CN116272431A - Preparation method of ultrafiltration membrane with controllable thickness of humidity sensing small pore layer and ultrafiltration equipment - Google Patents
Preparation method of ultrafiltration membrane with controllable thickness of humidity sensing small pore layer and ultrafiltration equipment Download PDFInfo
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Images
Classifications
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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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/00091—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching by evaporation
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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
- B01D69/02—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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of membrane separation, and relates to a preparation method of an ultrafiltration membrane with controllable thickness of a humidity sensing small pore layer and ultrafiltration equipment. The preparation method comprises the steps of casting a film casting liquid composition containing a hydrophilic additive, pre-evaporating the film casting liquid composition in a high relative humidity environment, and pre-evaporating the film casting liquid composition in a low relative humidity environment, wherein the relative humidity difference between the high relative humidity environment and the low relative humidity environment is not less than 10%. The invention prepares the virus-removing ultrafiltration membrane by matching high humidity with low humidity and regulating and controlling the thicknesses of the macroporous and compact layers, and the ultrafiltration membrane has good interception capability and excellent flux, is prepared by one step in the process, is easy to control, saves the cost, and can provide very good reference meaning and value for the field of virus removal in the future.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a preparation method of an ultrafiltration membrane with a controllable thickness of a humidity sensing small pore layer and ultrafiltration equipment.
Background
The membrane technology is a new technology of contemporary high-efficiency separation, and compared with the traditional distillation, rectification and other technologies, the membrane technology has the advantages of high separation efficiency, low energy consumption, small occupied area and the like, and the core of the membrane separation technology is the separation membrane. Wherein the polymer filter membrane is a separation membrane which is prepared by taking an organic high molecular polymer as a raw material according to a certain process; with the development of petroleum industry and science and technology, the application field of polymer filter membranes is expanding, and the currently applied fields include gas separation, sea water desalination, ultrapure water preparation, sewage and waste treatment, artificial organ manufacturing, medicine, food, agriculture, chemical industry and the like.
The ultrafiltration technology is used as one of membrane separation technologies, and can be used in the fields of wastewater treatment, medical products, food industry and the like due to the characteristics of high flux, mild operation conditions, easy amplification and the like. The polyether sulfone is used as special functional plastic, has excellent oxidation resistance, thermal stability, hydrolysis resistance and good mechanical properties, and plays an important role in the fields of biological medicine and water treatment. Although ultrafiltration membranes have achieved great success in the industry, studies on virus removal ultrafiltration membranes of polyethersulfones have been reported, because the virus removal ultrafiltration membranes require precise pore size design to ensure the virus retention effect and high flow rate to ensure recovery efficiency, while having both of these characteristics is difficult. Therefore, research on the polyethersulfone virus-removal ultrafiltration membrane is very necessary.
Disclosure of Invention
The invention aims to provide a preparation method and ultrafiltration equipment of an ultrafiltration membrane with controllable thickness of a humidity sensing small pore layer, and the specific technical scheme is as follows:
the first aspect of the invention provides a method for preparing an ultrafiltration membrane with controllable thickness of a humidity sensing pore layer, comprising the steps of casting a membrane liquid composition containing a hydrophilic additive, pre-evaporating the membrane liquid composition in a high relative humidity environment and then pre-evaporating the membrane liquid composition in a low relative humidity environment, wherein the difference between the relative humidity of the high relative humidity environment and the relative humidity of the low relative humidity environment is not less than 10%.
Preferably, the casting solution composition is pre-evaporated in an environment with a relative humidity of 80-90% after casting, and then pre-evaporated in an environment with a relative humidity of 55-70%.
More preferably, the casting solution composition is pre-evaporated for 60 seconds or less in an environment with a relative humidity of 80% to 90% after casting, and then pre-evaporated for 180 seconds or less in an environment with a relative humidity of 55% to 70%.
Further, the casting solution composition includes an amorphous polymer, an organic solvent, a hydrophilic polymer, and a hydrophilic additive.
Further, the amorphous polymer comprises polystyrene, polyvinyl chloride, polyethylene terephthalate, polyether, polyvinylidene fluoride and derivatives thereof;
and/or the organic solvent comprises one or more of dimethylformamide, dimethylacetamide, dimethyl sulfoxide, formamide and N-vinyl pyrrolidone; dimethylacetamide is preferred.
Further, the hydrophilic polymer comprises one or more of cuprammocellulose, viscose cellulose, lyocell, diacetylcellulose, triacetylcellulose, polyacrylic acid, polyacrylate, polyethylene glycol methacrylate, polymethacrylate or polyethylene glycol; cellulose acetate is preferred.
And/or the hydrophilic additive comprises one or more of polyethylene glycol, triethylene glycol, polyvinylpyrrolidone, isopropanol or water.
Further, the mass ratio of the amorphous polymer to the organic solvent to the hydrophilic polymer to the hydrophilic additive is (14-25) to (35-55) to (1-10) to (10-40).
Furthermore, the first aspect of the invention provides a preparation method of the ultrafiltration membrane with the controllable thickness of the humidity sensing pore layer, which further comprises the steps of immersing in a coagulating bath for phase separation film formation and drying after pre-evaporation, wherein the coagulating bath time is 0.5-3 min.
The second aspect of the invention provides a virus-removing ultrafiltration membrane prepared by the preparation method provided by the first aspect of the invention.
Further, the virus-removing ultrafiltration membrane comprises a compact layer and a supporting layer, wherein the aperture of the compact layer is 13-56nm, and the aperture of more than 50% of holes is less than or equal to 19nm; preferably, the pore size of the support layer is larger than the pore size of the dense layer.
Further, the ultrafiltration membrane comprises a macroporous layer, a compact layer and a supporting layer, wherein the compact layer is arranged between the macroporous layer and the supporting layer; the pore diameter of the macroporous layer is 56-1000nm, preferably 400-850nm; the aperture of the compact layer is 13-56nm, and the aperture of more than 50% of holes is less than or equal to 19nm; preferably, the macroporous layer has a pore size greater than the pore size of the dense layer, and the support layer has a pore size greater than the pore size of the dense layer.
In some embodiments of the present invention, the virus-removing ultrafiltration membrane provided in the second aspect of the present invention is not limited to the preparation method, and these features may be achieved: the virus-removing ultrafiltration membrane comprises a compact layer and a supporting layer, wherein the aperture of the compact layer is 13-56nm, and the aperture of more than 50% of holes is less than or equal to 19nm; preferably, the pore size of the support layer is larger than the pore size of the dense layer.
In other embodiments of the present invention, the virus-removing ultrafiltration membrane provided in the second aspect of the present invention is not limited to the preparation method, and these features may be achieved: the ultrafiltration membrane comprises a macroporous layer, a compact layer and a supporting layer, wherein the compact layer is arranged between the macroporous layer and the supporting layer; the pore diameter of the macroporous layer is 56-1000nm, preferably 400-850nm; the aperture of the compact layer is 13-56nm, and the aperture of more than 50% of holes is less than or equal to 19nm; preferably, the macroporous layer has a pore size greater than the pore size of the dense layer, and the support layer has a pore size greater than the pore size of the dense layer.
In particular, the second aspect of the invention provides an ultrafiltration membrane with a controllable thickness of a humidity sensing pore layer, which has two different structures. A two-layer distribution structure, which comprises a compact layer and a supporting layer; the first surface is a dense layer with virus entrapment, and extending along the dense layer is a support layer providing strength and capacity extending all the way to the second surface, wherein the pores of the second surface are larger than the pores of the first surface and the pores are continually enlarged; wherein the dense layer has pores ranging from 13 to 56nm, and wherein 50% or more of the pores are 19nm or less, thereby providing sufficient trapping ability. The other is a three-layer distribution structure, comprising a macroporous layer, a compact layer and a supporting layer; the first layer is a macroporous layer having a pore size along the first surface of 56-1000nm, preferably 400-850nm; the second layer is then a dense layer along the macroporous layer, and the third layer is a support layer along the dense layer.
Further, the virus removal ultrafiltration membrane is used for removing viruses in a protein solution, wherein the protein solution comprises immunoglobulin or bovine serum albumin. The retention rate LRV of the virus-removing ultrafiltration membrane on viruses is more than or equal to 4.5, and the recovery rate of the virus-removing ultrafiltration membrane on proteins is more than or equal to 98%.
The third aspect of the invention provides an ultrafiltration device, which comprises the ultrafiltration membrane with controllable thickness of the humidity-sensing small pore layer prepared by the preparation method provided by the first aspect of the invention or the virus-removing ultrafiltration membrane provided by the second aspect of the invention.
The beneficial effects of the invention are as follows: the invention provides a preparation method of an ultrafiltration membrane with controllable thickness of a humidity sensing small pore layer, which is used for preparing an ultrafiltration membrane with excellent virus removal field by regulating and controlling the thicknesses of a large pore layer and a compact layer through matching high humidity and low humidity, and the ultrafiltration membrane has excellent interception capability on performance, is prepared by one step in a process, is easy to control, saves cost and provides very good reference meaning and value for the virus removal field in the future.
Drawings
FIG. 1 is a scanning electron microscope image of a cross section of an ultrafiltration membrane prepared in example 1;
FIG. 2 is a scanning electron microscope image of a cross section of the ultrafiltration membrane prepared in example 3;
FIG. 3 is a scanning electron microscope image of a cross section of the ultrafiltration membrane prepared in example 5;
FIG. 4 is an electron microscope image of the ultrafiltration membrane prepared in comparative example 1.
Detailed Description
The invention provides a preparation method and ultrafiltration equipment of an ultrafiltration membrane with controllable thickness of a humidity sensing small pore layer, and the invention is further described below by combining with examples.
Example 1
Uniformly mixing 16g of polyethersulfone, 54g of dimethylacetamide, 8g of cellulose diacetate and 20g of polyethylene glycol 200, heating and stirring at 80 ℃ for 3 hours until the mixture is uniform, and forming a clear and transparent state at normal temperature; casting the prepared casting film on a metal plate, exposing the metal plate for 1s through a chamber with 80% humidity control, exposing the metal plate for 5s through a chamber with 55% humidity control, immersing the metal plate in a water coagulation bath for 1min, separating phases to form a film, and finally drying to obtain the required ultrafiltration film. FIG. 1 is a scanning electron microscope image of a cross section of an ultrafiltration membrane prepared in example 1; as can be seen from fig. 1, the ultrafiltration membrane prepared in example 1 has a two-layer distribution structure in cross section, the first surface is a dense layer for interception providing the capability of intercepting viruses, and the thickness of the dense layer is 0.94 μm; extending along the dense layer is a support layer that provides strength and capacity to a second surface that is opposite the first surface of the ultrafiltration membrane.
Example 2
Uniformly mixing 16g of polyethersulfone, 54g of dimethylacetamide, 8g of cellulose diacetate and 20g of polyethylene glycol 200, heating and stirring at 80 ℃ for 3 hours until the mixture is uniform, and forming a clear and transparent state at normal temperature; casting the prepared casting film on a metal plate, exposing the metal plate for 1s through a chamber with 80% humidity control, exposing the metal plate for 10s through a chamber with 60% humidity control, immersing the metal plate in a water coagulation bath for 1min, separating phases to form a film, and finally drying to obtain the required ultrafiltration film.
Example 3
Uniformly mixing 16g of polyethersulfone, 54g of dimethylacetamide, 8g of cellulose diacetate and 20g of polyethylene glycol 200, heating and stirring at 80 ℃ for 3 hours until the mixture is uniform, and forming a clear and transparent state at normal temperature; casting the prepared casting film on a metal plate, exposing the metal plate for 1s through a chamber with 80% humidity control, exposing the metal plate for 30s through a chamber with 70% humidity control, immersing the metal plate in a water coagulation bath for 1min, separating phases to form a film, and finally drying to obtain the required ultrafiltration film. FIG. 2 is a scanning electron microscope image of a cross section of the ultrafiltration membrane prepared in example 3; as can be seen from fig. 2, the cross section of the ultrafiltration membrane prepared in example 3 has a two-layer distribution structure, the first surface is a dense layer for interception, which provides the capability of intercepting viruses, and the thickness of the dense layer reaches 3.01 micrometers; extending along the dense layer is a support layer providing strength and capacity to the second surface.
Example 4
Uniformly mixing 16g of polyethersulfone, 54g of dimethylacetamide, 8g of cellulose diacetate and 20g of polyethylene glycol 200, heating and stirring at 80 ℃ for 3 hours until the mixture is uniform, and forming a clear and transparent state at normal temperature; casting the prepared casting film on a metal plate, exposing for 5s through a chamber with 85% humidity control, exposing for 5s through a chamber with 55% humidity control, immersing into a water coagulation bath for 1min, splitting phases for film formation, and finally drying to obtain the required ultrafiltration film.
Example 5
Uniformly mixing 16g of polyethersulfone, 54g of dimethylacetamide, 8g of cellulose diacetate and 20g of polyethylene glycol 200, heating and stirring at 80 ℃ for 3 hours until the mixture is uniform, and forming a clear and transparent state at normal temperature; casting the prepared casting film on a metal plate, regulating and controlling an optimal parameter according to the exposure time of the casting film and the metal plate, exposing the metal plate for 60s through a chamber with 85% humidity control, exposing the metal plate for 180s through a chamber with 60% humidity control, immersing the metal plate in a water coagulation bath for 1min, splitting phases for film formation, and finally drying to obtain the required ultrafiltration film. The scanning electron microscope image of the section of the ultrafiltration membrane is shown in figure 3, 3-a is an enlarged image of a partial section scanning electron microscope image of the ultrafiltration membrane, 3-b is a complete section scanning electron microscope image of the ultrafiltration membrane, and as can be seen from figure 3, the section of the ultrafiltration membrane prepared in the embodiment 5 has a three-layer distribution structure, the first surface is a macroporous layer with the aperture of 56-1000nm, the thickness of the macroporous layer is 7.68um, and the flow velocity can reach 850LMH/2bar; immediately following this is a dense layer that provides viral entrapment capabilities, followed by a support layer that forms the second surface of the ultrafiltration membrane.
Example 6
Uniformly mixing 18g of polyvinylidene fluoride, 40g of dimethylformamide, 10g of cellulose triacetate and 32g of polyethylene glycol 200, heating and stirring at 80 ℃ for 3 hours until the mixture is uniform, and making the mixture in a clear and transparent state at normal temperature; casting the prepared casting film on a metal plate, exposing the metal plate for 3s through a chamber with 85% humidity control, exposing the metal plate for 10s through a chamber with 70% humidity control, immersing the metal plate in a water coagulation bath for 1min, separating phases to form a film, and finally drying to obtain the required ultrafiltration film.
Example 7
Uniformly mixing 14g of polystyrene, 45g of dimethylacetamide, 7g of polymethacrylate and 34g of polyethylene glycol, heating and stirring for 3 hours at 80 ℃ until the mixture is uniform, and forming a clear and transparent state at normal temperature; casting the prepared casting film on a metal plate, exposing the metal plate for 10s through a chamber with 90% humidity control, exposing the metal plate for 15s through a chamber with 55% humidity control, immersing the metal plate in a water coagulation bath for 1min, splitting phases for film formation, and finally drying to obtain the required ultrafiltration film.
Example 8
Uniformly mixing 20g of polyvinyl chloride, 55g of dimethyl sulfoxide, 3g of polyethylene glycol methacrylate and 22g of water, heating and stirring for 3 hours at 80 ℃ until the mixture is uniform, and forming a clear and transparent state at normal temperature; casting the prepared casting film on a metal plate, exposing the metal plate for 7s through a chamber with 90% humidity control, exposing the metal plate for 60s through a chamber with 60% humidity control, immersing the metal plate in a water coagulation bath for 1min, splitting phases for film formation, and finally drying to obtain the required ultrafiltration film.
Example 9
Uniformly mixing 25g of polyethersulfone, 50g of dimethylacetamide, 1g of polyethylene glycol and 24g of polyvinylpyrrolidone, heating and stirring at 80 ℃ for 3 hours until the mixture is uniform, and forming a clear and transparent state at normal temperature; casting the prepared casting film on a metal plate, exposing the metal plate for 1s through a chamber with 90% humidity control, exposing the metal plate for 10s through a chamber with 70% humidity control, immersing the metal plate in a water coagulation bath for 1min, separating phases to form a film, and finally drying to obtain the required ultrafiltration film.
Example 10
Uniformly mixing 21g of polyethylene terephthalate, 48g N-vinyl pyrrolidone, 9g of polyacrylic acid and 30g of triethylene glycol, heating and stirring at 80 ℃ for 3 hours until the mixture is uniform, and making the mixture in a clear and transparent state at normal temperature; casting the prepared casting film on a metal plate, exposing the metal plate for 40s through a chamber with 85% humidity control, exposing the metal plate for 120s through a chamber with 55% humidity control, immersing the metal plate in a water coagulation bath for 1min, separating phases to form a film, and finally drying to obtain the required ultrafiltration film.
Comparative example 1
Uniformly mixing 16g of polyethersulfone, 54g of dimethyl sulfoxide, 8g of cuprammonium cellulose and 20g of polyethylene glycol, heating and stirring for 3 hours at 80 ℃ until the mixture is uniform, and forming a clear and transparent state at normal temperature; casting the prepared casting film on a metal plate, exposing the metal plate for 6s through a chamber with 85% humidity control, finally immersing the metal plate in a water coagulation bath for 1min, separating phases to form a film, and finally drying to obtain the required ultrafiltration film. As shown in the electron microscope image of the ultrafiltration membrane prepared in comparative example 1, as can be seen from the electron microscope image 4, the ultrafiltration membrane prepared in comparative example 1 has no dense layer and no macroporous layer.
Comparative example 2
Uniformly mixing 16g of polyethersulfone, 54g of dimethyl sulfoxide, 8g of cuprammonium cellulose and 20g of polyethylene glycol, heating and stirring for 3 hours at 80 ℃ until the mixture is uniform, and forming a clear and transparent state at normal temperature; casting the prepared casting film on a metal plate, exposing the metal plate for 6s through a chamber with 60% humidity control, finally immersing the metal plate in a water coagulation bath for 1min, separating phases to form a film, and finally drying to obtain the required ultrafiltration film. The performance of the ultrafiltration membrane prepared in comparative example 2 is shown in table 1, and the water flux and recovery rate of the ultrafiltration membrane prepared are low.
The ultrafiltration membranes prepared in examples 1-10, comparative example 1 were tested for membrane water flux, rejection (LRV), and data for rejection of dense layer thickness, macroporous layer thickness, as shown in table 1 below.
The method for testing each index comprises the following steps:
membrane water flux was tested using ultrafiltration cups. In the test, the air pressure was adjusted to 0.4MPa, 50ml of 25℃ultra-pure water was poured into the ultrafilter cup, and the water yield was measured within 1 min. The calculation is shown in the following formula 1:
in formula 1, J w -membrane water flux unit: l/h.times.m 2 The method comprises the steps of carrying out a first treatment on the surface of the V- -sample volume (L); Δt- -sampling time (h); a- -effective area of membrane (m) 2 )。
Interception experiment: the test was performed using a 25mm stainless steel disc filter at a constant pressure of 30Psi, and the data was automatically collected by a computer data acquisition device. The membrane was wetted with ultrapure water. All experiments were started with a buffer solution rinse for 2 to 5 minutes to equilibrate the membranes. The feed liquid is filtered from the open pore side of the membrane. A general purpose feed solution was 1mg/m1 human plasma lgG (Sigma, batch number: SLL 2006) containing 107pfu/mL PP7 (ATCC, batch number: 70039088) buffer system was 50mM acetate, pH 5. The PP7 phage retention challenge test was identified by plaque assay. The permeate was subjected to gradient dilution to determine its titer. LRV is calculated as the logarithm of the ratio of feedstock droplet size to permeate droplet size.
Structural characterization: the membrane structures of the nano-scale polymer filtration membranes obtained in each example and comparative example were morphologically characterized by scanning electron microscopy, and then the thicknesses of the dense layer and the macroporous layer were obtained.
IgG recovery to protein: the ratio of the concentration of IgG in the permeate to that in the raw feed.
TABLE 1
It is found from table 1 that as the exposure time to low humidity increases, the thickness of the dense layer is increased, but the flow rate is also reduced correspondingly; the exposure time of high humidity is increased, so that the thickness of the macroporous layer is increased, and the flow rate is increased; the interception capability is very excellent, and the method can be used in the field of virus removal. Even if the materials are different, the virus-removing ultrafiltration membrane with excellent performance can be prepared by regulating and controlling the exposure time of high and low humidity within a certain range. While comparative example 1 did not have a high and low humidity bond, the scraped film did not have the ability to retain PP7, no dense layer, no macroporous layer.
Claims (15)
1. The preparation method of the ultrafiltration membrane with the controllable thickness of the humidity sensing pore layer is characterized by comprising the steps of casting a membrane liquid composition containing a hydrophilic additive, pre-evaporating the membrane liquid composition in a high relative humidity environment, and pre-evaporating the membrane liquid composition in a low relative humidity environment, wherein the difference between the relative humidity of the high relative humidity environment and the relative humidity of the low relative humidity environment is not less than 10%.
2. The method of claim 1, wherein the casting solution composition is pre-evaporated in an environment having a relative humidity of 80% to 90% after casting, and then pre-evaporated in an environment having a relative humidity of 55% to 70%.
3. The method of claim 2, wherein the casting solution composition is pre-evaporated for less than 60 seconds in an environment with a relative humidity of 80% to 90% and then pre-evaporated for less than 180 seconds in an environment with a relative humidity of 55% to 70% after casting.
4. A method of preparing as claimed in claims 1 to 3 wherein the casting solution composition comprises an amorphous polymer, an organic solvent, a hydrophilic polymer and a hydrophilic additive.
5. The method of claim 4, wherein the amorphous polymer comprises polystyrene, polyvinyl chloride, polyethylene terephthalate, polyethersulfone, polyvinylidene fluoride, and derivatives thereof;
and/or the organic solvent comprises one or more of dimethylformamide, dimethylacetamide, dimethyl sulfoxide, formamide and N-vinyl pyrrolidone.
6. The preparation method according to claim 4, wherein the hydrophilic polymer is one or more of cuprammocellulose, viscose, lyocell, diacetylcellulose, triacetylcellulose, polyacrylic acid, polyacrylate, polyethylene glycol methacrylate, polymethacrylate and polyethylene glycol;
and/or the hydrophilic additive comprises one or more of polyethylene glycol, triethylene glycol, polyvinylpyrrolidone, isopropanol or water.
7. The method according to any one of claims 4 to 6, wherein the mass ratio of the amorphous polymer, the organic solvent, the hydrophilic polymer and the hydrophilic additive is (14-25): (35-55): (1-10): (10-40).
8. The method according to any one of claims 1 to 7, further comprising the steps of phase-separating film formation and drying in a coagulation bath after pre-evaporation, wherein the coagulation bath is for 0.5 to 3 minutes.
9. An ultrafiltration membrane for removing viruses, which is characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. The virus-removing ultrafiltration membrane is characterized by comprising a compact layer and a supporting layer, wherein the aperture of the compact layer is 13-56nm, and the aperture of more than 50% of holes is less than or equal to 19nm; preferably, the pore size of the support layer is larger than the pore size of the dense layer.
11. The virus-removing ultrafiltration membrane is characterized by comprising a macroporous layer, a compact layer and a supporting layer, wherein the compact layer is arranged between the macroporous layer and the supporting layer; the pore diameter of the macroporous layer is 56-1000nm, preferably 400-850nm; the aperture of the compact layer is 13-56nm, and the aperture of more than 50% of holes is less than or equal to 19nm; preferably, the macroporous layer has a pore size greater than the pore size of the dense layer, and the support layer has a pore size greater than the pore size of the dense layer.
12. The virus-removing ultrafiltration membrane according to claim 9, wherein the virus-removing ultrafiltration membrane comprises a compact layer and a supporting layer, the pore diameter of the compact layer is 13-56nm, and the pore diameter of more than 50% of pores is less than or equal to 19nm; preferably, the pore size of the support layer is larger than the pore size of the dense layer.
13. The virus-free ultrafiltration membrane of claim 9, wherein the ultrafiltration membrane comprises a macroporous layer, a dense layer, and a support layer, the dense layer disposed between the macroporous layer and the support layer; the pore diameter of the macroporous layer is 56-1000nm, preferably 400-850nm; the aperture of the compact layer is 13-56nm, and the aperture of more than 50% of holes is less than or equal to 19nm; preferably, the macroporous layer has a pore size greater than the pore size of the dense layer, and the support layer has a pore size greater than the pore size of the dense layer.
14. The virus-removing ultrafiltration membrane according to any one of claims 9 to 13, wherein the virus-removing ultrafiltration membrane is for removing viruses from a protein solution.
15. An ultrafiltration device, comprising the ultrafiltration membrane with controllable thickness of the humidity-sensitive pore layer prepared by the preparation method of any one of claims 1 to 8 or the virus-removing ultrafiltration membrane of any one of claims 9 to 14.
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| CN202311213964.XA CN116943442B (en) | 2023-04-10 | 2023-09-20 | Preparation method of ultrafiltration membrane with controllable thickness of humidity sensing small pore layer and ultrafiltration equipment |
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| DE3740871A1 (en) * | 1986-12-02 | 1988-06-16 | Fuji Photo Film Co Ltd | FINE-POROUS MEMBRANE AND METHOD FOR THEIR PRODUCTION |
| JP2530133B2 (en) * | 1986-12-02 | 1996-09-04 | 富士写真フイルム株式会社 | Microporous membrane |
| US20030038081A1 (en) * | 2001-08-14 | 2003-02-27 | I-Fan Wang | High strength asymmetric cellulosic membrane |
| WO2021083162A1 (en) * | 2019-11-01 | 2021-05-06 | 中国石油化工股份有限公司 | Polymer-based film, preparation method therefor, and use thereof |
| CN112892229A (en) * | 2021-01-27 | 2021-06-04 | 广州中国科学院先进技术研究所 | Virus composite filtering membrane and preparation method thereof |
| KR102525810B1 (en) * | 2021-04-21 | 2023-04-26 | 한국화학연구원 | Porous fluorine resin membrane and method for preparing the same |
| CN115041024A (en) * | 2021-06-02 | 2022-09-13 | 赛普(杭州)过滤科技有限公司 | Preparation method of asymmetric regenerated cellulose virus-removing flat filter membrane and product |
| CN114917764B (en) * | 2022-04-29 | 2023-10-24 | 浙江理工大学 | Method for preparing high-selectivity high-flux PES (polyether sulfone) ultrafiltration membrane by using monomer self-crosslinking |
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