CN112870988B - Air-permeable roller, liquid dropping hole discharging device and preparation method of nanofiber composite membrane - Google Patents
Air-permeable roller, liquid dropping hole discharging device and preparation method of nanofiber composite membrane Download PDFInfo
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- CN112870988B CN112870988B CN202011636375.9A CN202011636375A CN112870988B CN 112870988 B CN112870988 B CN 112870988B CN 202011636375 A CN202011636375 A CN 202011636375A CN 112870988 B CN112870988 B CN 112870988B
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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
- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0095—Drying
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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
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/39—Electrospinning
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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
- B01D2325/24—Mechanical properties, e.g. strength
Abstract
The invention provides a breathable roller, a dropping liquid hole-discharging device and a preparation method of a nanofiber composite membrane. The method adopts non-contact liquid feeding without damaging the pore structure of the nanofiber membrane, and the finally obtained nanofiber composite membrane keeps excellent filtering performance and has higher mechanical strength.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a breathable roller, a liquid drop hole discharging device and a preparation method of a nanofiber composite membrane.
Background
At present, water resources are increasingly in short supply, and the purification and the reutilization of the aqueous solution are particularly important. The water solution purification and filtration such as seawater desalination, sewage and wastewater treatment and the like all need to use high-efficiency and energy-saving membrane materials. Compared with the traditional water treatment method, the membrane method water treatment technology has the advantages of low cost, high separation precision, low investment, easy operation and management, small secondary pollution to the environment and the like, has good application prospect in the treatment and recycling of purified water and sewage, and the membrane method water treatment gradually becomes the development trend of the market.
The following types of membranes are mainly used at present: microfiltration Membranes (MF), ultrafiltration membranes (UF), nanofiltration membranes (NF), reverse osmosis membranes (RO), and the like. The filtration precision of the microfiltration Membrane (MF) is 0.1-10 μm, and suspended particles, bacteria, partial viruses and large-scale colloid can be removed; the ultrafiltration membrane (UF) has a filtration precision of 0.002-0.1 μm, and can be used for removing colloid, protein, microorganism and macromolecular organic substances; the filtering precision of the nanofiltration membrane (NF) is 0.001-0.003 mu m, and the NF is used for removing multivalent ions, partial monovalent ions and organic matters with the molecular weight of 200-1000D; the reverse osmosis membrane (RO) has a filtration precision of 0.0004-0.0006 μm and is used for removing soluble salts and organic substances with molecular weight greater than 100D. In the practical use process of various commercial membranes, in order to achieve higher water flux without damaging the membrane structure, namely, more liquid to be treated passes through the membrane, a working static pressure difference is required to be provided on two sides of the membrane, and as the filtration precision of the treatment membrane is improved, the pore diameter on the membrane is smaller and smaller, and the required operation pressure is larger and larger. The operating pressure of the micro-filtration Membrane (MF) is 0.01-0.1MPa, the operating pressure of the ultra-filtration membrane (UF) and the nano-filtration membrane (NF) is 0.1-0.5MPa, and the operating pressure of the reverse osmosis membrane (RO) is up to 1-10 MPa. These operating pressures not only make the operation flow more complicated, increase the energy consumption of the treatment process, but also have certain influence on the service life of the membrane.
Electrospun nanofiber membranes have their unique advantages over traditional commercial membranes. For example, the coating on the electrostatic spinning nanofiber base film is easy to realize, and the coating is smooth and has good quality; the diameter of the nano fiber is adjustable within the range of dozens to hundreds of nanometers; the pore diameter distribution is uniform, and the size can be freely adjusted, so that the filtration precision from the microfiltration membrane to the nanofiltration membrane is adjusted and controlled; most importantly, the porosity is high, the pore structures are communicated with each other, the flow of fluid in the pore structures is facilitated, the water flux of the film is obviously improved, and the water flux of the electrostatic spinning nanofiber non-woven fabric substrate is 1000-10000 times higher than that of a base film used by a traditional composite film. To sum up, the nanofiber membrane can effectively overcome the problem that the traditional commercial membrane is difficult to operate on the premise of ensuring the filtration precision. However, electrospun nanofibers generally have thin film thicknesses and lack sufficient mechanical strength, and therefore, there are still some problems to be solved during practical use.
The invention patent with the patent application number of CN201410457668.9 discloses a nanofiber membrane, which is obtained by electrostatic spinning of a mixture; the mixture includes a thermoplastic elastomer and a solvent. The nanofiber membrane provided by the invention is obtained by adopting the thermoplastic elastomer as the main raw material through electrostatic spinning, and can have higher strength without hot pressing after the electrostatic spinning, so that the phenomenon of hole blocking in the hot pressing process is avoided, and the obtained nanofiber membrane has better air permeability, the strength of the nanofiber membrane provided by the invention can reach 42MPa at most, and the elongation at break can reach about 470 percent, but the strength of the nanofiber membrane mainly depends on the thickness of the fiber membrane, and the material is the thermoplastic elastomer, so that the nanofiber membrane is an improvement on the material, the preparation method is complex, and the investment cost is higher.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a nanofiber composite membrane, which solves the problem of mechanical strength when an electrostatic spinning nanofiber membrane with excellent filtering performance is used for actual water treatment. The mechanical strength of the nanofiber composite membrane prepared by the method is mainly provided by the substrate, the thickness of the fiber membrane can be any, the strength of the substrate can be freely selected according to the using conditions, and the substrate is generally required to be more than 20N/m.
The utility model provides a ventilative roller, includes hollow cylinder, and hollow cylinder surface distributes has a plurality of through-holes, and the both ends of hollow cylinder are sealed the back and the tubular metal resonator intercommunication each other, tubular metal resonator outer end and vacuum pump connection.
Preferably, the through holes are regularly arranged at intervals, the diameter of each through hole is 0.1-5mm, and the distance between every two adjacent through holes is 5-30 mm.
In any of the above schemes, preferably, the diameter of the through hole is 0.1mm, and the distance between the adjacent through holes is 5 mm.
In any of the above schemes, preferably, the diameter of the through holes is 1mm, and the distance between adjacent through holes is 6 mm.
In any of the above schemes, preferably, the diameter of the through holes is 2mm, and the distance between adjacent through holes is 8 mm.
In any of the above schemes, preferably, the diameter of the through holes is 3mm, and the distance between adjacent through holes is 10 mm.
In any of the above embodiments, preferably, the diameter of the through holes is 4mm, and the distance between adjacent through holes is 20 mm.
In any of the above embodiments, preferably, the diameter of the through holes is 5mm, and the distance between adjacent through holes is 30 mm.
In any of the above embodiments, preferably, the ratio of the diameter of the metal tube to the diameter of the hollow cylinder is 1:3 to 10.
In any of the above embodiments, preferably, the ratio of the diameter of the metal tube to the diameter of the hollow cylinder is 1: 3.
In any of the above embodiments, preferably, the diameter ratio of the metal tube to the hollow cylinder is 1: 4.
In any of the above embodiments, preferably, the ratio of the diameter of the metal tube to the diameter of the hollow cylinder is 1: 5.
In any of the above embodiments, preferably, the ratio of the diameter of the metal tube to the diameter of the hollow cylinder is 1: 8.
In any of the above embodiments, preferably, the diameter ratio of the metal tube to the hollow cylinder is 1: 10.
The invention also provides a liquid dropping hole discharging device which comprises a liquid storage tank, wherein one end of the liquid storage tank is communicated with a liquid inlet pipe, the other end of the liquid storage tank is communicated with a liquid outlet pipe, one side of the liquid storage tank is provided with a liquid homogenizing tank, the other side of the liquid storage tank is provided with a flow control valve, the distance between the flow control valve and the liquid storage tank is h, the caliber of the liquid homogenizing tank is smaller than that of the liquid storage tank, one side of the liquid homogenizing tank is provided with a plurality of liquid dropping holes, and the liquid feeding speed is adjusted by adjusting the liquid inlet speed of the liquid inlet pipe and the distance of h.
Preferably, the distance between the adjacent dropping holes is 2mm-10 mm.
In any of the above embodiments, preferably, the distance between the adjacent drip holes is 2 mm.
In any of the above solutions, preferably, the distance between the adjacent drip holes is 5 mm.
In any of the above solutions, preferably, the distance between the adjacent drip holes is 10 mm.
In any of the above embodiments, preferably, the reservoir is at least one of a rectangular tank, a polygonal tank, and a circular tank.
In any of the above embodiments, the liquid homogenizing tank is preferably at least one of a rectangular tank, a polygonal tank, and a circular tank.
In any of the above schemes, preferably, the liquid homogenizing tank and the liquid storage tank are concentrically arranged.
In any of the above schemes, preferably, the liquid homogenizing tank and the liquid storage tank are of an integrated structure.
The invention also provides a preparation method of the nanofiber composite membrane, which comprises the following steps:
(1) compounding: depositing at least one layer of nanofiber film on a substrate by an electrostatic spinning technology to form nanofiber composite cloth;
(2) bonding: covering the nanofiber composite cloth obtained in the step (1) on a breathable roller, and dropwise adding an adhesive solution through a dropping hole discharging device to adhere the nanofiber film and the substrate;
(3) and (3) drying: and blowing the nanofiber composite cloth by using dry air to dry the nanofiber composite cloth.
Preferably, the substrate base material in the step (1) is at least one of non-woven fabric, woven fabric or paper.
Preferably, in any of the above schemes, the ventilation roller in the step (2) comprises a hollow cylinder, a plurality of through holes are distributed on the surface of the hollow cylinder, the two ends of the hollow cylinder are mutually communicated with the metal pipe after being sealed, and the outer end of the metal pipe is connected with the vacuum pump.
Preferably, in any of the above schemes, the plurality of through holes are regularly arranged at intervals, the diameter of each through hole is 0.1-5mm, and the distance between every two adjacent through holes is 5-30 mm.
In any of the above embodiments, preferably, the diameter of the through hole is 0.1, and the distance between adjacent through holes is 5 mm.
In any of the above schemes, preferably, the diameter of the through holes is 1mm, and the distance between adjacent through holes is 6 mm.
In any of the above schemes, preferably, the diameter of the through holes is 2mm, and the distance between adjacent through holes is 8 mm.
In any of the above schemes, preferably, the diameter of the through holes is 3mm, and the distance between adjacent through holes is 10 mm.
In any of the above embodiments, preferably, the diameter of the through holes is 4mm, and the distance between adjacent through holes is 20 mm.
In any of the above embodiments, preferably, the diameter of the through holes is 5mm, and the distance between adjacent through holes is 30 mm.
In any of the above embodiments, preferably, the diameter ratio of the metal tube to the hollow cylinder is 1:3 to 10.
In any of the above embodiments, preferably, the diameter ratio of the metal tube to the hollow cylinder is 1: 3.
In any of the above embodiments, preferably, the diameter ratio of the metal tube to the hollow cylinder is 1: 4.
In any of the above embodiments, preferably, the diameter ratio of the metal tube to the hollow cylinder is 1: 5.
In any of the above embodiments, preferably, the diameter ratio of the metal tube to the hollow cylinder is 1: 8.
In any of the above embodiments, preferably, the ratio of the diameter of the metal tube to the diameter of the hollow cylinder is 1: 10.
The preferable of any one of the above schemes is that the liquid dropping hole discharging device in the step (2) comprises a liquid storage tank, one end of the liquid storage tank is communicated with a liquid inlet pipe, the other end of the liquid storage tank is communicated with a liquid outlet pipe, one side of the liquid storage tank is provided with a liquid homogenizing tank, the other side of the liquid storage tank is provided with a flow control valve, the distance between the flow control valve and the liquid storage tank is h, the caliber of the liquid homogenizing tank is smaller than that of the liquid storage tank, one side of the liquid homogenizing tank is provided with a plurality of liquid dropping holes, and the liquid feeding speed is adjusted by adjusting the liquid inlet speed of the liquid inlet pipe and the distance of h.
In any of the above solutions, preferably, the distance between the adjacent drip holes is 2mm to 10 mm.
In any of the above embodiments, preferably, the distance between the adjacent drip holes is 2 mm.
In any of the above embodiments, preferably, the distance between the adjacent drip holes is 5 mm.
In any of the above solutions, preferably, the distance between the adjacent drip holes is 10 mm.
In any of the above embodiments, preferably, the liquid storage tank is at least one of a rectangular tank, a polygonal tank, and a circular tank.
In any of the above embodiments, preferably, the liquid homogenizing tank is at least one of a rectangular tank, a polygonal tank, and a circular tank.
In any of the above schemes, preferably, the homogenizing tank and the liquid storage tank are concentrically arranged.
In any of the above schemes, preferably, the liquid homogenizing tank and the liquid storage tank are of an integrated structure.
Preferably, in any of the above schemes, the dropping liquid hole discharging device is arranged on one side of the air permeable roller in the step (2), the dropping liquid hole side of the dropping liquid hole discharging device and the air permeable roller are arranged at a short distance, and the nanofiber film and the substrate pass through a gap between the dropping liquid hole and the air permeable roller.
In any of the above embodiments, the concentration of the binding solution in the step (2) is preferably 0.01 to 3%.
In any of the above embodiments, the concentration of the binding solution in the step (2) is preferably 0.01%.
In any of the above embodiments, the concentration of the binding solution in the step (2) is preferably 1%.
In any of the above embodiments, the concentration of the binding solution in the step (2) is preferably 2%.
In any of the above embodiments, the concentration of the binding solution in the step (2) is preferably 3%.
In any of the above schemes, preferably, the bonding solution in step (2) is any one or a mixture of two or more of a sodium polyacrylate solution, a polyacrylic acid solution, a polyvinyl chloride solution, a polyvinyl butyral solution, a polystyrene solution, a polymethyl methacrylate solution, a polyurethane solution, a polycarbonate solution, a polylactide solution, a polyvinyl alcohol solution, a polycaprolactone solution, a polyvinylpyrrolidone solution, a polyamide solution, and a polyethylene glycol solution.
In any of the above embodiments, preferably, in the step (3), the temperature of the drying air is 20 to 90 ℃, and the blowing flow rate of the drying air is 2 to 200 cm/s.
In any of the above embodiments, preferably, in the step (3), the temperature of the drying air is 30 to 80 ℃, and the blowing flow rate of the drying air is 5 to 180 cm/s.
In any of the above embodiments, preferably, in the step (3), the temperature of the drying air is 20 ℃ and the blowing flow rate of the drying air is 200 cm/s.
In any of the above embodiments, it is preferable that the temperature of the drying air in the step (3) is 40 ℃ and the blowing flow rate of the drying air is 100 cm/s.
In any of the above embodiments, preferably, in the step (3), the temperature of the drying air is 90 ℃, and the blowing flow rate of the drying air is 2 cm/s.
The invention deposits the nano-fiber film with excellent filtering performance but poor mechanical strength on the substrate with excellent mechanical performance and larger pores by the electrostatic spinning technology, and compounds the two materials to form the nano-fiber composite cloth. Since the nanofiber membrane and the substrate are merely compounded together by physical deposition through electrospinning, the combination between the two is very weak and easy to delaminate, and therefore, a bonding solution is required to further bond the two together. However, the use of the bonding solution often affects the air permeability of the nanofiber membrane, so that the nanofiber composite cloth is contacted and coated on the upper surface of the air permeable roller, in order to ensure that the bonding effect is good enough, the sufficient bonding solution is uniformly dripped from the upper part of the cloth to the surface of the cloth through the liquid dripping hole discharging device, and after the solution is dripped on the composite cloth, the solution can permeate the composite cloth and uniformly coat the fiber surface in the composite cloth due to the negative pressure effect in the air permeable roller, so that the nanofiber membrane and the substrate are effectively bonded, and meanwhile, the excessive bonding solution possibly generated in the bonding process and permeating the composite cloth can also enter the air permeable roller under the negative pressure effect, thereby avoiding the influence on the filtering performance of the nanofiber composite membrane caused by the residual excessive bonding solution in the gap in the nanofiber composite membrane. And finally, blowing the nanofiber composite cloth by using dry air to dry the nanofiber composite cloth, so that the finally obtained nanofiber composite membrane keeps excellent filtering performance and has higher mechanical strength.
The invention has the following beneficial effects:
(1) the invention ensures the effective adhesion between the nanofiber membrane and the substrate through supplying the adhesive solution in sufficient quantity, thereby improving the overall strength of the composite membrane;
(2) the ventilation roller is used, and the negative pressure is arranged in the ventilation roller, so that the bonding solution can fully permeate into the nanofiber composite cloth, and the influence on the filtering performance caused by the excessive bonding solution remained in the gaps of the nanofiber composite cloth can be prevented;
(3) the bonding solution is wrapped on the surface of the fiber, and after the fiber is dried, the overall strength of the composite membrane is improved; the surface adsorption activity of the fiber membrane is reduced, and the membrane material is prevented from being adhered to other contact surfaces to cause damage;
(4) the upper row holes slowly and repeatedly close the membrane surface to drop liquid, the liquid drops rapidly pass through the composite membrane material under the action of negative pressure, and the row holes are not contacted with the membrane material all the time, so that non-contact liquid feeding is realized. The method adopts non-contact liquid feeding without damaging the pore structure of the nanofiber membrane, and the finally obtained nanofiber composite membrane keeps excellent filtering performance and has higher mechanical strength.
Drawings
FIG. 1 is a schematic view of the construction of an air-permeable roll according to the present invention;
FIG. 2 is a schematic structural diagram of a liquid dropping hole discharging device;
FIG. 3 is a cross-sectional view of FIG. 2;
FIG. 4 is a schematic view of a process for processing a nanofiber composite membrane;
FIG. 5 is a graph showing the results of filtration of a suspension of polystyrene microspheres of 1 μm using a composite fiber membrane;
fig. 6 is a microscopic scanning electron microscope image of the composite fiber film of the present application.
In the figure, 1, a hollow cylinder; 2. a through hole; 3. a metal tube; 4. a liquid inlet pipe; 5. a liquid outlet pipe; 6. a flow control valve; 7. a liquid storage tank; 8. a liquid homogenizing tank; 9. a drip hole; 10. a breathable roll; 11. a liquid dropping hole discharging device; 12. a nanofiber composite membrane.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is made with reference to the accompanying drawings and specific embodiments.
Example 1
A schematic processing process diagram of a nanofiber composite membrane is shown in FIG. 4, and the method comprises the following steps:
(1) the compounding process comprises the following steps: depositing a layer of nanofiber film on a substrate by an electrostatic spinning technology to form nanofiber composite cloth;
(2) and (3) bonding process: covering the upper surface of an air-permeable roller in a contact manner by using nanofiber composite cloth, wherein the structure of the air-permeable roller is shown in figure 1, and sufficiently dripping an adhesive solution from the upper part of the cloth to the surface of the cloth by using a dripping hole discharging device shown in figures 2-3 to adhere a nanofiber film and a substrate;
(3) and (3) drying: and blowing the nanofiber composite cloth by using dry air to dry the nanofiber composite cloth.
The invention further optimizes that the electrostatic spinning technical parameters in the step (1) can be adjusted according to a common method (such as voltage of 10-100KV and spinning distance of 5-30cm), so as to regulate and control the fiber diameter, pore size, film thickness and the like of the deposited nanofiber film.
The invention further optimizes that the substrate base material in the step (1) is non-woven fabric with better mechanical strength. The thickness of the substrate base material is 0.1-0.5mm, and the tensile strength is more than 20N/m.
The invention is further optimized that the schematic structural diagram of the air-permeable roller in the step (2) is shown in fig. 1, the main structure of the air-permeable roller is a hollow cylinder 1 with two ends connected with metal pipes 3, and a plurality of small through holes 2 are distributed on the surface of the hollow cylinder 1; the metal tube 3 is connected with a vacuum pump to obtain a certain vacuum degree (0.05-0.10 bar); the diameter of the surface through hole 2 is 3mm, and the hole distance between the adjacent through holes 2 is 15 mm; the diameter ratio of the diameter of the metal tube 3 to the hollow cylinder 1 is 1: 5.
The invention further optimizes that the liquid dropping hole discharging device in the step (2) is arranged at one side of the air permeable roller, one side of the liquid dropping hole discharging device is arranged at a short distance with the air permeable roller but is not contacted with the air permeable roller, and the distance is 1-10 mm. The nanofiber film and the substrate pass through a gap between the dropping hole and the air-permeable roller.
The invention is further optimized that the structure of the dropping hole discharging device in the step (2) is schematically shown in figure 2, and the dropping hole discharging device consists of a liquid inlet pipe 4, a liquid outlet pipe 5, a liquid storage tank 7, a liquid homogenizing tank 8, a flow control valve 6 and a dropping hole 9; one end of the liquid storage tank 7 is communicated with the liquid inlet pipe 4, the other end of the liquid storage tank 7 is communicated with the liquid outlet pipe 5, one side of the liquid storage tank 7 is provided with a liquid homogenizing tank 8, the liquid level of the liquid homogenizing tank 8 is prevented from fluctuating when the liquid storage tank 7 is filled with liquid, the flow speed of the liquid dropping holes 9 is uneven 9, the other side of the liquid storage tank 7 is provided with a flow control valve 6, the distance between the flow control valve 6 and the liquid storage tank 7 is h, the caliber of the liquid homogenizing tank 8 is smaller than the caliber of the liquid storage tank 7, and one side of the liquid homogenizing tank 8 is provided with a plurality of liquid dropping holes 9. The distance between the adjacent drip holes 9 is 5 mm; the liquid feeding speed of the dropping liquid is controlled by adjusting the liquid feeding speed of the liquid feeding pipe 4 and the height (h) of the flow control valve 6, and the liquid feeding speed of the dropping liquid is 1-50 ml/min. The liquid dropping holes 9 slowly and repeatedly combine the membrane surface to drop liquid, the liquid drops rapidly pass through the composite membrane material under the action of negative pressure, and the liquid dropping holes 9 are not contacted with the membrane material all the time, so that non-contact liquid feeding is realized.
The invention further optimizes that the concentration of the bonding solution in the step (2) is 2 percent, and the bonding solution is a mixture of sodium polyacrylate solution, polyacrylic acid solution and PVC solution;
the invention further optimizes that the temperature of the drying air in the step (3) is 40 ℃, and the blowing flow rate of the drying air is 100 cm/s.
In order to verify the filtering effect of the composite fiber membrane prepared by the present application, experiments are performed to verify that fig. 5 is an optical effect diagram before and after the composite fiber membrane filters 1 μm polystyrene microsphere suspension under the action of gravity, it can be seen that the solution is clear and transparent after filtering, and the commercial filtering membrane in the market is difficult to allow the suspension to naturally permeate and filter under the action of gravity, so that the composite fiber membrane can also be used for replacing the traditional liquid filtering membrane. FIG. 6 is a microscopic scanning electron micrograph.
Example 2
A method for preparing a nanofiber composite membrane, similar to example 1, except that in step (1), the substrate is a fabric with good mechanical strength, the thickness is 0.1-0.5mm, and the tensile strength is more than 20N/m.
Example 3
A method for preparing a nanofiber composite membrane, similar to example 1, except that in step (1), the substrate is paper with good mechanical strength, the thickness is 0.1-0.5mm, and the tensile strength is more than 20N/m.
Example 4
A method of preparing a nanofiber composite membrane, similar to example 1, except that the diameter of the surface through-hole 2 in step (2) was 0.1 mm.
Example 5
A method of preparing a nanofiber composite membrane, similar to example 1, except that the diameter of the surface through-hole 2 in step (2) is 2 mm.
Example 6
A method for preparing a nanofiber composite membrane, similar to the example, except that the diameter of the surface through-hole 2 in the step (2) is 4 mm.
Example 7
A method of preparing a nanofiber composite membrane, similar to example 1, except that the diameter of the surface through-hole 2 in step (2) is 5 mm.
Example 8
A method for preparing a nanofiber composite membrane, similar to example 1, except that the hole pitch of the adjacent through holes 2 in the step (2) is 5 mm.
Example 9
A method for preparing a nanofiber composite membrane was carried out in a similar manner to example 1, except that the pitch between the adjacent through-holes 2 in the step (2) was 10mm
Example 10
A method for preparing a nanofiber composite membrane, similar to example 1, except that in step (2), the hole pitch of the adjacent through holes 2 is 20mm
Example 11
A method for preparing a nanofiber composite membrane, similar to example 1, except that the hole pitch of the adjacent through holes 2 in the step (2) is 30 mm.
Example 12
A method of preparing a nanofiber composite membrane, similar to example 1, except that the ratio of the diameter of the metal tube 3 to the diameter of the hollow cylindrical body 1 in step (2) is 1: 3.
Example 13
A method of preparing a nanofiber composite membrane, similar to example 1, except that the ratio of the diameter of the metal tube 3 to the diameter of the hollow cylindrical body 1 in step (2) is 1: 6.
Example 14
A method of preparing a nanofiber composite membrane, similar to example 1, except that the ratio of the diameter of the metal tube 3 to the diameter of the hollow cylindrical body 1 in step (2) is 1: 8.
Example 15
A method of preparing a nanofiber composite membrane, similar to example 1, except that the ratio of the diameter of the metal tube 3 to the diameter of the hollow cylinder 1 in step (2) is 1: 10.
Example 16
A method for preparing a nanofiber composite membrane, similar to example 1, except that the interval between the adjacent dropping holes 9 in the step (2) is 2 mm.
Example 17
A method for preparing a nanofiber composite membrane, similar to example 1, except that the interval between the adjacent dropping holes 9 in the step (2) is 7 mm.
Example 18
A method for preparing a nanofiber composite membrane, similar to example 1, except that the interval between the adjacent dropping holes 9 in the step (2) is 10 mm.
Example 19
A method of preparing a nanofiber composite membrane, similar to example 1, except that the concentration of the bonding solution in the step (2) is 0.01%.
Example 20
A method of preparing a nanofiber composite membrane, similar to example 1, except that the concentration of the bonding solution in step (2) is 1%.
Example 21
A nanofiber composite membrane was prepared in a similar manner to example 1, except that the concentration of the bonding solution in step (2) was 1.5%.
Example 22
A nanofiber composite membrane was prepared in a similar manner to example 1, except that the concentration of the bonding solution in step (2) was 2.5%.
Example 23
A nanofiber composite membrane was prepared in a similar manner to example 1, except that the concentration of the bonding solution in step (2) was 3%.
Example 24
A method for preparing a nanofiber composite membrane, similar to example 1, except that the bonding solution in step (2) is a mixture of a sodium polyacrylate solution, a polyacrylic acid solution, a PVC solution, a PVB solution, a PS solution, a PMMA solution, a Polyurethane (PU) solution, a Polycarbonate (PC) solution, a Polylactide (PLA) solution, a PVA solution, a Polycaprolactone (PCL) solution, a PVP solution, a Polyamide (PA) solution, and a PEG solution.
Example 25
A method of preparing a nanofiber composite membrane, similar to example 1, except that the bonding solution in step (2) is a Polyurethane (PU) solution.
Example 26
A method for preparing a nanofiber composite membrane, which is similar to that of example 1, except that the bonding solution in the step (2) is one or a mixture of more than one of sodium polyacrylate solution, polyacrylic acid solution, PVC solution, PVB solution, PS solution, PMMA solution, Polyurethane (PU) solution, Polycarbonate (PC) solution, Polylactide (PLA) solution, PVA solution, Polycaprolactone (PCL) solution, PVP solution, Polyamide (PA) solution and PEG solution.
Example 27
A method for preparing a nanofiber composite membrane was carried out in the same manner as in example 1, except that the temperature of the drying air in step (3) was 20 ℃ and the blowing flow rate of the drying air was 200 cm/s.
Example 28
A method of preparing a nanofiber composite membrane, similar to example 1, except that the temperature of the drying air in step (3) was 30 ℃ and the blowing flow rate of the drying air was 110 cm/s.
Example 29
A nanofiber composite membrane was prepared in a similar manner to example 1, except that the temperature of the drying air in step (3) was 50 ℃ and the blowing flow rate of the drying air was 100 cm/s.
Example 30
A method for preparing a nanofiber composite membrane was carried out in the same manner as in example 1, except that the temperature of the drying air in step (3) was 90 ℃ and the blowing flow rate of the drying air was 2 cm/s.
Example 31
A breathable roller comprises a hollow cylinder 1, wherein a plurality of through holes 2 are distributed on the surface of the hollow cylinder 1, two ends of the hollow cylinder 1 are communicated with metal pipes 3 (the metal pipes 3 can be replaced by plastic pipes and are made of other materials such as polyethylene) after being sealed, the metal pipes 3 at the two ends are arranged in parallel, the outer ends of the metal pipes 3 are connected with a vacuum pump, the through holes 2 are regularly arranged at intervals, the diameter of each through hole 2 is 1mm, the interval between every two adjacent through holes 2 is 6mm, and the diameter ratio of the metal pipes 3 to the diameter ratio of the hollow cylinder 1 is 1: 5.
Example 32
An air-permeable roll was fabricated in the same manner as in example 31, except that the diameter of the through-holes 2 was 0.1mm and the interval between the adjacent through-holes 2 was 5 mm.
Example 33
An air-permeable roll was fabricated in the same manner as in example 31, except that the through-holes 2 had a diameter of 3mm and the interval between the adjacent through-holes 2 was 10 mm.
Example 34
An air-permeable roll was fabricated in the same manner as in example 31, except that the through-holes 2 were 4mm in diameter and the interval between the adjacent through-holes 2 was 20 mm.
Example 35
An air-permeable roll was fabricated in the same manner as in example 31, except that the through-holes 2 were 5mm in diameter and the interval between the adjacent through-holes 2 was 30 mm.
Example 36
An air-permeable roll was similar to example 31 except that the diameter of the metal tube 3 was 1:3 in diameter to that of the hollow cylindrical body 1.
Example 37
An air-permeable roll was similar to example 31 except that the diameter of the metal tube 3 was 1:4 in diameter to that of the hollow cylindrical body 1.
Example 38
An air-permeable roll was similar to example 31 except that the diameter of the metal tube 3 was 1:8 in diameter to that of the hollow cylindrical body 1.
Example 39
An air-permeable roll was similar to example 31 except that the diameter of the metal tube 3 was 1:10 in diameter to that of the hollow cylindrical body 1.
Example 40
An air-permeable roll, similar to example 31, except that the diameter of the through-holes 2 was gradually increased from the outside to the inside.
Example 41
The dropping liquid hole discharging device comprises a liquid storage tank 7, wherein one end of the liquid storage tank 7 is communicated with a liquid inlet pipe 4, the other end of the liquid storage tank 7 is communicated with a liquid outlet pipe 5, a liquid homogenizing tank 8 is arranged on one side of the liquid storage tank 7, the liquid storage tank 7 and the liquid homogenizing tank 8 are both of rectangular groove structures and are communicated with each other in a transition mode through a slit, and the width of the slit is 0.5mm-5 mm. The other side of the liquid storage tank 7 is provided with a flow control valve 6, the distance between the flow control valve 6 and the liquid storage tank 7 is h, the caliber of the liquid homogenizing tank 8 is smaller than that of the liquid storage tank 7, one side of the liquid homogenizing tank 8 is provided with a plurality of liquid dropping holes 9, the liquid dropping holes 9 extend to the outside of the liquid homogenizing tank 8, the liquid supply speed is adjusted by adjusting the liquid inlet speed of the liquid inlet pipe 4 and the distance h, and the distance between the adjacent liquid dropping holes 9 is 5 mm.
Example 42
A drip hole discharging device similar to that of example 41 except that the interval between the adjacent drip holes 9 was 2 mm.
Example 43
A drip hole discharging device was constructed similarly to example 41 except that the interval between the adjacent drip holes 9 was 10 mm.
Example 44
A drip outlet device, similar to the embodiment 41, except that the reservoir 7 is at least one of a rectangular tank, a polygonal tank, and a circular tank.
Example 45
A dropping liquid discharging hole device is similar to that of embodiment 41 except that the liquid homogenizing tank 8 is at least one of a rectangular tank, a polygonal tank and a circular tank.
Example 46
A dropping hole discharging device is similar to that of embodiment 41 except that a liquid homogenizing tank 8 and a liquid storage tank 7 are concentrically arranged.
Example 47
A dropping liquid hole-discharging device is similar to that of embodiment 41 except that a liquid homogenizing tank 8 and a liquid storage tank 7 are provided in an integral structure.
Example 48
A liquid dropping hole discharging device is similar to that of embodiment 41 except that a liquid inlet pipe 4 and a liquid outlet pipe 5 are arranged in parallel with each other.
Example 49
A drip hole discharging device is similar to that of example 41 except that, as shown in FIG. 2, the diameter of the drip hole 9 is rectangular and gradually increases from top to bottom, so that the flow rate is relatively increased in a suitable flow rate range to accelerate the processing speed.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (7)
1. A preparation method of a nanofiber composite membrane is characterized by comprising the following steps:
(1) compounding: depositing at least one layer of nanofiber film on a substrate by an electrostatic spinning technology to form nanofiber composite cloth;
(2) bonding: covering the nanofiber composite cloth obtained in the step (1) on a breathable roller, wherein the breathable roller comprises a hollow cylinder, a plurality of through holes are distributed on the surface of the hollow cylinder, the two ends of the hollow cylinder are sealed and then are communicated with a metal pipe, the outer end of the metal pipe is connected with a vacuum pump, a bonding solution is dripped through a liquid dripping and hole discharging device to bond a nanofiber film and a substrate, the liquid dripping and hole discharging device comprises a liquid storage tank (7), one end of the liquid storage tank (7) is communicated with a liquid inlet pipe (4), the other end of the liquid storage tank is communicated with a liquid outlet pipe (5), a liquid homogenizing tank (8) is arranged on one side of the liquid storage tank (7), a flow control valve (6) is arranged on the other side of the liquid storage tank (7), the distance between the flow control valve (6) and the liquid storage tank (7) is h, the caliber of the liquid homogenizing tank (8) is smaller than that of the liquid storage tank (7), and a plurality of liquid dripping holes (9) are arranged on one side of the liquid homogenizing tank (8), the liquid feeding speed is adjusted by adjusting the liquid feeding speed of the liquid feeding pipe (4) and the size of h;
(3) and (3) drying: and blowing the nanofiber composite cloth by using dry air to dry the nanofiber composite cloth.
2. The method of claim 1, wherein the substrate in step (1) is at least one of a non-woven fabric, a woven fabric or a paper.
3. The method of claim 1, wherein the plurality of through holes are regularly arranged, the diameter of each through hole is 0.1-5mm, and the distance between every two adjacent through holes is 5-30 mm.
4. The method of claim 1, wherein the ratio of the diameter of the metal tube to the diameter of the hollow cylinder is 1:3 to 10.
5. The method of claim 1, wherein in the step (2), the dropping hole discharging unit is disposed at one side of the air-permeable roller, the dropping hole (9) side of the dropping hole discharging unit is disposed at a short distance from the air-permeable roller, and the nanofiber film and the substrate are passed through the gap between the dropping hole (9) and the air-permeable roller.
6. The method of claim 1, wherein the bonding solution in step (2) is one or a mixture of two or more selected from a group consisting of a sodium polyacrylate solution, a polyacrylic acid solution, a polyvinyl chloride solution, a polyvinyl butyral solution, a polystyrene solution, a polymethyl methacrylate solution, a polyurethane solution, a polycarbonate solution, a polylactide solution, a polyvinyl alcohol solution, a polycaprolactone solution, a polyvinyl pyrrolidone solution, a polyamide solution, and a polyethylene glycol solution.
7. The method for preparing a nanofiber composite membrane according to claim 1, wherein the temperature of the drying air in the step (3) is 20 to 90 ℃, and the blowing flow rate of the drying air is 2 to 200 cm/s.
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| WO2002096538A1 (en) * | 2001-05-29 | 2002-12-05 | Pall Corporation | Tubular membrane and method of making |
| TWI414345B (en) * | 2010-01-04 | 2013-11-11 | Taiwan Textile Res Inst | A nanofiber-containing membrane, a composite membrane, a process for producing them and their use |
| EP2694196B1 (en) * | 2011-04-01 | 2021-07-21 | EMD Millipore Corporation | Nanofiber containing composite structures |
| KR101556466B1 (en) * | 2014-02-18 | 2015-10-01 | 전북대학교산학협력단 | Composite nanofibrous membrane for water purification and method of fabricating the same |
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| 静电纺聚偏氟乙烯及其复合纳米纤维膜在过滤领域的研究进展;沈雪 等;《净水技术》;20190601;第38卷(第S1期);第1-6页 * |
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