CN113117534A - Preparation method of fiber-reinforced aromatic polyamide hollow fiber membrane and hollow fiber membrane prepared by same - Google Patents
Preparation method of fiber-reinforced aromatic polyamide hollow fiber membrane and hollow fiber membrane prepared by same Download PDFInfo
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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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
- D01F6/905—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides of aromatic polyamides
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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
- B01D2323/12—Specific ratios of components used
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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
- B01D2323/50—Control of the membrane preparation process
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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
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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
- B01D2325/30—Chemical resistance
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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
- B01D2325/32—Melting point or glass-transition temperatures
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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
- B01D2325/36—Hydrophilic membranes
Abstract
The invention discloses a preparation method of a fiber-reinforced aromatic polyamide hollow fiber membrane, which comprises the following steps: mixing the film-forming polymer, a pore-forming agent and an additive, dissolving in a spinning solvent, and defoaming to prepare a film casting solution; filtering the casting solution, and quantitatively injecting the casting solution into a hollow spinning jet by a metering pump; synchronously feeding three bundles of PPTA continuous fibers pre-impregnated by concentrated sulfuric acid into a hollow spinning jet to be compounded with PPTA casting solution; under the action of extrusion pressure and guide roller traction tension, PPTA complex and core liquid are extruded out through a spinning nozzle at the same time, and enter a coagulating bath for coagulation forming after passing through an air layer to prepare a nascent hollow fiber membrane; and soaking the nascent hollow fiber membrane in water for bathing, and fully removing residues to prepare the continuous fiber reinforced PPTA hollow fiber membrane. The method is simple and convenient, has low cost, and the prepared hollow fiber membrane has high tensile strength, heat resistance, chemical reagent resistance and hydrophilicity, is suitable for external pressure type filtration and internal pressure type filtration, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of enhancement of polymer hollow fiber membrane materials, in particular to a preparation method of a fiber-enhanced aromatic polyamide hollow fiber membrane and a hollow fiber membrane prepared by the same.
Background
The polymer hollow fiber membrane has the characteristics of large specific surface area, high component filling density, high separation efficiency and the like, and is widely applied to the field of water treatment. The poly-p-phenylene terephthalamide (PPTA) is typical para-aramid, has rigid macromolecules, is an important raw material for preparing high-strength, high-modulus and high-temperature-resistant para-aramid fibers, has excellent high-temperature resistance, chemical reagent resistance and hydrophilic characteristics, and is an ideal material for preparing high-performance hollow fiber porous membranes. But the melting point (more than 500 ℃) of the PPTA rigid macromolecule is lower than the decomposition temperature, so the PPTA rigid macromolecule can not be processed and formed by adopting the conventional melt spinning technology, and the entropy value of the free energy change of the PPTA rigid macromolecule in the dissolving process is smaller than that of the flexible macromolecule, so the PPTA rigid macromolecule is difficult to dissolve in the conventional solvent and can only dissolve in strong inorganic acids such as concentrated sulfuric acid, chlorosulfonic acid and the like. Zschocke et al [ Solvent resistant membranes from poly- (p-phenylene-tert. -amide), desalinization, 34 (1980): 69-75]PPTA flat membrane is prepared, the flux of the PPTA flat membrane in different solvents is tested, and the pure water flux of the membrane is only 12.8L/(m)2d) (3 MPa). Chinese patent publication No. CN104353372A discloses a method for preparing an aromatic polyamide hollow fiber porous membrane, which comprises premixing PPTA resin, a solvent, a pore-forming agent and inorganic particles in a dissolving kettle to prepare a membrane casting solution, injecting the membrane casting solution into a double-screw extruder, completely dissolving under the action of shearing force, entering a spinneret plate through a metering pump, and carrying out dry-wet spinning to prepare the PPTA hollow fiber porous membrane.
As described above, the solution spinning method is the most commonly used spinning film-making technique because the spinning film-making process is mature, the equipment investment cost is low, and the obtained film has small pore diameter and narrow distribution. However, the hollow fiber membrane obtained by the solution spinning method has poor mechanical property and low tensile strength, and the problem of membrane filament breakage is easy to occur in the using or cleaning process. In order to increase the tensile strength of the hollow fiber membrane, the most common technique is to use reinforcement. For example, chinese patent publication No. CN102600733A discloses a reinforced polyvinylidene fluoride hollow fiber membrane and a method for preparing the same, which comprises preparing a hollow fiber base membrane with excellent strength by a melt spinning method, then compounding a surface separation layer on the surface of the base membrane, and classifying into homogeneous reinforced hollow fiber membrane and heterogeneous reinforced hollow fiber membrane according to the surface separation layer and the polymer component of the base membrane. Chinese patent publication No. CN103100307A discloses a characterization of the interface bonding state of a reinforced hollow fiber membrane, which shows that the interface bonding state of a homogeneous reinforced hollow fiber membrane is obviously superior to that of a heterogeneous reinforced hollow fiber membrane. Chinese patent publication No. CN104801205A discloses a method for preparing homogeneous reinforced PPTA hollow fiber membrane, which weaves PPTA continuous fiber into hollow tube as reinforcement, and constructs a homogeneous surface separation layer on the outer surface of the reinforcement, wherein the surface separation layer is composed of PPTA resin, pore-forming agent and inorganic particles. The tensile strength of the PPTA hollow fiber membrane obtained by the method is obviously improved, but because the surface separation layer is compounded with the outer layer of the braided tube, the separation layer and the reinforcement body are easy to peel or slip in the backwashing or internal pressure type filtering process of the hollow fiber membrane, so that the membrane is suitable for external pressure type filtering. Meanwhile, the fiber reinforcement is a hollow braided tube, more PPTA fibers are consumed, and the membrane manufacturing cost is higher.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a preparation method of a fiber reinforced aromatic polyamide hollow fiber membrane.
Another object of the present invention is to provide a hollow fiber membrane prepared by the above preparation method.
Therefore, the technical scheme of the invention is as follows:
a preparation method of a fiber reinforced aromatic polyamide hollow fiber membrane comprises the following steps:
(1) uniformly mixing 1-15% of a film-forming polymer, 5-20% of a pore-forming agent and 0-5% of an additive in percentage by mass, dissolving the mixture in 60-94% of a spinning solvent at 70-90 ℃, and defoaming the mixture in vacuum to obtain a casting solution of the film-forming polymer, wherein the film-forming polymer is poly (p-phenylene terephthalamide) (PPTA);
(2) filtering the casting solution by a filter screen and quantitatively injecting the casting solution into a hollow spinning nozzle by a metering pump;
(3) when the casting solution enters a hollow spinning nozzle, three bundles of poly-p-phenylene terephthamide continuous fibers subjected to dipping pretreatment by a spinning solvent for 1-10 seconds enter the hollow spinning nozzle along equidistant positions on the cross section of a spinning hole (the enhancement effect can be better exerted, and the permeability of the film is not influenced), and are compounded with the casting solution to form a complex; or the three beams of PPTA continuous fibers which are not subjected to spinning solvent immersion pretreatment directly enter a hollow spinning jet along equidistant positions on the cross section of a spinning hole, stay in the casting solution for 0.1-2.0 seconds, and are compounded with the casting solution to form a complex, wherein the PPTA continuous fibers can be partially swelled or dissolved on the surface by being pre-immersed or stay in the casting solution, so that the PPTA continuous fibers are favorably compounded with the casting solution;
(4) under the action of extrusion pressure and traction tension of a guide roller, the complex is extruded by a spinneret, the introduced core liquid is extruded while the complex is extruded by the spinneret, the extruded complex enters a coagulating bath after passing through an air layer for coagulating and forming to prepare a nascent fiber reinforced aromatic polyamide hollow fiber membrane, wherein the air layer has the function of swelling or dissolving the surface of PPTA continuous fibers through a solvent in a casting solution, so that the bonding strength between the membrane wall and a homogeneous continuous fiber interface is improved;
(5) and fully treating the nascent fiber reinforced aromatic polyamide hollow fiber membrane in a water bath, and removing the residual spinning solvent, pore-forming agent and water-soluble additive to prepare the fiber reinforced aromatic polyamide hollow fiber membrane.
Wherein, in the step (1), the pore-foaming agent is a water-soluble polymer, and is selected from one of polyethylene glycol with an average molecular weight of 600-; the additive is hydrophilic silicon dioxide with the particle size of 20-200 nanometers, tween-80 or water;
in the step (1) and the step (3), the spinning solvent is concentrated sulfuric acid (98 wt%).
Preferably, the fineness of the continuous fiber of the paraphenylene terephthalamide is 100-1000D.
Preferably, in the step (3), the compounding temperature of the continuous p-phenylene terephthalamide fiber and the casting solution is 70-90 ℃; the three bundles of homogeneous continuous fibers are all parallel to the axial direction of the hollow fiber membrane, the distances from the three bundles of homogeneous continuous fibers to the central axis of the membrane are equal, the three bundles of homogeneous continuous fibers are uniformly distributed in the cross section of the membrane, and the three bundles of homogeneous continuous fibers are uniformly embedded in the wall of the hollow fiber membrane at equal intervals.
Preferably, in the step (4), the core solution is a sulfuric acid aqueous solution with the temperature of 20-70 ℃ and the concentration of 0-50 wt%; the coagulant in the coagulating bath is a sulfuric acid water solution with the concentration of 0-40 wt%, and the temperature of the coagulating bath is 20-60 ℃; the height of the air layer is 2-100 mm; in the step (5), the temperature of the water bath is 20-50 ℃, and the treatment time is not less than 48 hours.
The fiber-reinforced aromatic polyamide hollow fiber membrane prepared by the preparation method comprises a hollow fiber membrane formed by a membrane-forming polymer and three bundles of homogeneous continuous fibers which are uniformly distributed in parallel with the axial direction of the hollow fiber membrane at equal intervals along the circumferential direction, wherein the inner diameter of the fiber-reinforced aromatic polyamide hollow fiber membrane is 0.4-1.2mm, and the outer diameter of the fiber-reinforced aromatic polyamide hollow fiber membrane is 0.6-2.4 mm; the average pore diameter of the fiber reinforced aromatic polyamide hollow fiber membrane is 0.01-0.20 mu m, the tensile strength is more than 1000MPa, the bursting pressure is more than 0.4MPa, and the contact angle of pure water is less than 50 degrees.
The invention mainly compounds and forms three bundles of PPTA continuous fibers and PPTA membrane casting solution, so that the three bundles of PPTA continuous fibers are uniformly embedded in the wall of the PPTA hollow fiber membrane at equal intervals, and the homogeneous continuous fiber reinforced PPTA hollow fiber membrane is prepared. Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts the conventional solution spinning method, has simple and convenient preparation process, and solves the problem of low tensile strength of the membrane by compounding and forming the PPTA continuous fiber and the PPTA casting solution of the homogeneous membrane forming polymer, while keeping the characteristics of smaller and narrower pore diameter and distribution, mature preparation process, less equipment investment and the like of the membrane by the solution spinning method, and the prepared membrane has higher tensile strength.
(2) According to the invention, the PPTA continuous fiber and the homogeneous film-forming polymer PPTA casting solution are compounded and formed, and the solvent in the casting solution has partial swelling or dissolving effect on the surface of the PPTA continuous fiber while the casting solution and the fiber are compounded under the action of the cosolvent, so that the interface bonding strength between the surface separation layer and the fiber reinforcement after solidification and formation is improved, the reinforcement effect is uniform and symmetrical, and the problems of low interface bonding strength of a heterogeneous fiber reinforced membrane, easy interface peeling in the long-term use process and the like are solved.
(3) Compared with the heterogeneous or homogeneous fiber braided tube reinforced hollow fiber membrane compounded on the outer layer, the fiber reinforced aromatic polyamide hollow fiber membrane of the invention has the advantages that the PPTA continuous fiber is inlaid in the wall of the PPTA hollow fiber membrane, and a surface separation layer is not formed on the outer surface of the fiber braided tube, so the membrane can be used for external pressure type filtration and internal pressure type separation process, has good backwashing resistance and outstanding heat resistance, chemical reagent resistance and hydrophilicity (the contact angle of pure water is less than 50 degrees), and can be applied to the fields of municipal sewage and industrial wastewater treatment and reuse, drinking water pretreatment, water quality purification, seawater desalination pretreatment, biological medicine, food and beverage and the like.
(4) Compared with the fiber braided tube reinforced hollow fiber membrane, the fiber reinforced aromatic polyamide hollow fiber membrane has the advantages of less continuous fiber consumption and production cost reduction.
(5) Compared with heterogeneous fiber reinforced membrane filaments, the hollow fiber membrane has the advantages that the recycling process of the waste membrane filaments is greatly simplified, and during recycling, impurities attached to the membrane filaments can be recycled only after being removed, so that the waste membrane filaments are utilized as resources.
Drawings
FIG. 1 is a schematic diagram of the cross-sectional structure of a fiber-reinforced PPTA hollow fiber membrane prepared by the present invention;
figure 2 is a cross-sectional topography of a fiber reinforced PPTA hollow fiber membrane prepared according to the present invention (PPTA multifilament fiber at circle).
In the figure:
a PPTA membrane wall; PPTA multifilament fiber
Detailed Description
The following detailed description of the preparation method of the present invention is made with reference to the accompanying drawings and examples, which are not intended to limit the present invention. Those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or designing other structures for carrying out the same purposes of the present invention.
In step (1) and step (3) of the following examples, the spinning solvent used was concentrated sulfuric acid (98 wt%).
Example 1
(1) Preparing a PPTA casting solution: mixing 2.5 wt% of PPTA, 15 wt% of pore-forming agent polyethylene glycol (molecular weight 2000) and 1.5 wt% of hydrophilic silicon dioxide with the average particle size of 300nm, dissolving the mixture in concentrated sulfuric acid (98 wt%) (the content of concentrated sulfuric acid in the membrane casting solution is 81 wt%), stirring and dissolving the mixture for 4 hours at 80 ℃ until the mixture is uniformly mixed, and obtaining the PPTA membrane casting solution after vacuum defoaming.
(2) Filtering the PPTA casting solution by a filter screen and quantitatively injecting the PPTA casting solution into a hollow spinning jet by a metering pump under the action of 0.3MPa air pressure;
(3) when the casting solution enters a hollow spinning nozzle, three PPTA continuous fibers with the diameter of about 220D (134 single fibers) are soaked in concentrated sulfuric acid (98 wt%) for 0.5 second, then enter the hollow spinning nozzle along equidistant positions on the cross section of a spinning pore channel, are compounded with the casting solution, pass through an air layer of 5cm under the action of extrusion pressure and guide roller traction tension, and then enter a coagulating bath at 40 ℃ for coagulation forming, wherein a coagulating agent is a sulfuric acid water solution with the mass percent of 10 wt%, so that the nascent fiber reinforced aromatic polyamide hollow fiber membrane is prepared;
(4) extruding a complex of the casting solution and the PPTA continuous fiber by a spinning nozzle, and simultaneously extruding introduced core liquid, wherein the core liquid is a sulfuric acid aqueous solution with the mass percentage of 10 wt%, and the temperature of the core liquid is 30 ℃;
(5) and (3) immersing the nascent fiber reinforced aromatic polyamide hollow fiber membrane into a 30 ℃ water bath, treating for 72 hours, and removing soluble components in the membrane to prepare the fiber reinforced aromatic polyamide hollow fiber membrane.
The inner diameter and the outer diameter of the obtained fiber reinforced aromatic polyamide hollow fiber membrane are respectively 1.0mm and 1.4mm, the tensile strength of the membrane is about 1200MPa, the bursting pressure is about 0.4MPa, and the pure water flux at room temperature under 0.1MPa is 280L/(m)2H) a pure water contact angle of about 30 deg..
As shown in FIG. 1, the three bundles of homogeneous continuous fibers are all parallel to the axial direction of the hollow fiber membrane, are uniformly distributed in the cross section of the membrane, and are uniformly embedded in the wall of the hollow fiber membrane at equal intervals.
In the topographical map of fig. 2, the cross section shown is slightly deformed as compared with fig. 1, because the fibers embedded in the membrane wall have higher strength and are in a state of multi-strand dispersion, and therefore, when the cross section of the sample is made, the difficulty of interception is higher, resulting in slightly influenced strand position distribution.
Example 2
(1) Preparing a PPTA casting solution: mixing 4.5 wt% of PPTA, 10 wt% of composite pore-foaming agent polyethylene glycol (molecular weight 2000) and polyvinylpyrrolidone (molecular weight 58000) (polyethylene glycol/polyvinylpyrrolidone is 10/1), 0.5 wt% of hydrophilic silicon dioxide with the average particle size of 300nm, dissolving the mixture in concentrated sulfuric acid (the content of concentrated sulfuric acid in the casting solution is 85 wt%), stirring and dissolving the mixture for 4 hours at 80 ℃ until the mixture is uniform, and defoaming the mixture in vacuum to obtain the PPTA casting solution.
(2) Filtering the PPTA casting solution by a filter screen and quantitatively injecting the PPTA casting solution into a hollow spinning jet by a metering pump under the action of 0.3MPa air pressure;
(3) when the casting solution enters a hollow spinning nozzle, three PPTA continuous fibers with the diameter of about 400D (134 single fibers) are soaked in concentrated sulfuric acid (98 wt%) for 2 seconds, then enter the hollow spinning nozzle along equidistant positions on the cross section of a spinning pore channel, are compounded with the casting solution, pass through an air layer of 8cm under the action of extrusion pressure and traction tension of a guide roller, and then enter a coagulating bath at 50 ℃ for coagulation forming, wherein a coagulating agent is a sulfuric acid water solution with the mass percent of 5 wt%, so that a nascent fiber reinforced aromatic polyamide hollow fiber membrane is prepared;
(4) and extruding the composite of the casting solution and the PPTA continuous fiber by a spinning nozzle, and simultaneously extruding introduced core liquid, wherein the core liquid is a sulfuric acid aqueous solution with the mass percentage of 5 wt%, and the temperature of the core liquid is 30 ℃.
(5) And (3) immersing the nascent fiber reinforced aromatic polyamide hollow fiber membrane into a 30 ℃ water bath, treating for 72 hours, and removing soluble components in the membrane to prepare the fiber reinforced aromatic polyamide hollow fiber membrane.
The inner diameter and the outer diameter of the obtained fiber reinforced aromatic polyamide hollow fiber membrane are respectively 2.2mm and 2.6mm, the tensile strength of the membrane is about 2000MPa, the bursting pressure is about 0.7MPa, and the pure water flux at room temperature under 0.1MPa is 220L/(m)2H) pure water contact angle of about 48 °.
Example 3
(1) Preparing a PPTA casting solution: mixing 3 wt% of PPTA, 15 wt% of composite pore-foaming agent polyethylene glycol (molecular weight 2000) and polyvinylpyrrolidone (molecular weight 58000) (polyethylene glycol/polyvinylpyrrolidone is 10/3), 1 wt% of hydrophilic silicon dioxide with the average particle size of 300nm, dissolving the mixture in concentrated sulfuric acid (the content of concentrated sulfuric acid in the casting solution is 81 wt%), stirring and dissolving the mixture for 4 hours at 80 ℃ until the mixture is uniformly mixed, and defoaming the PPTA casting solution in vacuum to obtain the PPTA casting solution.
(2) Filtering the PPTA casting solution by a filter screen and quantitatively injecting the PPTA casting solution into a hollow spinning jet by a metering pump under the action of 0.3MPa air pressure;
(3) when the casting solution enters a hollow spinning nozzle, three PPTA continuous fibers with the diameter of about 300D (60 single fibers) are soaked in concentrated sulfuric acid (98 wt%) for 1 second, then enter the hollow spinning nozzle along equidistant positions on the cross section of a spinning pore channel, are compounded with the casting solution, pass through a 10cm air layer under the action of extrusion pressure and guide roller traction tension, and then enter a 50 ℃ solidification bath for solidification and forming, wherein a coagulant is a sulfuric acid water solution with the mass percent of 2 wt%, so that the nascent fiber reinforced aromatic polyamide hollow fiber membrane is prepared;
(4) extruding a complex of the casting solution and the PPTA continuous fiber by a spinning nozzle, and simultaneously extruding introduced core liquid, wherein the core liquid is a sulfuric acid aqueous solution with the mass percentage of 2 wt%, and the temperature of the core liquid is 30 ℃;
(5) and (3) immersing the nascent fiber reinforced aromatic polyamide hollow fiber membrane into a 30 ℃ water bath, treating for 72 hours, and removing soluble components in the membrane to prepare the fiber reinforced aromatic polyamide hollow fiber membrane.
The inner diameter and the outer diameter of the obtained fiber reinforced aromatic polyamide hollow fiber membrane are respectively 2.0mm and 2.4mm, the tensile strength of the membrane is about 1600MPa, the bursting pressure is about 0.6MPa, and the pure water flux at room temperature under 0.1MPa is 320L/(m)2H) a pure water contact angle of about 40 deg..
Claims (10)
1. A preparation method of a fiber reinforced aromatic polyamide hollow fiber membrane comprises the following steps:
(1) uniformly mixing 1-15% of film-forming polymer, 5-20% of pore-forming agent and 0-5% of additive in percentage by mass, dissolving the mixture in a spinning solvent at 70-90 ℃, and defoaming the mixture in vacuum to obtain a casting solution of the film-forming polymer, wherein the film-forming polymer is poly (p-phenylene terephthalamide);
(2) filtering the casting solution by a filter screen and quantitatively injecting the casting solution into a hollow spinning nozzle by a metering pump;
(3) when the casting solution enters a hollow spinning nozzle, three bundles of poly-p-phenylene terephthamide continuous fibers subjected to dipping pretreatment by a spinning solvent for 1-10 seconds enter the hollow spinning nozzle along the equidistant positions on the cross section of a spinning hole, and are compounded with the casting solution to form a complex; or the three-beam PPTA continuous fibers which are not subjected to spinning solvent immersion pretreatment directly enter a hollow spinning jet along equidistant positions on the cross section of a spinning hole, stay in the casting solution for 0.1-2.0 seconds, and are compounded with the casting solution to form a complex;
(4) under the action of extrusion pressure and guide roller traction tension, the complex is extruded by a spinneret, the introduced core liquid is extruded while the complex is extruded by the spinneret, and the extruded complex enters a coagulating bath after passing through a section of air layer for coagulating and forming to prepare the nascent fiber reinforced aromatic polyamide hollow fiber membrane;
(5) and fully treating the nascent fiber reinforced aromatic polyamide hollow fiber membrane in a water bath to prepare the fiber reinforced aromatic polyamide hollow fiber membrane.
2. The method of claim 1, wherein: in the step (1), the pore-forming agent is a water-soluble polymer, and is selected from one of polyethylene glycol with an average molecular weight of 600-.
3. The method of claim 1, wherein: in the step (1), the additive is hydrophilic silicon dioxide with the particle size of 20-200 nanometers, tween-80 or water.
4. The method of claim 1, wherein: in the step (1) and the step (3), the spinning solvent is concentrated sulfur.
5. The method of claim 1, wherein: the fineness of the terephthalic terephthalamide continuous fiber is 100-1000D.
6. The method of claim 1, wherein: in the step (3), the compounding temperature of the continuous p-phenylene terephthalamide fiber and the membrane casting solution is 70-90 ℃.
7. The method of claim 1, wherein: in the step (3), the three bundles of homogeneous continuous fibers are all parallel to the axial direction of the hollow fiber membrane, are uniformly distributed in the cross section of the membrane, and are uniformly embedded in the wall of the hollow fiber membrane at equal intervals.
8. The method of claim 1, wherein: in the step (4), the core solution is a sulfuric acid aqueous solution with the temperature of 25-70 ℃ and the concentration of 0-50 wt%; the coagulant in the coagulating bath is a sulfuric acid water solution with the concentration of 0-40 wt%, and the temperature of the coagulating bath is 20-60 ℃; the height of the air layer is 2-100 mm.
9. The method of claim 1, wherein: in the step (5), the temperature of the water bath is 20-50 ℃, and the treatment time is not less than 48 hours.
10. A fiber-reinforced aromatic polyamide hollow fiber membrane produced by the production method according to any one of claims 1 to 9, characterized in that: the fiber-reinforced aromatic polyamide hollow fiber membrane consists of a hollow fiber membrane formed by a membrane-forming polymer and three bundles of homogeneous continuous fibers which are parallel to the axis of the hollow fiber membrane and are uniformly distributed along the circumferential direction at equal intervals, wherein the inner diameter of the fiber-reinforced aromatic polyamide hollow fiber membrane is 0.4-1.2mm, and the outer diameter of the fiber-reinforced aromatic polyamide hollow fiber membrane is 0.6-2.4 mm; the average pore diameter of the fiber reinforced aromatic polyamide hollow fiber membrane is 0.01-0.20 mu m, the tensile strength is more than 1000MPa, the bursting pressure is more than 0.4MPa, and the contact angle of pure water is less than 50 degrees.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114632427A (en) * | 2022-03-25 | 2022-06-17 | 深圳世纪盛源环境科技有限公司 | Composite filament, reinforced hollow fiber composite membrane and preparation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102266726A (en) * | 2011-08-23 | 2011-12-07 | 浙江大学 | Method for preparing long fiber reinforced hollow fibrous membrane |
| CN103263857A (en) * | 2013-05-16 | 2013-08-28 | 天津工业大学 | Device for preparing fiber-reinforced hollow fiber membrane |
| CN104801205A (en) * | 2015-04-20 | 2015-07-29 | 天津工业大学 | Preparation method for homogeneous enhanced PPTA hollow fiber membrane |
| JP2016010792A (en) * | 2014-06-04 | 2016-01-21 | Nok株式会社 | Method for production of porous hollow fiber membrane of fiber-reinforced polyvinylidene fluoride |
| CN112604509A (en) * | 2020-11-24 | 2021-04-06 | 上海工程技术大学 | Preparation facilities of many monofilament reinforcing hollow fiber membrane |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102266726A (en) * | 2011-08-23 | 2011-12-07 | 浙江大学 | Method for preparing long fiber reinforced hollow fibrous membrane |
| CN103263857A (en) * | 2013-05-16 | 2013-08-28 | 天津工业大学 | Device for preparing fiber-reinforced hollow fiber membrane |
| JP2016010792A (en) * | 2014-06-04 | 2016-01-21 | Nok株式会社 | Method for production of porous hollow fiber membrane of fiber-reinforced polyvinylidene fluoride |
| CN104801205A (en) * | 2015-04-20 | 2015-07-29 | 天津工业大学 | Preparation method for homogeneous enhanced PPTA hollow fiber membrane |
| CN112604509A (en) * | 2020-11-24 | 2021-04-06 | 上海工程技术大学 | Preparation facilities of many monofilament reinforcing hollow fiber membrane |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114632427A (en) * | 2022-03-25 | 2022-06-17 | 深圳世纪盛源环境科技有限公司 | Composite filament, reinforced hollow fiber composite membrane and preparation method |
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