CN112691559A - Preparation method of antibacterial composite PVDF ultrafiltration membrane - Google Patents
Preparation method of antibacterial composite PVDF ultrafiltration membrane Download PDFInfo
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- CN112691559A CN112691559A CN202011142442.1A CN202011142442A CN112691559A CN 112691559 A CN112691559 A CN 112691559A CN 202011142442 A CN202011142442 A CN 202011142442A CN 112691559 A CN112691559 A CN 112691559A
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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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
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- 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
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
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Abstract
The invention relates to the technical field of membrane separation, and provides a preparation method of an antibacterial composite PVDF ultrafiltration membrane. The preparation method comprises the following steps: adding a stabilizer into water, and stirring for dissolving; adding nano silver, stirring and dispersing; then adding Ag-MOF, and performing ultrasonic oscillation to enable the Ag-MOF to fully adsorb the nano silver to obtain an antibacterial dispersion liquid containing an Ag-MOF/nano silver compound; dipping the PVDF-g-PAA ultrafiltration membrane in the antibacterial dispersion liquid, and drying to obtain an antibacterial composite PVDF ultrafiltration membrane; wherein the stabilizer is at least one of gelatin, guar gum, gum arabic and pectin. The antibacterial composite PVDF ultrafiltration membrane prepared by the invention has good hydrophilicity and high mechanical strength, has excellent antibacterial function and can be used in the field of water treatment.
Description
Technical Field
The invention relates to the technical field of membrane separation, in particular to a preparation method of an antibacterial composite PVDF ultrafiltration membrane.
Background
The polymer separation membrane is a material applied to modern high-efficiency separation, concentration, purification and purification equipment, is widely applied to the fields of chemical industry, environmental protection, food, biology, pharmacy, electronics, electric power, metallurgy, light spinning and seawater desalination, and plays an important role in modern energy and resource and solving the problem of environmental pollution. Polyvinylidene fluoride (PVDF), polysulfone, polyvinyl chloride membrane materials and the like are mainly used.
The metal organic framework compounds (MOFs) are materials with supermolecular microporous network structures formed by utilizing the complexation of metal-ligand between organic ligands and metal ions, and have the advantages of high porosity, large specific surface area, convenient synthesis, variable framework scale and size and the like due to the special topological structure, regular internal arrangement and pore channels with specific sizes and shapes, so the metal organic framework compounds are widely applied to the fields of adsorption, catalysis, membrane separation and the like.
For example, CN111135733A discloses a MOFs polymer hollow fiber composite ultrafiltration membrane and a preparation method thereof, wherein a high-strength polyvinylidene fluoride/polyacrylic acid ultrafiltration membrane, namely a PVDF/PAA ultrafiltration membrane, is prepared by a thermally induced phase separation method, and then an ultrathin MOFs separation layer is grown in situ on the outer surface of the separation membrane by a chelation-assisted interface reaction method, which can be applied to the field of water treatment. However, the composite ultrafiltration membrane has no antibacterial function.
At present, in the process of preparing purified water by using an ultrafiltration membrane as a reverse osmosis pretreatment, on one hand, the ultrafiltration membrane can only adsorb proteins, fine microorganisms and the like in drinking water on the surface of the ultrafiltration membrane to prevent the proteins, the fine microorganisms and the like from passing through the ultrafiltration membrane, but cannot kill the proteins, the fine microorganisms and the like, so that the drinking water contains a large number of bacterial microorganisms, and the large number of bacterial microorganisms seriously threaten the health of drinking water of people. Therefore, it is required to develop a method for preparing an ultrafiltration membrane having an antibacterial function.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the preparation method of the antibacterial composite PVDF ultrafiltration membrane, and the obtained composite ultrafiltration membrane simultaneously contains Ag-MOF and nano silver, and has the advantages of excellent antibacterial performance, stable and lasting antibacterial effect and the like.
In order to achieve the above object, the present invention adopts the following technical solutions.
In one aspect, the invention provides a preparation method of an antibacterial composite PVDF ultrafiltration membrane, which comprises the following steps:
(1) preparation of an antibacterial Dispersion
Adding a stabilizer into water, and stirring for dissolving; adding nano silver, stirring and dispersing; then adding Ag-MOF, and performing ultrasonic oscillation to enable the Ag-MOF to fully adsorb the nano silver to obtain an antibacterial dispersion liquid containing an Ag-MOF/nano silver compound;
(2) preparation of antibacterial composite PVDF ultrafiltration membrane
Dipping the PVDF-g-PAA ultrafiltration membrane in the antibacterial dispersion liquid, and drying to obtain an antibacterial composite PVDF ultrafiltration membrane;
wherein the stabilizer is at least one of gelatin, guar gum, gum arabic and pectin.
According to the preparation method of the antibacterial composite PVDF ultrafiltration membrane provided by the invention, on one hand, the stabilizer can prevent the aggregation of nano silver and play a role in stabilizing the nano silver, and meanwhile, hydroxyl contained in the stabilizer can interact with Ag-MOF to play a role in stabilizing the Ag-MOF; on the other hand, Ag-MOF (silver-containing metal organic framework) is used as a carrier of nano silver, so that the dispersibility and stability of the nano silver can be improved, and Ag + in the Ag-MOF and the nano silver have a synergistic antibacterial effect, so that the antibacterial property of the antibacterial agent is more durable and efficient; on the other hand, the PVDF-g-PAA ultrafiltration membrane contains hydroxyl, so that the binding force of the Ag-MOF/nano silver compound and the ultrafiltration membrane can be increased, and carbonyl in the PVDF-g-PAA ultrafiltration membrane can be bonded with the hydroxyl in the stabilizer, so that the binding of the Ag-MOF/nano silver compound and the ultrafiltration membrane is firmer.
As a preferable embodiment of the invention, the mass ratio of the stabilizing agent to water is 1-5:100, and the content of the stabilizing agent is not easy to be too high, so as to prevent the viscosity from being too large after dissolution, which is not beneficial to the dispersion of the subsequent nano silver ions and the mixing of Ag-MOF.
In a preferred embodiment of the present invention, the mass ratio of Ag-MOF to water is 10 to 30: 100.
In a preferred embodiment of the present invention, the mass ratio of the nano silver to the water is 5-10: 100.
Preferably, the average particle size of the nano silver is 1 to 20 nm. The nano silver with smaller average grain diameter can more easily enter bacterial cell membranes, the antibacterial effect is good, and the nano silver with small average grain diameter can be more easily absorbed into the interior of Ag-MOF, so that the antibacterial effect is more durable.
In a preferred embodiment of the present invention, the conditions for dissolving the stabilizer in water by stirring are as follows: stirring and dissolving for 10-40min at 40-60 deg.C.
As a preferred embodiment of the present invention, the conditions for stirring and dispersing the nano silver in water are as follows: stirring and dispersing for 4-12h at 40-60 ℃ and the stirring speed is 1000-10000 rpm.
As a preferred embodiment of the present invention, the Ag-MOF adsorbing nano silver conditions are: ultrasonic vibration is dispersed for 3-6h at 40-60 ℃.
The PVDF is subjected to graft modification by using hydrophilic monomer Acrylic Acid (AA), the modification method can refer to CN105311970A, the PVDF is subjected to alkali treatment and then polymerized with acrylic acid under the action of an initiator to obtain acrylic acid graft-modified PVDF-g-PAA, and then the PVDF-g-PAA ultrafiltration membrane is prepared by a phase separation method; also can refer to CN110975650A, and adopt a one-pot method to prepare a PVDF-g-PAA ultrafiltration membrane; or referring to CN110975649A, irradiation is carried out on PVDF to graft acrylic acid, and then PVDF-g-PAA ultrafiltration membrane is prepared by a phase separation method.
Preferably, the PVDF-g-PAA ultrafiltration membrane has a porosity of 50-80% and a thickness of 100-300 μm.
In a preferred embodiment of the present invention, the PVDF-g-PAA ultrafiltration membrane has a mass ratio of PVDF to PAA of 100:5 to 20, more preferably 100:10 to 20, such as 100:10, 100:11, 100:12, 100:13, 100:14, 100:15, 100:16, 100:17, 100:18, 100:19, 100:20, and the like.
In a preferred embodiment of the present invention, the PVDF-g-PAA ultrafiltration membrane is impregnated with the antibacterial dispersion under the following conditions: soaking at room temperature for 0.5-1h, wherein the soaking can be assisted by vacuumizing.
As a preferred embodiment of the invention, the drying is vacuum drying at 60-100 ℃ for 4-12 h.
On the other hand, the invention provides the antibacterial composite PVDF ultrafiltration membrane prepared by the preparation method.
On the other hand, the invention provides application of the antibacterial composite PVDF ultrafiltration membrane in water treatment.
Compared with the prior art, the invention has the following technical effects:
(1) in the preparation method of the antibacterial composite PVDF ultrafiltration membrane provided by the invention, on one hand, the stabilizer can prevent the aggregation of nano silver and play a role in stabilizing the nano silver, and meanwhile, hydroxyl contained in the stabilizer can interact with Ag-MOF to play a role in stabilizing the Ag-MOF; on the other hand, Ag-MOF (silver-containing metal organic framework) is used as a carrier of nano silver, so that the dispersibility and stability of the nano silver can be improved, and Ag + in the Ag-MOF and the nano silver have a synergistic antibacterial effect, so that the antibacterial property of the antibacterial agent is more durable and efficient; on the other hand, the PVDF-g-PAA ultrafiltration membrane contains hydroxyl, so that the binding force of the Ag-MOF/nano silver compound and the ultrafiltration membrane can be increased, and carbonyl in the PVDF-g-PAA ultrafiltration membrane can be bonded with the hydroxyl in the stabilizer, so that the binding of the Ag-MOF/nano silver compound and the ultrafiltration membrane is firmer.
(2) The antibacterial composite PVDF ultrafiltration membrane prepared by the invention has good hydrophilicity, high mechanical strength and excellent antibacterial performance, can kill bacterial microorganisms in drinking water, and is suitable for the field of water treatment.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety. The term "comprising" or "comprises" is open-ended, i.e. comprising what is specified in the present invention, but not excluding other aspects.
The following is a detailed description of the method for preparing the antibacterial composite PVDF ultrafiltration membrane according to the embodiment provided by the invention.
(1) Preparation of an antibacterial Dispersion
Adding a stabilizer into water, and stirring for dissolving; adding nano silver, stirring and dispersing; and then adding Ag-MOF, and performing ultrasonic oscillation to enable the Ag-MOF to fully adsorb the nano silver, thereby obtaining the antibacterial dispersion liquid containing the Ag-MOF/nano silver compound.
According to an embodiment of the invention, the stabilizer is at least one of gelatin, guar gum, gum arabic, pectin, preferably gelatin.
According to an embodiment of the invention, the mass ratio of the stabilizer to water is 1-5:100, for example: 1:100, 2:100, 3:100, 4:100, 5:100, etc.
According to an embodiment of the present invention, the conditions for dissolving the stabilizer in water by stirring are as follows: stirring and dissolving for 10-40min at 40-60 deg.C.
According to an embodiment of the present invention, the mass ratio of the nano silver to the water is 5-10:100, for example: 5:100, 6:100, 7:100, 8:100, 9:100, 10:100, etc.
According to an embodiment of the present invention, the average particle size of the nano silver is 1 to 20nm, for example: 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, etc.
In some embodiments, the nanosilver has an average particle size of 5 to 20 nm.
According to the embodiment provided by the invention, the conditions for stirring and dispersing the nano silver in the water are as follows: stirring and dispersing for 4-12h at 40-60 ℃ and the stirring speed is 1000-10000 rpm.
In some embodiments, the conditions for stirring and dispersing the nano silver in water are as follows: stirring and dispersing for 4-8h at 40-60 ℃, wherein the stirring speed is 5000-10000 rpm.
The preparation method of the Ag-MOF is not particularly limited, and the Ag-MOF can be prepared according to a method well known in the art, such as a hydrothermal method.
According to the embodiment of the invention, the mass ratio of the Ag-MOF to the water is 10-30: 100, for example: 10:100, 15:100, 20:100, 25:100, 30:100, etc.
According to the embodiment provided by the invention, the conditions for adsorbing the nano silver by the Ag-MOF are as follows: ultrasonic vibration is dispersed for 3-6h at 40-60 ℃.
2. Preparation of antibacterial composite PVDF ultrafiltration membrane
And dipping the PVDF-g-PAA ultrafiltration membrane in the antibacterial dispersion liquid, and drying to obtain the antibacterial composite PVDF ultrafiltration membrane.
According to an embodiment provided by the present invention, the PVDF-g-PAA ultrafiltration membrane has a porosity of 50-80% and a thickness of 100-300 μm.
According to the embodiment provided by the invention, the impregnation is carried out for 0.5-1h at room temperature, and the impregnation can be assisted by vacuumizing.
According to the embodiment provided by the invention, the drying is vacuum drying for 4-12h at 60-100 ℃.
In some embodiments, the drying is vacuum drying at 60-80 ℃ for 4-8 h.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples were carried out under the conditions described in the specification, under the conventional conditions or under the conditions recommended by the manufacturer, unless otherwise specified. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The preparation method of the antibacterial composite PVDF ultrafiltration membrane provided by the embodiment comprises the following steps:
(1) preparation of an antibacterial Dispersion
Adding gelatin and deionized water into deionized water according to the mass ratio of 1:100, and stirring at 50 ℃ for 30min to dissolve the gelatin; adding nano silver with the average particle size of 10nm according to the mass ratio of the nano silver to the water of 5:100, stirring and dispersing for 4 hours at 50 ℃ at the stirring speed of 5000rpm to fully and uniformly disperse the nano silver; then adding Ag-MOF according to the mass ratio of the Ag-MOF to the water of 20:100, and carrying out ultrasonic oscillation at 45 ℃ for 5 hours to enable the Ag-MOF to fully adsorb the nano silver, thereby obtaining the antibacterial dispersion liquid containing the Ag-MOF/nano silver compound.
(2) Preparation of antibacterial composite PVDF ultrafiltration membrane
And (3) dipping the PVDF-g-PAA ultrafiltration membrane (the mass ratio of PVDF to PAA is 100:10) in the antibacterial dispersion liquid for 40min at room temperature, and then drying in vacuum at 85 ℃ for 6h to obtain the antibacterial composite PVDF ultrafiltration membrane.
Example 2
The preparation method of the antibacterial composite PVDF ultrafiltration membrane provided by the embodiment is different from the preparation method of the antibacterial composite PVDF ultrafiltration membrane provided by the embodiment 1 in that: the mass ratio of the gelatin to the deionized water is 3: 100.
Example 3
The preparation method of the antibacterial composite PVDF ultrafiltration membrane provided by the embodiment is different from the preparation method of the antibacterial composite PVDF ultrafiltration membrane provided by the embodiment 1 in that: the mass ratio of the gelatin to the deionized water is 5: 100.
Example 4
The preparation method of the antibacterial composite PVDF ultrafiltration membrane provided by the embodiment is different from the preparation method of the antibacterial composite PVDF ultrafiltration membrane provided by the embodiment 2 in that: the mass ratio of the nano silver to the water is 10: 100.
Comparative example 1
The preparation method of the antibacterial composite PVDF ultrafiltration membrane provided by the comparative example is different from that of the example 2 in that: gelatin as a stabilizer was not added.
Comparative example 2
The preparation method of the antibacterial composite PVDF ultrafiltration membrane provided by the comparative example is different from that of the example 2 in that: in the step (2), a PVDF ultrafiltration membrane is used for replacing a PVDF-g-PAA ultrafiltration membrane.
Performance testing
1. Water flux test
Placing the prepared composite ultrafiltration membrane in deionized water for a period of time, shearing a circular membrane with the diameter of 7.5cm, placing the circular membrane into an YL-300 ultrafiltration cup, prepressing for 40min under the pressure of 0.1MPa until the water flux is basically stable, and then measuring under the pressure of 0.1MPa, wherein the test results are shown in Table 1.
2. Anti-pollution Performance test
The test was carried out using an ultraviolet-visible-infrared spectrophotometer, and external pressure measurement was carried out at 0.1MPa, using bovine serum albumin having a molecular weight of 80000 at 1g/L as a test object. The retention rate of the ultrafiltration membrane is determined by testing the residue of bovine serum albumin on the membrane. Retention rateWherein C ispAs the concentration of bovine serum albumin in the feed water, CfThe results are shown in Table 1 for the concentration of bovine serum albumin in the purified water.
3. Hydrophilic Property test
The contact angle of the prepared ultrafiltration membrane with water was measured by a contact angle tester, and the test results are shown in table 1.
4. Tensile strength
The tensile strength of the prepared ultrafiltration membrane was tested using a universal material tensile machine, and the test results are shown in table 1.
5. Test of antibacterial Property
Escherichia coli is used as indicator bacteria, the filtered solution of the prepared membrane is cultured, the number of the Escherichia coli in the filtered solution is calculated by a plate counting method, the antibacterial rate is calculated, and the test result is shown in table 1.
TABLE 1
Example one another | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 |
Pure water flux (L/m)2·h) | 277 | 273 | 271 | 275 | 274 | 213 |
Retention (%) | 95.7 | 94.6 | 93.7 | 94.3 | 96.1 | 86.7 |
Contact angle (°) | 43.8 | 43.2 | 42.7 | 43.6 | 53.8 | 60.3 |
Tensile Strength (MPa) | 5.02 | 5.19 | 5.37 | 5.13 | 3.19 | 3.27 |
Antibacterial ratio (E.coli%) | 99.97 | 99.98 | 99.98 | 99.99 | 80.13 | 85.87 |
As can be seen from the data in Table 1, the antibacterial composite PVDF ultrafiltration membrane obtained in the embodiment of the invention has the advantages of good hydrophilicity, large water flux, high rejection rate, good pollution resistance, excellent antibacterial performance and excellent mechanical performance.
In the comparative example 1, no stabilizer is added into the anti-averaging dispersion liquid, nano silver is easy to agglomerate, the stability of Ag-MOF is poor, and the nano silver is not sufficiently adsorbed, so that the antibacterial performance, the hydrophilic performance and the mechanical performance of the ultrafiltration membrane are greatly reduced.
In comparative example 2, since the PVDF ultrafiltration membrane was not modified to contain hydroxyl and carboxyl, the binding force with the Ag-MOF/nano silver complex was poor, and both the hydrophilic property and the mechanical property of the obtained ultrafiltration membrane were deteriorated.
In the description herein, references to the description of the terms "some embodiments," "other embodiments," "an embodiment," "an example," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention and examples have been shown and described above, it is understood that the above embodiments, examples are illustrative and not to be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments, examples by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A preparation method of an antibacterial composite PVDF ultrafiltration membrane is characterized by comprising the following steps:
(1) preparation of an antibacterial Dispersion
Adding a stabilizer into water, and stirring for dissolving; adding nano silver, stirring and dispersing; then adding Ag-MOF, and performing ultrasonic oscillation to enable the Ag-MOF to fully adsorb the nano silver to obtain an antibacterial dispersion liquid containing an Ag-MOF/nano silver compound;
(2) preparation of antibacterial composite PVDF ultrafiltration membrane
Dipping the PVDF-g-PAA ultrafiltration membrane in the antibacterial dispersion liquid, and drying to obtain an antibacterial composite PVDF ultrafiltration membrane;
wherein the stabilizer is at least one of gelatin, guar gum, gum arabic and pectin.
2. The method for preparing the antibacterial composite PVDF ultrafiltration membrane according to claim 1, wherein in the PVDF-g-PAA ultrafiltration membrane, the mass ratio of PVDF to PAA is 100: 5-20.
3. The preparation method of the antibacterial composite PVDF ultrafiltration membrane according to claim 1, wherein the mass ratio of the stabilizer to water is 1-5: 100; the mass ratio of the Ag-MOF to the water is 10-30: 100.
4. The preparation method of the antibacterial composite PVDF ultrafiltration membrane according to claim 1, wherein the mass ratio of the nano silver to the water is 5-10: 100; the average grain diameter of the nano silver is 1-20 nm.
5. The preparation method of the antibacterial composite PVDF ultrafiltration membrane according to claim 1, wherein the stirring and dissolving conditions are as follows: stirring and dissolving for 10-40min at 40-60 deg.C.
6. The preparation method of the antibacterial composite PVDF ultrafiltration membrane according to claim 1, wherein the stirring and dispersing conditions are as follows: stirring and dispersing for 4-12h at 40-60 ℃ and the stirring speed is 1000-10000 rpm.
7. The preparation method of the antibacterial composite PVDF ultrafiltration membrane according to claim 1, wherein the ultrasonic oscillation condition is as follows: ultrasonic vibration is dispersed for 3-6h at 40-60 ℃.
8. The preparation method of the antibacterial composite PVDF ultrafiltration membrane according to claim 1, wherein the impregnation is carried out at room temperature for 0.5-1 h; the drying is vacuum drying at 60-100 ℃ for 4-12 h.
9. The antibacterial composite PVDF ultrafiltration membrane obtained by the preparation method of any one of claims 1-8.
10. The use of the antimicrobial composite PVDF ultrafiltration membrane of claim 9 in water treatment.
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CN114887494A (en) * | 2022-06-14 | 2022-08-12 | 西北农林科技大学 | Preparation method and application of metal ion leaching-free response release type MIL-53 modified membrane |
CN115253730A (en) * | 2022-09-05 | 2022-11-01 | 江西国膜环保科技有限公司 | Preparation method of ultrafiltration membrane |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN114887494A (en) * | 2022-06-14 | 2022-08-12 | 西北农林科技大学 | Preparation method and application of metal ion leaching-free response release type MIL-53 modified membrane |
CN114887494B (en) * | 2022-06-14 | 2024-02-13 | 西北农林科技大学 | Preparation method and application of metal ion leaching-free release-type MIL-53 modified membrane |
CN115253730A (en) * | 2022-09-05 | 2022-11-01 | 江西国膜环保科技有限公司 | Preparation method of ultrafiltration membrane |
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