting solution containing the carbon nano tube;
coating the casting solution containing the carbon nano tube on an insulating smooth substrate, putting the insulating smooth substrate into a high-voltage electric field device for acting, and putting the insulating smooth substrate into a water coagulation bath to obtain a base film with the oriented carbon nano tube;
preparing an interfacial polymerization nanofiltration membrane by an interfacial polymerization method: respectively preparing an aqueous phase solution and an oil phase solution, and soaking the base membrane with the oriented carbon nano tubes in the prepared aqueous phase solution to obtain the base membrane with the surface covered with the aqueous phase solution; placing a sealed reaction tank on the upper surface of the membrane, pouring the prepared oil phase solution into the reaction tank for reaction, and taking out the base membrane to obtain an interfacial polymerization nanofiltration membrane; placing the interfacial polymerization nanofiltration membrane into n-hexane to remove residual solution, then performing thermal curing in a vacuum oven for 10-30min, and placing into deionized water for storage; the heat curing temperature is 60-80 ℃;
the high-voltage electric field device comprises a power supply part, a conductive upper polar plate, a conductive lower polar plate, an insulating support column arranged between the conductive upper polar plate and the conductive lower polar plate, and an insulating net rack used for supporting an insulating smooth substrate coated with a casting solution; the insulating support columns are used for supporting the conductive upper polar plate and the conductive lower polar plate, and a cavity capable of accommodating the insulating smooth substrate coated with the casting solution is formed between the conductive upper polar plate and the conductive lower polar plate, and the height of the cavity is 10-30 cm; the insulating net frame is arranged in the cavity; the conductive upper polar plate and the conductive lower polar plate are connected with the power supply part through the conductive electrode; the electric field intensity range is 2000-2800V/cm;
in the film casting solution, the mass of the carbon nano tube accounts for 1-1.5% of the total mass of the carbon nano tube, the film additive, the film material and the organic solvent;
the action time of the high-voltage electric field device is 0.5-5 min;
the solute of the aqueous solution comprises at least one of m-phenylenediamine, piperazine, diethylenetriamine and triethylene tetramine, and the solvent is water; the solute concentration is 0.2-2 wt%; soaking in water phase solution for 1-10 min;
the solute of the oil phase solution comprises at least one of benzene diacid chloride and trimesoyl chloride, and the solvent is n-hexane; the solute concentration is 0.02-0.2 wt%; pouring the prepared oil phase solution into a reaction tank, and reacting for 0.5-2 min.
2. The method of claim 1, wherein: in the casting solution, the mass ratio of the carbon nano tube, the film additive and the film material is as follows: (0.5-1.5): (0-2): (10-30).
3. The method of claim 1, wherein: the carbon nano tube is a multi-wall carbon nano tube or a single-wall carbon nano tube, the outer diameter of the carbon nano tube is 10-20nm, the length of the carbon nano tube is 10-30 mu m, and the purity of the carbon nano tube is more than 98 wt%;
and/or the film additive comprises at least one of polyvinylpyrrolidone, methyl pyrrolidone, ethanol, lithium chloride and polyethylene glycol;
and/or the membrane material comprises at least one of polysulfone, polyethersulfone, polyvinylidene fluoride and polyacrylonitrile;
and/or the organic solvent comprises at least one of N-N-dimethylformamide, N-N-dimethylacetamide, methyl pyrrolidone, dimethyl sulfoxide and hexamethyl phosphoramide;
and/or, ultrasonically dispersing for 1-2h by an ultrasonic dispersion machine, wherein the ultrasonic power is 100-200W.
4. The interface polymeric nanofiltration membrane prepared by the preparation method of claim 1.
5. Use of the interfacially polymerized nanofiltration membrane of claim 4 in water treatment.
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| KR20210088040A (en) | 2020-01-03 | 2021-07-14 | 삼성디스플레이 주식회사 | Glass article and method of manufacturing for the same |
| CN111298666B (en) * | 2020-03-16 | 2020-11-10 | 中国人民解放军火箭军工程设计研究院 | Hollow fiber forward osmosis composite membrane containing oriented carbon nanotubes and preparation method thereof |
| CN111825347A (en) * | 2020-07-03 | 2020-10-27 | 广东工业大学 | Device and method for orienting glass flakes by electric field |
| CN113070022B (en) * | 2021-03-22 | 2023-02-17 | 齐齐哈尔大学 | Batch circulating type ultrathin film unfolding preparation device |
| CN114699925B (en) * | 2022-03-22 | 2024-01-26 | 天津工业大学 | Method for preparing self-cleaning polyvinylidene fluoride piezoelectric ultrafiltration membrane by one-step method |
| CN115368594B (en) * | 2022-09-02 | 2024-01-26 | 哈尔滨工业大学 | Directional carbon-based electric heating composite film and preparation method and application thereof |
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