CN117643801A - Hollow fiber membrane with high water flux and preparation method thereof - Google Patents
Hollow fiber membrane with high water flux and preparation method thereof Download PDFInfo
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- 239000012510 hollow fiber Substances 0.000 title claims abstract description 164
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 230000004907 flux Effects 0.000 title claims abstract description 33
- 238000007716 flux method Methods 0.000 title description 2
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 7
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- 229920000136 polysorbate Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
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- 239000013078 crystal Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 238000004898 kneading Methods 0.000 description 1
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- RAYLUPYCGGKXQO-UHFFFAOYSA-N n,n-dimethylacetamide;hydrate Chemical compound O.CN(C)C(C)=O RAYLUPYCGGKXQO-UHFFFAOYSA-N 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a hollow fiber membrane with high water flux and a preparation method thereof, wherein the preparation method comprises the following steps: s1: preparation of a hollow fiber primary membrane: preparing spinning solution and spinning, wherein the spinning solution is extruded out of an outer annular space of a spinneret plate, a core solution is conveyed at a central tube of the spinneret plate through a constant flow pump, and the primary solution is obtained through a water vapor atmosphere pipeline; s2: preparation of a composite hollow fiber primary membrane: preparing electrostatic spinning solution, and spraying and adhering the electrostatic spinning solution on the surface of the hollow fiber primary membrane by an electrostatic spinning machine to obtain a composite hollow fiber primary membrane; s3: post-treatment: immersing the composite hollow fiber primary membrane prepared in the step S2 in water for water bath for 1-12h to obtain the hollow fiber membrane. According to the invention, the surface of the membrane is roughened, hydrophilic nano particles are attached to the surface of the membrane, and the hydrophilicity of the membrane body is improved, so that the deep hydrophilization from the surface of the membrane to the inside of the membrane is achieved, and the water flux of the hollow fiber membrane is improved to a greater extent.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a hollow fiber membrane with high water flux and a preparation method thereof.
Background
As a novel green and environment-friendly separation technology, the membrane separation technology has the characteristics of small occupied area, high integration degree, capability of realizing efficient concentration and purification functions and the like, so that the membrane separation technology is increasingly applied to the aspects of industry and people living. Currently, the most widely used types of separation membranes in membrane separation technology are flat sheet membranes, roll membranes and hollow fiber membranes. Compared with common flat plate and rolled separation membranes, the hollow fiber membrane has a self-supporting structure, has higher specific surface area and packing density, and has easier processing and simpler and more various membrane cleaning modes, so that the hollow fiber membrane is always favored by people. However, as the hydrophilicity of the polymer raw materials adopted by most hollow fiber separation membranes is poor, the water flux of the hollow fiber membranes is required to be further improved when sewage is treated, and meanwhile, the development period of novel hydrophilic polymers is long and the difficulty is high, so that how to improve the hydrophilicity and the water flux of the hollow fiber membranes from the aspect of the separation membrane structure is improved, and the method becomes a more effective solution way, wherein the modification of the surfaces of the hollow fiber membranes is a key breakthrough of the hydrophilic separation membranes to the high water flux separation membranes.
Chinese patent CN106256416a discloses a spinning solution containing polypropylene resin, a diluent and a water-insoluble modifying additive, and a hydrophilic polypropylene hollow fiber separation membrane is prepared through spinning and extraction processes, and the hydrophilic hollow fiber membrane related to the patent changes the composition of the spinning solution, and is a preparation method for a porous polypropylene hollow fiber membrane, but does not modify the surface of the fiber membrane.
Chinese patent document CN115920670a provides an anti-pollution hydrophilic hollow fiber membrane and a preparation method thereof, which comprises mixing, kneading and extruding thermoplastic high molecular polymer resin, organic pore-forming agent, inorganic pore-forming agent and nano titanium dioxide; extracting and extracting the filiform hollow fiber, immersing a base film in a titanium crystal growth solution, forming a titanium crystal nano layer with pollution resistance under an acidic condition, immersing the film in an aqueous solution of a polymer with hydrophilic groups, and forming a hydrophilic composite layer after hydrogen bonding reaction. The hydrophilic hollow fiber membrane related to the patent forms a titanium crystal nano layer on the surface of the membrane, and is a preparation method aiming at thermoplastic melt extrusion processing rather than solution type dry-wet spinning hollow fiber membrane.
Chinese patent document CN115920670A prepares high-strength hydrophilic hollow fiber membrane, polysulfone polymer and organic solvent are mixed to form first homogeneous liquid, and then acid ester reinforcing agent is added into the first homogeneous liquid to be cooled and shaped through coagulating bath; finally, the hollow fiber membrane is extracted by deionized water, and the high-strength hydrophilic hollow fiber membrane is obtained after drying. The mechanical property and the hydrophilic property of the polymer film are synergistically enhanced. The hydrophilic hollow fiber membrane related to the patent introduces an acid ester reinforcing agent into the spinning solution, is a preparation method for the polysulfone GAP molecular hollow fiber membrane, and the method needs to adopt a specific membrane surface titanium crystal growth device for production, and needs to stir a flammable solvent to possibly cause risks.
In summary, there is no more suitable method for improving the surface hydrophilicity of a hollow fiber membrane by modifying the surface of the hollow fiber membrane formed by solution type wet and dry spinning.
Disclosure of Invention
The invention provides a hollow fiber membrane with high water flux and a preparation method thereof, which are used for solving the problems.
The technical scheme adopted by the invention is as follows: a method for preparing a hollow fiber membrane with high water flux, which at least comprises the following steps:
s1: preparation of a hollow fiber primary membrane: preparing spinning solution of the hollow fiber primary membrane, spinning the spinning solution, extruding the spinning solution from an outer annular space of a spinneret plate, conveying core solution at a central tube of the spinneret plate through a constant flow pump, and obtaining the hollow fiber primary membrane after the primary solution extruded from the outer annular space of the spinneret plate passes through a steam atmosphere pipeline;
s2: preparation of a composite hollow fiber primary membrane: preparing electrostatic spinning solution of the composite layer, and spraying and adhering the electrostatic spinning solution on the surface of the hollow fiber primary membrane prepared in the step S1 by an electrostatic spinning machine to obtain a composite hollow fiber primary membrane with the outer surface sprayed with the composite layer;
s3: post-treatment: immersing the composite hollow fiber primary membrane prepared in the step S2 into water for water bath for 1-12h, wherein the water temperature is 40-70 ℃, and winding to obtain the hollow fiber membrane. The water bath causes the water-soluble fibers on the surface of the membrane to dissolve, and at the same time, the nanoparticles stay on the outer surface of the membrane, and the inside of the membrane is solidified in the water bath, so that the surface of the hollow fiber membrane is roughened and particulated.
Preferably, the spinning solution in the step S1 comprises the following components in parts by weight: 8-25 parts of polymer, 1-10 parts of pore-forming agent, 0.5-2 parts of nanoparticle additive and 63-90.5 parts of solvent, mixing the pore-forming agent, the nanoparticle additive and the solvent, then performing ultrasonic dispersion for 0.5-3 hours, adding the polymer, placing the obtained mixed solution in a spinning kettle, stirring and dissolving at 30-90 ℃ until a transparent viscous solution is formed, performing vacuum defoaming for 6-48 hours to obtain spinning solution of the hollow fiber primary membrane, heating and stabilizing the spinning solution to 30-60 ℃, extruding the spinning solution by a metering pump under compressed nitrogen, and performing spinning.
Preferably, the electrostatic spinning solution of the composite layer in the step S2 comprises the following components in parts by weight: 4-20 parts of water-soluble polymer, 60-90 parts of water, 0.5-2 parts of nanoparticle additive and 6-20 parts of diluent, and dissolving the components at 30-80 ℃ for 0.5-4 hours to prepare uniform and transparent electrostatic spinning solution.
Preferably, the preparation method of the composite hollow fiber primary membrane in the step S2 comprises the following steps: after the hollow fiber primary membrane prepared in the step S1 is discharged from a water vapor atmosphere pipeline, an electrostatic spinning machine is arranged on two sides of the hollow fiber primary membrane, the direct current voltage of the electrostatic spinning machine is 10-30kV, the extrusion rate of electrostatic spinning solution is 0.5-3.0ml/h, the receiving distance is 10-30cm, the electrostatic spinning time is 5-30 minutes, and the central axes of the needle heads of the two electrostatic spinning machines along the length direction are mutually perpendicular to the central axis of the hollow fiber primary membrane along the length direction.
Preferably, the polymer in the spinning solution is selected from at least one of polysulfone, polyamide, polyethersulfone, polyvinyl chloride and its copolymer, polyvinylidene fluoride and its copolymer, polyimide, polycarbonate, polyacrylate, polytetrafluoroethylene.
Preferably, the solvent in the spinning solution is at least one selected from N-methylpyrrolidone, dimethyl sulfoxide, acetone, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, benzene and toluene; the nanoparticle additive in the spinning solution is at least one selected from nano zinc oxide, carboxylated graphene oxide and carboxylated carbon nanotubes.
Preferably, the nanoparticle additive in the electrostatic spinning solution is at least one selected from nano zinc oxide, carboxylated graphene oxide and carboxylated carbon nanotubes; the water-soluble polymer in the electrostatic spinning solution is at least one of polyvinyl alcohol, polyacrylamide and polyethylene glycol; the diluent is one or a mixture of two of acetone and tetrahydrofuran.
Preferably, the core solution in the step S1 is an aqueous solution of an organic solvent, the content of the organic solvent is 0-30wt%, and the organic solvent is at least one selected from N-methylpyrrolidone, dimethyl sulfoxide, acetone, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, benzene and toluene.
Preferably, the pore-forming agent in the spinning solution comprises the following components in parts by weight: 1-10 parts of high molecular polymer, 0.1-2 parts of inorganic matter and 0.1-1 part of surfactant, wherein the high molecular polymer is at least one selected from polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol; the inorganic matters are at least one selected from lithium chloride, zinc chloride, copper chloride and pure water; the surfactant is at least one selected from sodium dodecyl sulfate, tween and span.
In another aspect, the invention provides a hollow fiber membrane obtained by the preparation method.
Compared with the prior art, the invention has the following advantages:
(1) The hollow fiber membrane prepared by the invention is subjected to roughening treatment on the surface of the membrane, hydrophilic nano particles are attached to the surface of the membrane, and the hydrophilicity of the membrane body is improved, so that the deep hydrophilization from the surface of the membrane to the inside of the membrane is achieved, the water flux of the hollow fiber membrane is improved to a greater extent, and meanwhile, the water contact angle of the surface of the hollow fiber membrane can reach below 30 degrees, so that the hydrophilicity of the hollow fiber membrane is further shown;
(2) The invention utilizes the prior equipment to prepare the hollow fiber primary membrane and carries out roughening treatment on the surface of the hollow fiber primary membrane, the two operations can be continuously carried out, the process is simple, the integration degree is high, the process time is greatly shortened, and the production efficiency is improved;
(3) The coarse structure of the surface of the hollow fiber membrane prepared by the invention comprises ravines and network depressions formed by dissolving water-soluble nano fibers and protrusions formed by nano particles attached to the surface of the hollow fiber membrane, so that the coarse structure of the surface of the hollow fiber membrane is more complicated and diversified, and the hydrophilicity and water flux of the surface of the hollow fiber membrane are further improved to a certain extent;
(4) The outer surface of the hollow fiber primary membrane is in a gelled state, and the hollow fiber primary membrane is firmly combined with the nano particles; the hollow fiber membrane can be used as a hollow fiber microfiltration membrane, an ultrafiltration membrane, a hollow fiber composite nanofiltration membrane, a composite reverse osmosis membrane base membrane and the like in water treatment.
Detailed Description
For a better description of the invention, it will now be further described with reference to examples.
A method for preparing a hollow fiber membrane with high water flux, which at least comprises the following steps:
s1: preparation of a hollow fiber primary membrane: preparing spinning solution of the hollow fiber primary membrane, spinning the spinning solution by using a hollow fiber spinning machine, extruding the spinning solution from an outer annular space of a spinneret plate, conveying core solution at a central tube of the spinneret plate through a constant flow pump, and obtaining the hollow fiber primary membrane after the primary solution extruded from the outer annular space of the spinneret plate passes through a water vapor atmosphere pipeline;
s2: preparation of a composite hollow fiber primary membrane: preparing electrostatic spinning solution of a composite layer, spraying and adhering the electrostatic spinning solution on the surface of the hollow fiber primary membrane prepared in the step S1 by an electrostatic spinning machine to obtain a composite hollow fiber primary membrane with the surface sprayed with the composite layer, wherein the outer surface of the hollow fiber primary membrane is gelled but not completely fixed;
s3: post-treatment: immersing the composite hollow fiber primary membrane prepared in the step S2 into water for water bath for 1-12h, wherein the water temperature is 40-70 ℃, and winding to obtain the hollow fiber membrane. The water bath causes the water-soluble fibers on the surface of the membrane to dissolve, and at the same time, the nanoparticles stay on the outer surface of the membrane, and the inside of the membrane is solidified in the water bath, so that the surface of the hollow fiber membrane is roughened and particulated.
The spinning solution in the step S1 comprises the following components in parts by weight: 8-25 parts of polymer, 1-10 parts of pore-forming agent, 0.5-2 parts of nanoparticle additive and 63-90.5 parts of solvent, mixing the pore-forming agent, the nanoparticle additive and the solvent, then performing ultrasonic dispersion for 0.5-3 hours, adding the polymer, placing the obtained mixed solution in a spinning kettle, stirring and dissolving at 30-90 ℃ until a transparent viscous solution is formed, performing vacuum defoaming for 6-48 hours to obtain spinning solution of the hollow fiber primary membrane, heating and stabilizing the spinning solution to 30-60 ℃, extruding the spinning solution by a metering pump under compressed nitrogen, and performing spinning.
The electrostatic spinning solution of the composite layer in the step S2 comprises the following components in parts by weight: 4-20 parts of water-soluble polymer, 60-90 parts of water, 0.5-2 parts of nanoparticle additive and 6-20 parts of diluent, and dissolving the components at 30-80 ℃ for 0.5-4 hours to prepare uniform and transparent electrostatic spinning solution.
The preparation method of the composite hollow fiber primary membrane in the step S2 comprises the following steps: after the hollow fiber primary membrane prepared in the step S1 is discharged from a water vapor atmosphere pipeline, an electrostatic spinning machine is arranged on two sides of the hollow fiber primary membrane, the direct current voltage of the electrostatic spinning machine is 10-30kV, the extrusion rate of electrostatic spinning solution is 0.5-3.0ml/h, the receiving distance is 10-30cm, the electrostatic spinning time is 5-30 minutes, and the central axes of the needle heads of the two electrostatic spinning machines along the length direction are mutually perpendicular to the central axis of the hollow fiber primary membrane along the length direction. Specifically, the hollow fiber primary membrane is spun by a hollow fiber spinning machine, and discharged from top to bottom after being subjected to water vapor atmosphere surrounding pipe, at this time, the central axis of the prepared hollow fiber primary membrane along the length direction is vertical to the ground, the electrostatic spinning machines are arranged at two sides corresponding to the hollow fiber primary membrane, and the needle heads of the two electrostatic spinning machines are not on the same horizontal plane, that is, the distances between the two electrostatic spinning machines and the ground are different, but the needle head connecting line of the two electrostatic spinning machines passes through the central axis of the hollow fiber primary membrane along the length direction. In addition, in order to improve the coverage rate of the composite layer on the surface of the hollow fiber primary membrane, more than two electrostatic spinning machines can be arranged, the electrostatic spinning machines are arranged on the periphery of the hollow fiber primary membrane, and the electrostatic spinning technological parameters of the electrostatic spinning machines are consistent, including direct current voltage, electrostatic spinning solution extrusion rate, receiving distance and electrostatic spinning time.
The polymer in the spinning solution is at least one selected from polysulfone, polyamide, polyethersulfone, polyvinyl chloride and copolymer thereof, polyvinylidene fluoride and copolymer thereof, polyimide, polycarbonate, polyacrylate and polytetrafluoroethylene.
The solvent in the spinning solution is at least one selected from N-methylpyrrolidone, dimethyl sulfoxide, acetone, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, benzene and toluene; the nanoparticle additive in the spinning solution is at least one selected from nano zinc oxide, carboxylated graphene oxide and carboxylated carbon nanotubes.
The nanoparticle additive in the electrostatic spinning solution is at least one selected from nano zinc oxide, carboxylated graphene oxide and carboxylated carbon nanotubes; the water-soluble polymer in the electrostatic spinning solution is at least one of polyvinyl alcohol, polyacrylamide and polyethylene glycol; the diluent is one or a mixture of two of acetone and tetrahydrofuran.
The core liquid in the step S1 is an aqueous solution of an organic solvent, the content of the organic solvent is 0-30wt%, and the organic solvent is at least one selected from N-methylpyrrolidone, dimethyl sulfoxide, acetone, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, benzene and toluene.
The pore-forming agent in the spinning solution comprises the following components in parts by weight: 1-10 parts of high molecular polymer, 0.1-2 parts of inorganic matter and 0.1-1 part of surfactant, wherein the high molecular polymer is at least one selected from polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol; the inorganic matters are at least one selected from lithium chloride, zinc chloride, copper chloride and pure water; the surfactant is at least one selected from sodium dodecyl sulfate, tween and span, wherein specific types of the span and the emesis are not particularly limited herein.
The hollow fiber membrane is prepared by the preparation method.
Example 1
A high water flux hollow fiber membrane, the method of making comprising the steps of: 1 part of polyvinylpyrrolidone, 0.25 part of zinc chloride, 0.25 part of copper chloride, 0.1 part of sodium dodecyl sulfate, 0.5 part of nano zinc oxide and 87.9 parts of dimethyl sulfoxide are added into a container and dispersed for 1h by ultrasound, and are added into a spinning kettle together with 10 parts of polyethersulfone, stirred and dissolved for 6h at 50 ℃ to form a transparent viscous solution, and the transparent viscous solution is defoamed for 10h by vacuum to obtain spinning solution.
Heating and keeping the spinning solution constant to 35 ℃, extruding the spinning solution through a metering pump under compressed nitrogen, extruding the spinning solution through an outer ring of a spinneret plate, outputting core solution through a constant flow pump at the same time, wherein the core solution is 10wt% of dimethyl sulfoxide aqueous solution, the flow rate of the core solution is 10ml/min, and obtaining the hollow fiber primary membrane after the primary solution extruded through the outer ring passes through a 30cm long room temperature saturated steam atmosphere pipeline. Then, 6 parts of polyvinyl alcohol, 83.5 parts of water, 0.5 part of nano zinc oxide and 10 parts of acetone are placed in a beaker, dissolved for 2 hours at 50 ℃ to obtain uniform and transparent electrostatic spinning solution, electrostatic spinning machines are arranged on two sides of a hollow fiber primary membrane discharged through a water vapor atmosphere pipeline, spinning is carried out on the two electrostatic spinning machines for 10 minutes under the conditions of 20kV direct current voltage, 0.8ml/h of electrostatic spinning solution extrusion rate and 10cm of receiving distance, so that a composite hollow fiber primary membrane with a composite layer sprayed on the surface is obtained, the composite hollow fiber primary membrane is immersed in a hot water bath for 6 hours, the water temperature is 50 ℃, and the final hollow fiber membrane is obtained after winding.
Comparative example 1
The composition of the spinning solution and the preparation method thereof are the same as those of the example 1, the spinning solution is heated to be kept constant to 35 ℃, the spinning solution is extruded by a metering pump under the condition of compressed nitrogen, the core solution is extruded by an outer annular space of a spinneret plate and is simultaneously discharged from a central pipe of the spinneret plate by a constant flow pump, the core solution is 10wt% of dimethyl sulfoxide aqueous solution, the flow rate of the core solution is 10ml/min, the primary solution extruded by the outer annular space is immersed into a hot water bath for 6 hours after passing through a 30cm long room temperature saturated steam atmosphere pipeline, the water temperature is 50 ℃, and the final hollow fiber membrane is obtained after winding.
Example 2
A high water flux hollow fiber membrane, the method of making comprising the steps of: 5 parts of polyethylene glycol, 2 parts of lithium chloride, 0.2 part of Tween 40, 0.4 part of carboxylated graphene oxide and 77.4 parts of N-methylpyrrolidone are added into a container and are dispersed for 1.5 hours by ultrasonic, the obtained mixture and 15 parts of polyvinylidene fluoride are added into a spinning kettle together, stirring and dissolving are carried out for 10 hours at 60 ℃ to form a transparent viscous solution, and vacuum defoaming is carried out for 6 hours to obtain spinning solution.
Heating and keeping the spinning solution constant to 50 ℃, extruding the spinning solution by a metering pump under compressed nitrogen, extruding the spinning solution by an outer ring of a spinneret plate, outputting core solution by a constant flow pump at the central tube of the spinneret plate, wherein the core solution is water, the flow rate of the core solution is 22ml/min, and obtaining the hollow fiber primary membrane after the primary solution extruded by the outer ring passes through a 30cm long room temperature saturated steam atmosphere pipeline. Then, 10 parts of polyacrylamide, 74 parts of water, 1 part of carboxylated carbon nano tube and 15 parts of tetrahydrofuran are placed in a beaker, dissolved for 1.5 hours at 70 ℃ to obtain uniform transparent electrostatic spinning solution, electrostatic spinning machines are arranged on two sides of a hollow fiber primary membrane discharged through a water vapor atmosphere pipeline, spinning is carried out for 5 minutes under the conditions that the direct current voltage is 30kV, the extrusion rate of the electrostatic spinning solution is 1.5ml/h and the receiving distance is 30cm, a composite hollow fiber primary membrane with a composite layer sprayed on the surface is obtained, the composite hollow fiber primary membrane is immersed in a hot water bath for 12 hours, the water temperature is 60 ℃, and the final hollow fiber membrane is obtained after winding.
Comparative example 2
The composition of the spinning solution and the preparation method thereof are the same as those of the embodiment 2, the spinning solution is heated to be kept constant to 50 ℃, the spinning solution is extruded by a metering pump under the condition of compressed nitrogen, the core solution is extruded by an outer annular space of a spinneret plate and is output by a constant flow pump at the central tube of the spinneret plate, the core solution is water, the flow rate of the core solution is 22ml/min, the primary solution extruded by the outer annular space is immersed into a hot water bath for 12 hours after passing through a room temperature saturated steam atmosphere pipeline with the length of 30cm, the water temperature is 60 ℃, and the final hollow fiber membrane is obtained after winding.
Example 3
A high water flux hollow fiber membrane, the method of making comprising the steps of: 0.8 part of polyvinylpyrrolidone, 7.2 parts of polyethylene glycol, 1.7 parts of copper chloride, 0.15 part of span 40, 0.28 part of nano zinc oxide, 1.12 parts of carboxylated graphene oxide and 68.75 parts of N, N-dimethylacetamide are added into a container and dispersed for 3 hours by ultrasound, and the obtained mixture, 14 parts of polyvinylidene fluoride and 6 parts of polyvinylidene fluoride are added into a spinning kettle together, stirred and dissolved for 8 hours at 80 ℃ to form a transparent viscous solution, and the transparent viscous solution is defoamed for 24 hours by vacuum to obtain spinning solution.
Heating and keeping the spinning solution constant to 60 ℃, extruding the spinning solution through a metering pump under compressed nitrogen, extruding the spinning solution through an outer ring of a spinneret plate, outputting core solution through a constant flow pump at the same time, wherein the core solution is 15wt% of N-methyl pyrrolidone aqueous solution, the flow rate of the core solution is 18ml/min, and obtaining the hollow fiber primary membrane after the primary solution extruded through the outer ring passes through a 30cm long room temperature saturated steam atmosphere pipeline. Then, 3.2 parts of polyvinyl alcohol, 0.8 part of polyacrylamide, 80.4 parts of water, 0.6 part of carboxylated carbon nano tube, 10.5 parts of acetone and 4.5 parts of tetrahydrofuran are placed in a beaker, dissolved for 1.0h at 80 ℃ to obtain uniform and transparent electrostatic spinning solution, electrostatic spinning machines are arranged on two sides of a hollow fiber primary membrane discharged through a water vapor atmosphere pipeline, spinning is carried out for 8 minutes under the conditions that the direct current voltage is 20kV, the extrusion rate of the electrostatic spinning solution is 0.7ml/h and the receiving distance is 15cm, a composite hollow fiber primary membrane with a composite layer sprayed on the surface is obtained, the composite hollow fiber primary membrane is immersed in a hot water bath for 12h, the water temperature is 45 ℃, and the final hollow fiber membrane is obtained after winding.
Comparative example 3
The composition of the spinning solution and the preparation method thereof are the same as those of the embodiment 3, the spinning solution is heated to be kept constant to 60 ℃, the spinning solution is extruded by a metering pump under the condition of compressed nitrogen, the core solution is extruded by an outer annular space of a spinneret plate and is simultaneously discharged from a central pipe of the spinneret plate by a constant flow pump, the core solution is 15wt% of N-methylpyrrolidone aqueous solution, the flow rate of the core solution is 18ml/min, the primary solution extruded by the outer annular space is immersed into a hot water bath for 12h after passing through a 30cm long room temperature saturated steam atmosphere pipeline, the water temperature is 45 ℃, and the final hollow fiber membrane is obtained after winding.
Example 4
A high water flux hollow fiber membrane, the method of making comprising the steps of: 4 parts of polyvinyl alcohol, 0.32 part of lithium chloride, 0.48 part of zinc chloride, 0.3 part of tween 60, 0.9 part of nano zinc oxide, 32 parts of N-methylpyrrolidone and 48 parts of toluene are added into a container and are dispersed for 2 hours by ultrasound, the obtained mixture and 14 parts of polysulfone are added into a spinning kettle together, stirring and dissolving are carried out for 18 hours at 50 ℃ to form a transparent viscous solution, and vacuum defoaming is carried out for 12 hours to obtain spinning solution.
Heating and keeping the spinning solution constant to 40 ℃, extruding the spinning solution through a metering pump under compressed nitrogen, extruding the spinning solution through an outer ring of a spinneret plate, outputting core solution through a constant flow pump at the same time, wherein the core solution is 20wt% of N, N-dimethylformamide water solution, the flow rate of the core solution is 8ml/min, and obtaining the hollow fiber primary membrane after the primary solution extruded through the outer ring passes through a 30cm long room temperature saturated steam atmosphere pipeline. Then, 13 parts of polyethylene glycol, 73.7 parts of water, 1.3 parts of carboxylated carbon nano tubes and 12 parts of tetrahydrofuran are placed in a beaker, dissolved for 4.0 hours at 60 ℃ to obtain uniform and transparent electrostatic spinning solution, electrostatic spinning machines are arranged on two sides of a hollow fiber primary membrane discharged through a water vapor atmosphere pipeline, spinning is carried out on the two electrostatic spinning machines for 30 minutes under the conditions of 10kV direct current voltage, 2.6ml/h electrostatic spinning solution extrusion rate and 26cm receiving distance, so as to obtain a composite hollow fiber primary membrane with a composite layer sprayed on the outer surface, the composite hollow fiber primary membrane is immersed in a hot water bath for 10 hours, the water temperature is 50 ℃, and the final hollow fiber membrane is obtained after winding.
Comparative example 4
The composition of the spinning solution and the preparation method thereof are the same as those of the example 4, the spinning solution is heated to be kept constant to 40 ℃, the spinning solution is extruded by a metering pump under the condition of compressed nitrogen, the core solution is extruded by an outer annular space of a spinneret plate and is simultaneously discharged from a central pipe of the spinneret plate by a constant flow pump, the core solution is an N, N-dimethylformamide water solution with the weight percent of 20%, the flow rate of the core solution is 8ml/min, the primary solution extruded by the outer annular space is immersed into a hot water bath for 10 hours after passing through a 30cm long room temperature saturated steam atmosphere pipeline, the water temperature is 50 ℃, and the final hollow fiber membrane is obtained after winding.
Example 5
A high water flux hollow fiber membrane, the method of making comprising the steps of: 4.5 parts of polyvinyl alcohol, 4.5 parts of polyethylene glycol, 0.5 part of sodium dodecyl sulfate, 0.5 part of pure water, 0.4 part of nano zinc oxide and 75.6 parts of N, N-dimethylacetamide are added into a container and dispersed for 0.5h by ultrasonic, the obtained mixture, 12.6 parts of polysulfone and 1.4 parts of polycarbonate are added into a spinning kettle together, stirred and dissolved for 10h at 70 ℃ to form a transparent viscous solution, and vacuum defoaming is carried out for 36h to obtain a spinning solution.
Heating and keeping the spinning solution constant to 40 ℃, extruding the spinning solution through a metering pump under compressed nitrogen, extruding the spinning solution through an outer ring of a spinneret plate, outputting core solution through a constant flow pump at the same time, wherein the core solution is 15wt% of N, N-dimethylacetamide aqueous solution, the flow rate of the core solution is 30ml/min, and obtaining the hollow fiber primary membrane after the primary solution extruded from the outer ring passes through a room temperature saturated steam atmosphere pipeline with the length of 30 cm. Then, 20 parts of polyvinyl alcohol, 68 parts of water, 2 parts of carboxylated graphene oxide and 10 parts of acetone are placed in a beaker, dissolved for 0.5h at 80 ℃ to obtain uniform transparent electrostatic spinning solution, electrostatic spinning machines are arranged on two sides of a hollow fiber primary membrane discharged through a water vapor atmosphere pipeline, spinning is carried out for 15 minutes under the conditions that the direct current voltage is 15kV, the extrusion rate of the electrostatic spinning solution is 0.9ml/h and the receiving distance is 15cm, a composite hollow fiber primary membrane with a composite layer sprayed on the surface is obtained, the composite hollow fiber primary membrane is immersed in a hot water bath for 8h, the water temperature is 45 ℃, and the final hollow fiber membrane is obtained after winding.
Comparative example 5
The composition of the spinning solution and the preparation method thereof are the same as those of the example 5, the spinning solution is heated to be kept constant to 40 ℃, the spinning solution is extruded by a metering pump under the condition of compressed nitrogen, the core solution is extruded by an outer annular space of a spinneret plate and is simultaneously discharged from a central pipe of the spinneret plate by a constant flow pump, the core solution is 15wt% of N, N-dimethylacetamide water solution, the flow rate of the core solution is 30ml/min, the primary solution extruded by the outer annular space is immersed into a hot water bath for 8 hours after passing through a 30cm long room temperature saturated steam atmosphere pipeline, the water temperature is 45 ℃, and the final hollow fiber membrane is obtained after winding.
Example 6
A high water flux hollow fiber membrane, the method of making comprising the steps of: 2.1 parts of polyvinylpyrrolidone, 4.9 parts of polyvinyl alcohol, 0.85 part of lithium chloride, 0.85 part of pure water, 0.4 part of sodium dodecyl sulfate, 0.7 part of nano zinc oxide, 0.7 part of carboxylated graphene oxide, 54.95 parts of N-methylpyrrolidone and 23.55 toluene are added into a container and dispersed for 2.5 hours ultrasonically, and the obtained mixture is added into a spinning kettle together with 6.6 parts of polysulfone and 4.4 parts of polyvinyl chloride, stirred and dissolved for 11 hours at 70 ℃ to form a transparent viscous solution, and vacuum defoaming is carried out for 48 hours to obtain a spinning solution.
Heating and keeping the spinning solution constant to 60 ℃, extruding the spinning solution through a metering pump under compressed nitrogen, extruding the spinning solution through an outer ring of a spinneret plate, outputting core solution through a constant flow pump at the same time, wherein the core solution is 30wt% of N-methyl pyrrolidone aqueous solution, the flow rate of the core solution is 28ml/min, and obtaining the hollow fiber primary membrane after the primary solution extruded through the outer ring passes through a 30cm long room temperature saturated steam atmosphere pipeline. Then, 12 parts of polyacrylamide, 79.3 parts of water, 0.35 part of zinc oxide, 0.35 part of carboxylated carbon nano tube, 5.6 parts of acetone and 2.4 parts of tetrahydrofuran are placed in a beaker, dissolved for 1h at 80 ℃ to obtain uniform transparent electrostatic spinning solution, electrostatic spinning machines are arranged on two sides of a hollow fiber primary membrane discharged through a water vapor atmosphere pipeline, spinning is carried out for 8 minutes under the conditions that the direct current voltage is 20kV, the extrusion rate of the electrostatic spinning solution is 3.0ml/h and the receiving distance is 10cm, so that a composite hollow fiber primary membrane with a composite layer sprayed on the surface is obtained, the composite hollow fiber primary membrane is immersed in a hot water bath for 8h, the water temperature is 60 ℃, and the final hollow fiber membrane is obtained after winding.
Comparative example 6
The composition of the spinning solution and the preparation method thereof are the same as those of the example 6, the spinning solution is heated to be kept constant to 60 ℃, the spinning solution is extruded by a metering pump under the condition of compressed nitrogen, the core solution is extruded by an outer annular space of a spinneret plate and is simultaneously discharged from a central pipe of the spinneret plate by a constant flow pump, the core solution is 30wt% of N-methylpyrrolidone aqueous solution, the flow rate of the core solution is 28ml/min, the primary solution extruded by the outer annular space is immersed into a hot water bath for 8 hours after passing through a 30cm long room temperature saturated steam atmosphere pipeline, the water temperature is 60 ℃, and the final hollow fiber membrane is obtained after winding.
Example 7
A high water flux hollow fiber membrane, the method of making comprising the steps of: 1.6 parts of polyvinylpyrrolidone, 1.6 parts of polyvinyl alcohol, 4.8 parts of polyethylene glycol, 0.3 part of cupric chloride, 0.06 part of tween 80, 0.14 part of span 80, 0.28 part of nano zinc oxide, 0.42 part of carboxylated graphene oxide, 34.4 parts of tetrahydrofuran and 34.4 parts of N, N-dimethylformamide are added into a container and dispersed for 2.5 hours by ultrasound, and the obtained mixture is added into a spinning kettle together with 17.6 parts of polyimide and 4.4 parts of polyacrylate, stirred and dissolved for 20 hours at 50 ℃ to form a transparent viscous solution, and the transparent viscous solution is defoamed for 48 hours by vacuum, so as to obtain spinning liquid.
Heating and keeping the spinning solution constant to 30 ℃, extruding the spinning solution through a metering pump under compressed nitrogen, extruding the spinning solution through an outer ring of a spinneret plate, outputting core solution through a constant flow pump at the central tube of the spinneret plate, wherein the core solution is water, the flow rate of the core solution is 24ml/min, and obtaining the hollow fiber primary membrane after the primary solution extruded through the outer ring passes through a 30cm long room temperature saturated steam atmosphere pipeline. Then, 15 parts of polyethanol amine, 77.1 parts of water, 0.9 part of carboxylated carbon nano tube, 3 parts of acetone and 4 parts of tetrahydrofuran are placed in a beaker, dissolved for 1h at 80 ℃ to obtain uniform transparent electrostatic spinning solution, electrostatic spinning machines are arranged on two sides of a hollow fiber primary membrane discharged through a water vapor atmosphere pipeline, spinning is carried out on the two electrostatic spinning machines for 22 minutes under the conditions that the direct current voltage is 10kV, the extrusion rate of the electrostatic spinning solution is 1.0ml/h and the receiving distance is 12cm, a composite hollow fiber primary membrane with a composite layer sprayed on the outer surface is obtained, the composite hollow fiber primary membrane is immersed in a hot water bath for 10h, the water temperature is 45 ℃, and the final hollow fiber membrane is obtained after winding.
Comparative example 7
The composition of the spinning solution and the preparation method thereof are the same as those of the embodiment 7, the spinning solution is heated to be kept constant to 30 ℃, the spinning solution is extruded by a metering pump under the condition of compressed nitrogen, the core solution is extruded by an outer annular space of a spinneret plate and is output by a constant flow pump at the central tube of the spinneret plate, the core solution is water, the flow rate of the core solution is 24ml/min, the primary solution extruded by the outer annular space is immersed into a hot water bath for 10 hours after passing through a 30cm long room temperature saturated steam atmosphere pipeline, the water temperature is 45 ℃, and the final hollow fiber membrane is obtained after winding.
Example 8
A high water flux hollow fiber membrane, the method of making comprising the steps of: 2.52 parts of polyvinylpyrrolidone, 2.52 parts of polyvinyl alcohol, 3.36 parts of polyethylene glycol, 0.3 part of zinc chloride, 0.3 part of pure water, 0.12 part of sodium dodecyl sulfate, 0.16 part of tween 20, 0.12 part of span 20, 0.24 part of nano zinc oxide, 0.16 part of carboxylated carbon nano tube, 40.6 parts of tetrahydrofuran and 40.6 parts of toluene are added into a container and dispersed for 2 hours by ultrasound, and the obtained mixture, 8.1 parts of polysulfone and 0.9 part of polytetrafluoroethylene are added into a spinning kettle together, stirred and dissolved for 12 hours at 70 ℃ to form a transparent viscous solution, and the vacuum defoaming is carried out for 36 hours to obtain a spinning solution.
Heating and keeping the spinning solution constant to 50 ℃, extruding the spinning solution through a metering pump under compressed nitrogen, extruding the spinning solution through an outer annular space of a spinneret plate, outputting core solution through a constant flow pump at the central tube of the spinneret plate, wherein the core solution is 20wt% of acetone aqueous solution, the flow rate of the core solution is 6ml/min, and obtaining the hollow fiber primary membrane after the primary solution extruded through the outer annular space passes through a 30cm long room temperature saturated steam atmosphere pipeline. Then, 4.9 parts of polyvinyl alcohol, 1.4 parts of polyacrylamide, 0.7 part of polyethylene glycol, 72.2 parts of water, 0.8 part of carboxylated carbon nano tube and 20 parts of tetrahydrofuran are placed in a beaker, dissolved for 1.5 hours at 60 ℃ to obtain uniform transparent electrostatic spinning solution, electrostatic spinning machines are arranged on two sides of a hollow fiber primary membrane discharged through a water vapor atmosphere pipeline, spinning is carried out for 10 minutes under the conditions that the direct current voltage is 10kV, the extrusion rate of the electrostatic spinning solution is 0.7ml/h and the receiving distance is 14cm, a composite hollow fiber primary membrane with a composite layer sprayed on the surface is obtained, the composite hollow fiber primary membrane is immersed in a hot water bath for 6 hours, the water temperature is 65 ℃, and the final hollow fiber membrane is obtained after winding.
Comparative example 8
The composition of the spinning solution and the preparation method thereof are the same as those of the example 8, the spinning solution is heated to be kept constant to 50 ℃, the spinning solution is extruded by a metering pump under the condition of compressed nitrogen, core solution is extruded by an outer annular space of a spinneret plate and is simultaneously discharged from a central tube of the spinneret plate by a constant flow pump, the core solution is 20wt% of acetone aqueous solution, the flow rate of the core solution is 6ml/min, the primary solution extruded by the outer annular space is immersed into a hot water bath for 6h after passing through a 30cm long room temperature saturated steam atmosphere pipeline, the water temperature is 65 ℃, and the final hollow fiber membrane is obtained after winding.
The calculation of the membrane water flux J according to the invention is based on the following formula:
wherein V is the volume of permeated water (L), A is the membrane area (m 2), t is the test time (h), and the test pressure is 0.1MPa
The water contact angle of the surface of the film is measured by adopting a three-point measurement method, five different positions are selected for each sample to be measured respectively, and the final average value is obtained.
The rejection of Bovine Serum Albumin (BSA) by the membrane was measured by uv absorption. Before the test, the surface of the membrane is cleaned by deionized water, the prepared BSA solution is filtered after being pre-pressed for 30 minutes under 0.1Mpa, the stock solution and the penetrating fluid are respectively collected every 10 minutes, the absorbance of the stock solution and the penetrating fluid is tested under an ultraviolet-visible light spectroscope (UV-2450, SHIMADZU, japan), and the retention rate is calculated by the following formula:
wherein: r is the retention rate (%); c (C) p The absorbance value of the stock solution; c (C) f The absorbance value of the permeate was obtained.
The test data of pure water flux, water contact angle, bovine Serum Albumin (BSA) and the like of the hollow fiber membranes prepared in examples 1 to 8 and comparative examples 1 to 8 are shown in Table 1.
Table 1 comparison of hollow fiber membrane properties prepared in examples and comparative examples
Table 1 (subsequent) comparison of hollow fiber membrane properties prepared in examples and comparative examples
The foregoing description of the preferred embodiments of the present invention will be readily apparent to those skilled in the art that variations and modifications may be made without departing from the general inventive concept, and these should also be considered as being within the scope of the invention.
Claims (10)
1. A preparation method of a hollow fiber membrane with high water flux is characterized by comprising the following steps: the preparation method at least comprises the following steps:
s1: preparation of a hollow fiber primary membrane: preparing spinning solution of the hollow fiber primary membrane, spinning the spinning solution, extruding the spinning solution from an outer annular space of a spinneret plate, conveying core solution at a central tube of the spinneret plate through a constant flow pump, and obtaining the hollow fiber primary membrane after the primary solution extruded from the outer annular space of the spinneret plate passes through a steam atmosphere pipeline;
s2: preparation of a composite hollow fiber primary membrane: preparing electrostatic spinning solution of the composite layer, and spraying and adhering the electrostatic spinning solution on the surface of the hollow fiber primary membrane prepared in the step S1 by an electrostatic spinning machine to obtain a composite hollow fiber primary membrane with the outer surface sprayed with the composite layer;
s3: post-treatment: immersing the composite hollow fiber primary membrane prepared in the step S2 in water for water bath for 1-12h to obtain the hollow fiber membrane.
2. The method for preparing the high water flux according to claim 1, wherein: the spinning solution in the step S1 comprises the following components in parts by weight: 8-25 parts of polymer, 1-10 parts of pore-forming agent, 0.5-2 parts of nanoparticle additive and 63-90.5 parts of solvent, mixing the pore-forming agent, the nanoparticle additive and the solvent, then performing ultrasonic dispersion for 0.5-3 hours, adding the polymer, placing the obtained mixed solution in a spinning kettle, stirring and dissolving at 30-90 ℃ until a transparent viscous solution is formed, performing vacuum defoaming for 6-48 hours to obtain spinning solution of the hollow fiber primary membrane, heating and stabilizing the spinning solution to 30-60 ℃, extruding the spinning solution by a metering pump under compressed nitrogen, and performing spinning.
3. A method of high water flux preparation according to claim 2, wherein: the electrostatic spinning solution of the composite layer in the step S2 comprises the following components in parts by weight: 4-20 parts of water-soluble polymer, 60-90 parts of water, 0.5-2 parts of nanoparticle additive and 6-20 parts of diluent, and dissolving the components at 30-80 ℃ for 0.5-4 hours to prepare uniform and transparent electrostatic spinning solution.
4. A method of high water flux preparation according to claim 3, wherein: the preparation method of the composite hollow fiber primary membrane in the step S2 comprises the following steps: after the hollow fiber primary membrane prepared in the step S1 is discharged from a water vapor atmosphere pipeline, at least two electrostatic spinning machines are arranged on the periphery of the hollow fiber primary membrane, the direct current voltage of each electrostatic spinning machine is 10-30kV, the extrusion rate of electrostatic spinning liquid is 0.5-3.0ml/h, the receiving distance is 10-30cm, the electrostatic spinning time is 5-30 minutes, and the central axis of a needle head of each electrostatic spinning machine along the length direction is mutually perpendicular to the central axis of the hollow fiber primary membrane along the length direction.
5. The method for preparing the high water flux according to claim 4, wherein: the polymer in the spinning solution is at least one selected from polysulfone, polyamide, polyethersulfone, polyvinyl chloride and copolymer thereof, polyvinylidene fluoride and copolymer thereof, polyimide, polycarbonate, polyacrylate and polytetrafluoroethylene.
6. The method for preparing the high water flux according to claim 5, wherein: the solvent in the spinning solution is at least one selected from N-methylpyrrolidone, dimethyl sulfoxide, acetone, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, benzene and toluene; the nanoparticle additive in the spinning solution is at least one selected from nano zinc oxide, carboxylated graphene oxide and carboxylated carbon nanotubes.
7. A method of high water flux preparation according to claim 3, wherein: the nanoparticle additive in the electrostatic spinning solution is at least one selected from nano zinc oxide, carboxylated graphene oxide and carboxylated carbon nanotubes; the water-soluble polymer in the electrostatic spinning solution is at least one of polyvinyl alcohol, polyacrylamide and polyethylene glycol; the diluent is one or a mixture of two of acetone and tetrahydrofuran.
8. The method for preparing the high water flux according to claim 7, wherein: the core liquid in the step S1 is an aqueous solution of an organic solvent, the content of the organic solvent is 0-30wt%, and the organic solvent is at least one selected from N-methylpyrrolidone, dimethyl sulfoxide, acetone, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, benzene and toluene.
9. A method of preparing a high water flux according to any one of claims 2-8, characterized in that: the pore-forming agent in the spinning solution comprises the following components in parts by weight: 1-10 parts of high molecular polymer, 0.1-2 parts of inorganic matter and 0.1-1 part of surfactant, wherein the high molecular polymer is at least one selected from polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol; the inorganic matters are at least one selected from lithium chloride, zinc chloride, copper chloride and pure water; the surfactant is at least one selected from sodium dodecyl sulfate, tween and span.
10. A high water flux hollow fiber membrane characterized in that: the hollow fiber membrane is obtained by the preparation method of any one of claims 1 to 9.
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