CN113117525A - Amino-functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane as well as preparation method and application thereof - Google Patents

Amino-functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane as well as preparation method and application thereof Download PDF

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CN113117525A
CN113117525A CN201911391509.2A CN201911391509A CN113117525A CN 113117525 A CN113117525 A CN 113117525A CN 201911391509 A CN201911391509 A CN 201911391509A CN 113117525 A CN113117525 A CN 113117525A
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walled carbon
functionalized single
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朱少信
张信花
陈昌伟
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Nanjing Qixiantong Environmental Protection Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D—SEPARATION
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    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • 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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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/68—Polysulfones; Polyethersulfones
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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Abstract

The invention discloses an amino functionalized single-walled carbon nanotube modified film nano composite nanofiltration membrane as well as a preparation method and application thereof. The purified amino functionalized single-walled carbon nanotube and piperazine are mixed to serve as a liquid phase, so that the interfacial polymerization reaction is promoted, and the high-flux thin film nano composite nanofiltration membrane is prepared. The amino functionalized single-walled carbon nano-tubes with different contents are introduced into a thin polyamide selection layer formed on the surface of a polysulfone carrier by optimized piperazine with low monomer concentration and trimesoyl chloride, so that the surface performance and the structure of the polyamide active layer can be accurately adjusted, the whole formation of the polyamide layer is promoted, and the roughness, the hydrophilicity and the surface charge of the membrane are improved. The prepared novel amino functionalized single-walled carbon nanotube modified film nano composite nanofiltration membrane can show excellent water permeability and salt interception capability under the low-pressure operation condition. At the same time, the high performance membrane, which is easy to manufacture, can be mass-produced, also exhibits excellent long-term stability and anti-contamination capability.

Description

Amino-functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane as well as preparation method and application thereof
Technical Field
The invention belongs to the field of membrane water treatment, and particularly relates to an amino functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane, a preparation method thereof and application thereof in nanofiltration separation of divalent salt solution.
Background
In recent decades, as the world population has grown, the standard of living has improved, changes in consumption patterns and the development of irrigation agriculture have greatly increased the demand for fresh water. The purification of various water sources (e.g., seawater, industrial wastewater and other contaminated water) by membrane filtration techniques is an economically efficient method of increasing the fresh water supply. In recent years, nanofiltration membranes have been globally recognized and widely used due to their advantages of high water flux, high rejection rate of divalent ions, easy operation, and long service life. Thin film composite membranes are the most recent nanofiltration membranes, where an ultra-thin polyamide layer is formed by interfacial polymerization on a porous support (e.g., polysulfone or polyethersulfone) as the rejection layer for the selective stop layer, while the underlying support membrane provides sufficient mechanical integrity.
Despite their excellent separation performance, thin film composite nanofiltration membranes still face two major challenges that limit their widespread use: this trade-off between membrane water flux and separation capacity, and high operating pressures (between 6 and 30 bar) to achieve the required water flux. To solve both problems, one possible strategy is to make the selection layer as thin as possible, according to the classical hargen-powayy equation, in order to reduce the resistance to water transport, on the one hand. On the other hand, the hydrophilicity and roughness of the membrane surface may be increased to promote the interaction between the membrane and water molecules, thereby improving permeability. However, it remains a challenge to simultaneously adjust the hydrophilicity, roughness and thickness of the polyamide active layer of the membrane without introducing membrane defects.
In various studies, the introduction of hydrophilic nanomaterials into polyamide layers has proven to be a very potential strategy for designing high efficiency membranes. The surface roughness and free volume of the selective layer can be increased significantly as long as a small amount of nanomaterial is used. Meanwhile, the transport resistance of water is reduced along with the increase of hydrophilicity, so that the performance of the nanofiltration membrane is greatly improved. Among various nanomaterials, carbon nanotubes have been one of the most remarkable research hotspots due to their excellent properties, such as smoothness, regularity, ceramic-like stability, polymer-like flexibility, high mechanical strength, good electrical/thermal properties, electrical conductivity, sterilization and oxidation resistance. However, carbon nanotubes are limited by low hydrophilicity and lack good dispersibility and solubility in many common solvents, as well as weak interfacial interactions with the polymer matrix.
Disclosure of Invention
The invention aims to solve the problems in the prior art, optimize a non-functional group carbon nano tube and a traditional nanofiltration membrane, and provide an amino-functionalized single-wall carbon nano tube modified polyamide nanofiltration membrane, a preparation method thereof and application thereof in nanofiltration separation of divalent salt solution.
In order to achieve the purpose, the invention adopts the technical scheme that:
the amino-functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane consists of a polysulfone supporting layer and a modified polyamide layer, wherein the polysulfone supporting layer is prepared from a polysulfone membrane, and the modified polyamide layer is prepared by preparing a polyamide layer from piperazine hexahydrate and trimesoyl chloride through in-situ interfacial polymerization and then modifying by doping amino-functionalized single-walled carbon nanotube powder.
The thickness of the modified polyamide active layer is 24.7-36.2 nm.
The preparation method of the amino functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane comprises the following steps:
(1) dispersing amino functionalized single-walled carbon nanotubes in piperazine hexahydrate aqueous solution, and ultrasonically dispersing for 60 minutes at room temperature;
(2) sealing the polysulfone membrane on glass, attaching the polysulfone membrane, and immersing the polysulfone membrane in the piperazine hexahydrate aqueous solution obtained in the step (1) for 4-6 minutes;
(3) pouring out the aqueous phase solution in the step (2), sucking excessive aqueous phase droplets on the surface of the polysulfone membrane by using a smooth rolling rod, and completely drying the surface of the polysulfone membrane in the air to obtain a piperazine hexahydrate saturated membrane;
(4) immersing a piperazine hexahydrate saturated membrane into a trimesoyl chloride and n-hexane solution to carry out interfacial polymerization reaction, and heating the prepared membrane at 85 ℃ for 5-10 minutes;
(5) and (4) rinsing the membrane prepared in the step (4) by using deionized water to obtain the needed amino functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane.
Further, the mass concentration of piperazine hexahydrate in the step (1) is 0.6-0.80 wt%, and the preferred mass concentration is 0.75 wt%; the mass concentration of trimesoyl chloride in the step (4) is 0.02-0.04 wt%, and the preferred mass concentration is 0.038 wt%.
The mass concentration of the amino functionalized single-walled carbon nanotube is 0.001-0.01 wt%;
further, the mass concentration of the amino functionalized single-walled carbon nanotube is 0.001, 0.002, 0.005 and 0.01 wt%.
Furthermore, the amino functionalized single-walled carbon nanotube is powder with the purity of more than 95 percent, the diameter of 1-2nm and the length of 1-3 mu m.
Further, the cut-off molecular weight of the polysulfone membrane is 50000 Da.
The optimum purity of the piperazine hexahydrate and trimesoyl chloride selected by the invention is 98 percent.
The purity of the selected n-ethane is more than or equal to 97 percent.
The piperazine and trimesoyl chloride with low monomer concentration used in the invention form an ultrathin polyamide layer (24.7-36.2 nm) on the surface of the polysulfone membrane. In addition, the reaction of the amino group on the amino functionalized single-walled carbon nanotube with the acyl chloride group on trimesoyl chloride makes the polyamide layer more complete, thereby improving the retention capacity.
The amino functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane is applied to nanofiltration separation of divalent salt solution.
The rejection rate and the water flux are two of the evaluation reverse osmosis membranesAn important parameter. The retention rate R (%) is defined as: under certain operating conditions, 1 minus the concentration of solute (C) in the permeatep) With the concentration of solute in the feed liquid (C)f) The ratio is multiplied by 100%.
Figure 746258DEST_PATH_IMAGE002
The water flux is defined as: the volume of water per unit membrane area per unit pressure per unit time under certain operating conditions is L m in the present invention-2 h-1 bar-1。
The nanofiltration membrane pair MgSO finally prepared by the invention4(2000 ppm) a retention of 96.34% was achieved, with an operating pressure of 3.5 bar of 17.8L m-2 h-1 bar-1The water flux of (c).
Has the advantages that:
compared with the prior art, the invention attaches the polar functional group of the amino group on the surface of the carbon nano tube, which not only can effectively improve the dispersibility in water, but also can improve the hydrophilicity, the stability and the chemical compatibility with other polymers, thereby overcoming the defects of the carbon nano tube without the functional group. In the case of water production, a membrane with a larger effective area can provide more adsorption sites and diffusion channels for water, thereby significantly enhancing water transport. In addition, the reaction of the amino groups with the acid chloride groups on trimesoyl chloride results in a more complete polyamide layer and thus in an improved retention capacity. The results show that the prepared membrane has significantly improved stability of desalting performance and antifouling ability, and can be operated at lower pressure.
Drawings
FIG. 1 is a schematic diagram of the preparation of an amino functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane;
FIG. 2 is a scanning electron microscope atlas of amino functionalized single-walled carbon nanotube with the content of 0wt%, 0.001wt%, 0.002wt%, 0.005wt% respectively.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is obvious that the described embodiments are only some embodiments of the present invention, not all 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.
In the following examples or comparative examples, unless otherwise specified, piperazine hexahydrate (PIP) and trimesoyl chloride (TMC) were 98% pure, and n-ethane was 97% pure.
The amino functionalized single-walled carbon nanotube is powder with the purity of more than 95 percent, the diameter is 1-2nm, the length is 1-3 mu m, and the amino functionalized single-walled carbon nanotube is purchased from Nanjing Xiancheng nanometer material science and technology Limited.
Polysulfone membranes have a molecular weight cut-off of 50000Da, available from Deltata technologies, Inc. (Suzhou, China).
Example 1
The invention relates to a preparation method of an amino functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane, which comprises the following steps:
(1) firstly, dispersing amino functionalized single-walled carbon nanotubes (with the mass concentration of 0.001 wt%) in piperazine hexahydrate aqueous solution (with the mass concentration of 0.75 wt%), and performing ultrasonic dispersion for 60 minutes at room temperature;
(2) preparing an active layer of the polyamide nanofiltration membrane by using the amino-functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane through in-situ interfacial polymerization between piperazine hexahydrate and trimesoyl chloride;
(2) after sealing the polysulfone membrane on glass and attaching, immersing the polysulfone membrane in the piperazine hexahydrate aqueous solution in (1) for 5 minutes;
(3) pouring out the aqueous phase solution, sucking off excessive aqueous phase droplets on the surface of the polysulfone membrane by using a smooth rolling rod, and completely drying the surface of the polysulfone membrane in the air to obtain a piperazine hexahydrate saturated membrane;
(4) immersing a piperazine hexahydrate saturated membrane into trimesoyl chloride (mass concentration of 0.038 wt%) and a normal hexane solution for 2 minutes to perform an interfacial polymerization reaction, and heating the prepared membrane at 85 ℃ for 5 minutes;
(5) and finally, rinsing with deionized water to remove unreacted monomers and solvents on the surface of the membrane, thereby obtaining the needed amino functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane.
Initial performance of the membrane against MgSO 5 bar was tested using 2000ppm aqueous sodium sulfate and magnesium sulfate at a pressure of 3.5 bar4And Na2SO4The retention rates of the components are respectively 93.32 percent and 98.01 percent, and the pure water flux is 16.29L m-2 h-1 bar-1。
Example 2
The invention relates to a preparation method of an amino functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane, which comprises the following steps:
(1) firstly, dispersing amino functionalized single-walled carbon nanotubes (with the mass concentration of 0.002 wt%) in piperazine hexahydrate aqueous solution (with the mass concentration of 0.75 wt%), and performing ultrasonic dispersion for 60 minutes at room temperature;
(2) preparing an active layer of the polyamide nanofiltration membrane by using the amino-functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane through in-situ interfacial polymerization between piperazine hexahydrate and trimesoyl chloride;
(2) after sealing the polysulfone membrane on glass and attaching, immersing the polysulfone membrane in the piperazine hexahydrate aqueous solution in (1) for 5 minutes;
(3) pouring out the aqueous phase solution, sucking off excessive aqueous phase droplets on the surface of the polysulfone membrane by using a smooth rolling rod, and completely drying the surface of the polysulfone membrane in the air to obtain a piperazine hexahydrate saturated membrane;
(4) immersing a piperazine hexahydrate saturated membrane into trimesoyl chloride (mass concentration of 0.038 wt%) and a normal hexane solution for 2 minutes to perform an interfacial polymerization reaction, and heating the prepared membrane at 85 ℃ for 5 minutes;
(5) and finally, rinsing with deionized water to remove unreacted monomers and solvents on the surface of the membrane, thereby obtaining the needed amino functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane.
Initial performance of the membrane against MgSO 5 bar was tested using 2000ppm aqueous sodium sulfate and magnesium sulfate at a pressure of 3.5 bar4And Na2SO4The retention rates of the components are 91.00 percent and 96.34 percent respectively, and the pure water flux is 17.8L m-2 h-1 bar-1。
Example 3
The invention relates to a preparation method of an amino functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane, which comprises the following steps:
(1) firstly, dispersing amino functionalized single-walled carbon nanotubes (with the mass concentration of 0.005 wt%) in piperazine hexahydrate aqueous solution (with the mass concentration of 0.75 wt%), and performing ultrasonic dispersion for 60 minutes at room temperature;
(2) preparing an active layer of the polyamide nanofiltration membrane by using the amino-functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane through in-situ interfacial polymerization between piperazine hexahydrate and trimesoyl chloride;
(2) after sealing the polysulfone membrane on glass and attaching, immersing the polysulfone membrane in the piperazine hexahydrate aqueous solution in (1) for 5 minutes;
(3) pouring out the aqueous phase solution, sucking off excessive aqueous phase droplets on the surface of the polysulfone membrane by using a smooth rolling rod, and completely drying the surface of the polysulfone membrane in the air to obtain a piperazine hexahydrate saturated membrane;
(4) immersing a piperazine hexahydrate saturated membrane into trimesoyl chloride (mass concentration of 0.038 wt%) and a normal hexane solution for 2 minutes to perform an interfacial polymerization reaction, and heating the prepared membrane at 85 ℃ for 5 minutes;
(5) and finally, rinsing with deionized water to remove unreacted monomers and solvents on the surface of the membrane, thereby obtaining the needed amino functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane.
Initial performance of the membrane against MgSO 5 bar was tested using 2000ppm aqueous sodium sulfate and magnesium sulfate at a pressure of 3.5 bar4And Na2SO4The retention rates of the filter are 92.43 percent and 97.76 percent respectively, and the pure water flux is 14.76L m-2 h-1 bar-1. Example 4
The invention relates to a preparation method of an amino functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane, which comprises the following steps:
(1) firstly, dispersing amino functionalized single-walled carbon nanotubes (with the mass concentration of 0.01 wt%) in piperazine hexahydrate aqueous solution (with the mass concentration of 0.75 wt%), and performing ultrasonic dispersion for 60 minutes at room temperature;
(2) preparing an active layer of the polyamide nanofiltration membrane by using the amino-functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane through in-situ interfacial polymerization between piperazine hexahydrate and trimesoyl chloride;
(2) after sealing the polysulfone membrane on glass and attaching, immersing the polysulfone membrane in the piperazine hexahydrate aqueous solution in (1) for 5 minutes;
(3) pouring out the aqueous phase solution, sucking off excessive aqueous phase droplets on the surface of the polysulfone membrane by using a smooth rolling rod, and completely drying the surface of the polysulfone membrane in the air to obtain a piperazine hexahydrate saturated membrane;
(4) immersing a piperazine hexahydrate saturated membrane into trimesoyl chloride (mass concentration of 0.038 wt%) and a normal hexane solution for 2 minutes to perform an interfacial polymerization reaction, and heating the prepared membrane at 85 ℃ for 5 minutes;
(5) and finally, rinsing with deionized water to remove unreacted monomers and solvents on the surface of the membrane, thereby obtaining the needed amino functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane.
Initial performance of the membrane against MgSO 5 bar was tested using 2000ppm aqueous sodium sulfate and magnesium sulfate at a pressure of 3.5 bar4And Na2SO4The retention rates of the filter are 92.17 percent and 97.32 percent respectively, and the pure water flux is 14.26L m-2 h-1 bar-1。
According to the application, the optimized low monomer concentration PIP and TMC forms a thin and complete polyamide layer on the surface of the polysulfone membrane, the nano material is embedded to enhance the hydrophilicity and the stain resistance of the membrane, and the amino functionalized single-walled carbon nanotube forms a tubular bulge on the surface of the membrane, so that the water flux of the membrane is greatly improved.
Example 5
Except for the difference from example 2 in that the concentrations of the piperazine hexahydrate aqueous solutions in this example were 0.6wt%, respectively, and the other steps were the same as in example 2, the initial performance of the membrane, which was MgSO 2, was measured at a pressure of 3.5 bar using 2000ppm magnesium sulfate aqueous solution488.23% and pure water flux of 14.26L m-2 h-1 bar-1。
Example 6
The difference from embodiment 2 is that in this embodimentThe concentrations of the piperazine hexahydrate solutions were 0.8% by weight, respectively, and other steps were the same as in example 2, and the initial performance of the membrane, which was subjected to MgSO 5, was measured using 2000ppm of an aqueous solution of magnesium sulfate at a pressure of 3.5 bar487.04%, pure water flux of 12.13L m-2 h-1 bar-1。
Comparative example 1
Except for the difference from example 2 in that the concentrations of the piperazine hexahydrate aqueous solutions in this example were 0.25wt%, respectively, and the other steps were the same as in example 2, the initial performance of the membrane, which was MgSO 2, was measured at a pressure of 3.5 bar using 2000ppm magnesium sulfate aqueous solution485.53% and pure water flux of 10.62L m-2 h-1 bar-1。
Comparative example 2
Except for the difference from example 2 in that the concentrations of the piperazine hexahydrate aqueous solutions in this example were 0.5wt%, respectively, and the other steps were the same as in example 2, the initial performance of the membrane, which was MgSO 2, was measured at a pressure of 3.5 bar using 2000ppm magnesium sulfate aqueous solution482.41%, pure water flux of 11.14L m-2 h-1 bar-1。
Comparative example 3
Except for the difference from example 2 in that the concentrations of the piperazine hexahydrate aqueous solutions in this example were 1.0wt%, respectively, and the other steps were the same as in example 2, the initial performance of the membrane, which was MgSO 2, was measured at a pressure of 3.5 bar using 2000ppm magnesium sulfate aqueous solution497.12%, pure water flux 11.34L m-2 h-1 bar-1。
Comparative example 4
Except for the difference from example 2 in that the purity of piperazine hexahydrate and trimesoyl chloride in this example was 90%, the initial performance of the membrane, which was MgSO 2, was tested at 3.5 bar pressure using 2000ppm aqueous magnesium sulfate solution in the same procedure as in example 2483.21% and pure water flux of 11.86L m-2 h-1 bar-1. Therefore, when the purity of piperazine hexahydrate and trimesoyl chloride is reduced, the integrity of a membrane interception layer is relatively reduced, and the interception rate is greatly reduced.
Example 7 Effect of amino-functionalized Single-walled carbon nanotube content on Membrane hydrophilicity
The contents of amino functionalized single-walled carbon nanotubes are respectively 0wt%, 0.001wt%, 0.002wt%, 0.005wt% and 0.01wt%, and other steps for preparing the film are the same as those of example 1, and the water contact angles are sequentially 44.63 degrees, 41.2 degrees, 36.24 degrees, 31.56 degrees and 30.76 degrees according to the water contact reaction. The higher the content of the amino functionalized single-walled carbon nanotube is, the better the hydrophilicity of the membrane surface is.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (10)

1. The amino-functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane is characterized by comprising a polysulfone supporting layer and a modified amide active layer, wherein the polysulfone supporting layer is prepared from a polysulfone membrane, and the modified polyamide active layer is prepared by preparing a polyamide layer from piperazine hexahydrate and trimesoyl chloride through in-situ interfacial polymerization and then modifying by doping amino-functionalized single-walled carbon nanotube powder.
2. The amino-functionalized single-walled carbon nanotube-modified polyamide nanofiltration membrane according to claim 1, wherein the polyamide layer has a thickness of 24.7 to 36.2 nm.
3. The preparation method of the amino-functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane of claim 1, which is characterized by comprising the following steps:
(1) dispersing amino functionalized single-walled carbon nanotubes in piperazine hexahydrate aqueous solution, and performing ultrasonic dispersion;
(2) sealing the polysulfone membrane on glass, attaching the polysulfone membrane, and immersing the polysulfone membrane in the piperazine hexahydrate aqueous solution obtained in the step (1) for 4-6 minutes;
(3) pouring out the aqueous phase solution in the step (2), sucking off excessive aqueous phase droplets on the surface of the polysulfone membrane, and completely drying the surface of the polysulfone membrane in the air to obtain a piperazine hexahydrate saturated membrane;
(4) immersing a piperazine hexahydrate saturated membrane into a trimesoyl chloride and n-hexane solution to carry out interfacial polymerization reaction, and heating the prepared membrane at 85 ℃ for 5-10 minutes;
(5) and (4) rinsing the membrane prepared in the step (4) by using deionized water to obtain the needed amino functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane.
4. The method according to claim 3, wherein the mass concentration of piperazine hexahydrate in step (1) is 0.6-0.80 wt%, and the mass concentration of trimesoyl chloride in step (4) is 0.02-0.04 wt%.
5. The preparation method of claim 3, wherein the mass concentration of the amino-functionalized single-walled carbon nanotubes is 0.001 to 0.01 wt%.
6. The method of claim 3 wherein the amino functionalized single-walled carbon nanotubes are powder with a purity > 95%, a diameter of 1-2nm and a length of 1-3 μm.
7. The method according to claim 3, wherein the polysulfone membrane has a molecular weight cut-off of 50000 Da.
8. The method according to claim 3, wherein the modified polyamide active layer has a thickness of 24.7 to 36.2 nm.
9. Use of the amino functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane according to claim 1 or 2 in nanofiltration separation of divalent salt solutions.
10. Use according to claim 9, wherein the operating pressure is 3.5 bar.
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