CN105056773B - The preparation method of the embedded hollow composite membrane of enhancing in original position - Google Patents
The preparation method of the embedded hollow composite membrane of enhancing in original position Download PDFInfo
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- CN105056773B CN105056773B CN201510443598.6A CN201510443598A CN105056773B CN 105056773 B CN105056773 B CN 105056773B CN 201510443598 A CN201510443598 A CN 201510443598A CN 105056773 B CN105056773 B CN 105056773B
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Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Prepared the present invention relates to separation membrane material and enhancing modification technology, it is desirable to provide a kind of preparation method of the embedded hollow composite membrane of enhancing in situ.Including：It will obtain coating feed liquid after the mixing of fluoropolymer resin, pore-foaming agent, hydrophilizing agent and solvent, stirring, filtering, vacuum defoamation；By the smooth cross winding of multi-strand yarns on the plug of rotation, yarn crossovers point is bonded with ultra-sonic welded, is formed after network tubrOar enhancing base materials, is moved down along plug and continuously enter coating head；Coating feed liquid penetrates into yarn and coats enhancing base materials completely, leaves continuously from coating head and enters after coagulating bath, surface feed liquid and the water coke slurry film forming in coagulating bath, final that the embedded hollow composite membrane of enhancing in situ is made.The preparation method of the present invention is simple, continuous, and can realize industrialized production；Peeling is not present in the present invention, the problem of overcoming the peel strength deficiency of composite membrane in the prior art；The embedded network tubrOar enhancing base materials cost in original position is relatively low, final reduction membrane material cost.
Description
Technical Field
The invention belongs to the technical field of preparation and enhancement modification of separation membrane materials, and relates to a preparation method of an in-situ embedded enhanced hollow composite membrane.
Background
At present, a polymer separation membrane as an important separation material is widely applied to the fields of sewage treatment, medicines, beverages, chemical industry, electronics, food, paper making and the like. The hollow fiber membrane has the advantages of large specific surface area, high packing density, small volume, high treatment efficiency and simple production process, and is a main membrane material. In order to make the transmembrane resistance low, the wall thickness of the hollow fiber membrane is generally thin (about tens of microns), and although the hollow fiber membrane belongs to a self-supporting membrane material and has certain mechanical strength, the polymer separation membrane has a porous structure with high porosity, so that the hollow fiber membrane has the defect of insufficient mechanical strength when applied to high-pressure fluid treatment or high-frequency vibration. In order to improve the mechanical strength of the hollow fiber polymer membrane, Canada Zenon company (U.S. Pat. No.5,472,607, US2003/0098275A1, WO 00/78437A 1) discloses a preparation technology of a composite polymer hollow fiber membrane for the first time, the polymer composite hollow fiber membrane prepared by the technology only has a thin polymer separation layer, the thickness of the polymer separation layer is 0.01-0.1 mm, therefore, the water flux of the obtained membrane is greatly increased, and the transmembrane pressure is greatly reduced. However, since the hollow fiber membrane is formed by merely compounding the polymer separation membrane on the outer surface of the fiber woven tube which is woven in advance, the binding ability between the polymer separation membrane and the fiber woven tube is not good, and the polymer separation membrane and the fiber woven tube are likely to fall off during the reverse cleaning of the membrane. Kolon industries, Kolon, Korea, (US2008/0292823A1, US2008/0305290A1, WO 2008/097011A1) discloses a technique for controlling the amount of dope solution to be permeated by adjusting the ratio of the traveling speed of a fiber-woven tube to the amount of dope solution extruded. The penetration of the casting solution can be controlled within 30% by the technology, and the obtained composite hollow fiber microporous membrane has a layer of polymer separation membrane with the thickness of less than 0.2 mm. Chinese patent CN100546702C discloses a composite membrane prepared by coating a casting solution on a capillary-shaped woven fabric, so that the coating solution penetrates into the woven fabric to improve the strength of the composite membrane. Chinese patents CN101357303B and CN102784566B disclose that a composite membrane is prepared by pre-modifying and coating a braided tube, and then coating a membrane preparation solution for the second time. Although the similar technology strengthens the binding force between the separation membrane and the fiber braided tube to a certain extent, the problem that the polymer separation membrane is separated from the fiber braided tube in the backwashing process of the composite hollow fiber microporous membrane is not thoroughly solved. The above-mentioned methods generally prepare tubular braided tubes first, and then coat the membrane casting solution to prepare the composite membrane, and the process gap is relatively complicated. The tubular braid is woven at a slower rate, perhaps 1/10, which is the rate at which composite films are made, requiring more braiding machines. In order to ensure the rigidity and roundness of the tubular braided fabric, a certain thickness of the braided fabric is required, the wall thickness of the correspondingly prepared composite membrane is increased, and the relatively high filling density of the hollow fiber membrane is preferably smaller in outer diameter, so that the inner diameter of the composite membrane is correspondingly smaller, and the usable length of the hollow fiber membrane in the packaging membrane module is limited. In addition, the tubular braided fabric has high raw material and manufacturing cost, and the cost of the composite membrane is increased.
Chinese patent CN101543731B discloses a method for preparing a fiber braided tube embedded reinforced polymer hollow fiber microporous membrane, which is characterized in that a fiber braiding-co-extrusion integrated film forming process is adopted, namely a core liquid tube is fixed in the middle of a braided tube, fiber bundles are braided into a fiber braided tube along the core liquid tube, then a casting film liquid, the core liquid and the fiber braided tube are co-extruded through an extrusion die, and the fiber braided tube embedded reinforced polymer hollow fiber microporous membrane is prepared through a phase transition method. The method successfully embeds the fiber braided tube into the body of the hollow fiber membrane, introduces the core liquid into the inner cavity of the braided tube and effectively controls the inner diameter of the hollow fiber membrane, thereby solving the technical problems that a polymer layer and the braided fiber tube are easy to separate, the inner cavity of the hollow fiber is easy to block and the like in the fiber braided tube reinforced hollow fiber membrane prepared by the traditional coating process. Chinese patents CN100393397C and CN101837248B disclose that a hollow fiber membrane is prepared first, and then a fiber is wound on the outer surface of the hollow fiber membrane to form a net or fiber yarns are adhered to the outer surface of the hollow fiber membrane to be coated with a membrane preparation solution for the second time to prepare a composite membrane.
Disclosure of Invention
The invention aims to solve the technical problems of insufficient peel strength, difficult industrial production and higher membrane material cost of the composite membrane in the prior art and provide a preparation method of an in-situ embedded reinforced hollow composite membrane.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the in-situ embedded reinforced hollow composite membrane comprises the following steps:
(1) mixing polymer resin, a pore-forming agent, a hydrophilic agent and a solvent according to the weight ratio of 15-20: 5-20: 1-5: 55-79, then stirring, filtering and defoaming in vacuum to obtain a coating material liquid;
(2) flatly and crossly winding a plurality of strands of yarns on a rotating mandrel along a guide groove, and bonding the cross points of the yarns by ultrasonic welding to form a network tubular reinforcing base material wrapped on the mandrel;
(3) continuously conveying the coating liquid to the hollow coating head by using a metering pump, and enabling the network tubular reinforcing base material to move downwards along the core rod by using traction force and continuously enter the coating head; the coating liquid permeates into the yarns and completely coats the network tubular reinforced base material, and meanwhile, the rotating core rod is used as a scraper to scrape a coating layer on the inner surface of the network tubular reinforced base material;
(5) under the action of traction force, the network tubular reinforced base material coated by the coating liquid continuously leaves the coating head and enters the coagulating bath, the surface liquid of the network tubular reinforced base material exchanges with water in the coagulating bath to form a film, and finally the in-situ embedded reinforced hollow composite film is prepared.
In the invention, the polymer resin is one or two of polyether sulfone, modified polyether sulfone, polyvinylidene fluoride, polysulfone, polyvinyl chloride, polyacrylonitrile or cellulose acetate.
In the invention, the pore-foaming agent is two or three of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, ethylene glycol, diethylene glycol or triethylene glycol.
In the invention, the hydrophilic agent is one of sulfonated polyether sulfone, polymethyl methacrylate, polyoxyethylene-polyoxypropylene block copolymer or polyether siloxane.
In the invention, the solvent is one or two of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, trimethyl phosphate or triethyl phosphate.
In the invention, the yarn is a composite yarn with the denier of 200-1000, and the material of the yarn is one of polypropylene, polyester or nylon.
In the invention, the network tubular reinforcing base material is formed by cross winding and welding 4-32 strands of yarns, the inner diameter of the base material is 1-12 mm, the outer diameter of the base material is 1.6-20 mm, and the aperture of meshes between the yarns is 0.1-2 mm.
In the invention, when the outer diameter of the core rod is more than 3mm, the core rod adopts a hollow tubular structure; the core liquid is introduced from the upper end part of the core rod, so that the core liquid flows downwards along the inner part of the core rod; after the coating of the network tubular reinforced substrate in the coating head is finished, the network tubular reinforced substrate is pulled to be separated from the tail end of the core rod; the core liquid flows out from the lower end part of the core rod and exchanges solvent with the surface of the coating layer on the inner side of the network tubular reinforced base material to realize solidification;
the core solution is one or two mixed solution of water, N-dimethylacetamide, N-dimethylformamide or triethyl phosphate;
when the outer diameter of the core rod is less than 3mm, the core liquid is not introduced, and the coating material is only used for wrapping the network tubular reinforcing base material.
In the invention, the prepared reinforcing network structure of the in-situ embedded reinforced hollow composite membrane is formed in situ in the process of preparing the composite membrane; the in-situ embedded reinforced hollow composite membrane has the inner diameter of 1-12 mm, the outer diameter of 1.6-20 mm and the average pore diameter of 0.01-1 micron.
In the present invention, the stirring in the step (1) means that the stirring is continued at 80 ℃ for 12 hours.
The in-situ embedded reinforced hollow composite membrane product prepared by the method is a hollow fiber membrane with the inner diameter of 1-2mm and the outer diameter of 1.6-3mm, and is mainly packaged as an external pressure type component applied to an immersed MBR (membrane bioreactor); if the inner diameter is 2-12mm and the outer diameter is 3-20mm, the membrane is a tubular membrane which is mainly packaged in an internal pressure mode and is applied to treatment of high-solid-content liquid materials such as garbage percolate, sewage containing activated sludge, fruit juice and the like. When the outer diameter of the core rod is larger than 3mm, a hollow rigid pipe can be adopted; when the outer diameter of the core rod is less than 3mm, a solid rigid rod can be adopted, and the process of adding the core liquid is not needed.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method is simple and continuous, and can realize industrial production;
(2) the invention has no peeling phenomenon, and overcomes the problem of insufficient peeling strength of the composite film in the prior art;
(3) the in-situ embedded network tubular reinforced base material has lower cost, and finally, the cost of the membrane material is reduced.
Drawings
FIG. 1 is a schematic diagram of a process for preparing an in-situ embedded reinforced hollow composite membrane.
FIG. 2 is a schematic view of an in-situ embedded reinforced hollow composite membrane manufacturing apparatus.
In the figure: the device comprises a coating material dissolving tank 1, a coating material metering and conveying device 2, a coating material 21, a yarn pay-off device 3, a yarn pay-off barrel 31, a yarn pay-off rotating system 32, a core liquid tank 4, a core liquid metering and conveying device 5, a core liquid pipe 51, a core rod 6, a core rod rotating device 7, a rotating system 71, a core rod rotating connecting piece 72, a rotating joint 8, an ultrasonic welding device 9, an ultrasonic generator 91, an ultrasonic welding joint 92, a core rod fixing device 10, a coating head 11, a gel water bath 12, a wire winding machine 13 and a reinforced hollow composite membrane 14.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
It should be noted that the apparatus for preparing the in-situ embedded reinforced hollow composite membrane described below is only an illustrative content of the present invention and should not be construed as relying on the apparatus to implement the present invention. Therefore, the description about the apparatus should not be regarded as a technical limitation of the present invention. The skilled person in the art can design or manufacture the device by the skills of the person in the field after understanding the implementation method of the present invention.
In this embodiment, the apparatus for preparing the in-situ embedded reinforced hollow composite membrane comprises a gel water bath 12, a filament winding machine 13, a coating system, a yarn paying-off device and a feed liquid conveying system; wherein,
the coating system comprises a mandrel 6, an ultrasonic welding device 9, a mandrel fixing device 10 and a coating head 11.
The core rod 6 is a stainless steel hollow tube or a solid tube, the outer diameter of the core rod is 1.5-12 mm, and the hollow tube is preferably larger than 3 mm. The outer surface of the upper end of the core rod 6 is uniformly distributed with thread-shaped grooves as yarn guide grooves, and the arrangement purpose of the thread-shaped grooves is that a plurality of strands of yarns are smoothly and crossly wound on the rotating core rod along the guide grooves.
The mandrel 6 is vertically suspended above the gel water bath 12, the upper end of the mandrel 6 is connected with the core liquid pipe 51 through a mandrel rotary connecting piece 72 and a rotary joint 8, and the mandrel rotary connecting piece 72 is connected with a rotary system 71.
The core rod 6 downwards sequentially passes through the ultrasonic welding device 9, the core rod fixing device 10 and the coating head 11; the ultrasonic welding apparatus 9 includes an ultrasonic generator 91 and an ultrasonic horn 92. The mandrel bar fixing device 10 is spaced from the mandrel bar 6 so that the mandrel bar 6 can be fixed and rotated around its own axis. The coating head 11 is of a hollow structure, and the inner space of the coating head is connected with an output pipeline of the coating material metering and conveying device 1; the core rod 6 passes through the inner space of the coating head 11 from top to bottom.
The yarn pay-off device comprises a yarn pay-off drum 31 and a yarn pay-off rotating system 32, and the number of the yarn pay-off devices can be 1-8 groups. Each group of yarn pay-off devices is provided with at least 2 yarn pay-off drums 31 which are respectively arranged at two sides of the upper part of the core rod 6;
the feed liquid conveying system comprises a coating feed liquid dissolving tank 1 and a core liquid tank 4, the tank bottom of the coating feed liquid dissolving tank 1 is connected to a coating head 11 through a pipeline and a coating material metering and conveying device 2, and the tank bottom of the core liquid tank 4 is connected to a core liquid pipe 51 through a pipeline and a core liquid metering and conveying device 5. The coating material metering and conveying device 2 and the core liquid metering and conveying device 5 can adopt metering pumps.
The realization principle of the invention is as follows:
after the core liquid is sent to the core liquid pipe 51 by the core liquid metering and conveying device 5, the core liquid flows downwards along the hollow interior of the core rod 6 through the rotary joint 8 and the core rod rotary connecting piece 72. The rotation system 71 carries the mandrel rotation connection 72, causing the mandrel 6 to rotate about its own axis (the mandrel pipe 51 and the rotary joint 8 are stationary). The yarns on the plurality of yarn pay-off drums 31 are flatly and crossly wound on the outer surface of the rotating mandrel, and the cross points of the yarns are welded and bonded by the ultrasonic welding device 9, so that the network tubular reinforcing base material is formed. The network tubular reinforcing base material which is welded before is dragged by the wire winding machine 13 to continuously descend along the core rod 6 and finally separated from the lower end part after being coated with the feed liquid. The coating solution is delivered to the coating head 11 by the coating solution metering delivery device 2 and fills the cavity of the same, as the network tubular reinforcing substrate continues through the coating head 11. The rotating core rod 6 is used as a scraper to scrape a coating layer with a certain thickness on the inner surface of the network tubular reinforced base material. Then, the core liquid and the inner surface of the coating layer are subjected to solvent phase exchange at the lower end portion of the mandrel bar 6 and solidified, and the outermost layer of the liquid enters the gel water bath 12 to continue exchange film formation.
In the invention, when the outer diameter of the core rod 6 is more than 3mm, the core rod 6 adopts a hollow tubular structure; introducing a core liquid curing process; when the outer diameter of the core rod 6 is less than 3mm, the core liquid is not introduced, and only the coating material is used for wrapping the network tubular reinforcing base material.
Example 1:
adding 20% of polyether sulfone resin (BASF 6020P), 55% of N, N-dimethylformamide, 11% of polyethylene glycol 200, 9% of polyvinylpyrrolidone K-30 and 5% of sulfonated polyether sulfone into a stirring tank according to the weight percentage, stirring for 12 hours at 80 ℃, filtering and defoaming in vacuum to obtain the coating liquid. The polyester composite yarns with 8 deniers and 750 are respectively guided by a rotating mandrel to be flatly and crossly wound on a stainless steel hollow mandrel with the outer diameter of 4mm, and the cross points are ultrasonically welded and bonded to form a network tubular base material. The web-like substrate is continuously fed into the coating head under the action of a traction force, while the coating liquid is fed to the coating head by means of a metering pump. The coating liquid permeates into the yarns and completely infiltrates the coated network tubular base material, the coated network tubular base material continuously leaves the coating head, the rotating core rod is used as a scraper to scrape a coating layer with a certain thickness on the inner surface of the tubular base material, the core liquid (water) and the coating layer are subjected to solvent phase exchange and solidification, the outer surface liquid enters a coagulating bath to be exchanged and formed into a film, the average pore diameter of the film is 0.02 micron, the inner diameter is 4mm, the outer diameter is 6mm, and the pure water internal pressure flux under the conditions of 0.2MPa and 25 ℃ is 740L/m2 .h。
Example 2:
adding 20 percent of polyether sulfone resin (basf 6020P), 50 percent of N, N-dimethylacetamide, 20 percent of trimethyl phosphate, 6 percent of polyethylene glycol 200, 3 percent of polyvinylpyrrolidone K-30 and 1 percent of sulfonated polyether sulfone in percentage by weight into a stirring tank, stirring for 12 hours at 80 ℃,and filtering and vacuum defoaming to obtain the coating liquid. The polyester composite yarns with 8 deniers and 750 are respectively guided by a rotating mandrel to be flatly and crossly wound on a stainless steel hollow mandrel with the outer diameter of 4mm, and the cross points are ultrasonically welded and bonded to form a network tubular base material. The web-like substrate is continuously fed into the coating head under the action of a traction force, while the coating liquid is fed to the coating head by means of a metering pump. The coating liquid permeates into the yarns and completely infiltrates the coated network tubular base material, the coated network tubular base material continuously leaves the coating head, a rotating core rod is used as a scraper to scrape a coating layer with a certain thickness on the inner surface of the tubular base material, core liquid formed by mixing 10% of N, N-dimethylacetamide and 90% of water is subjected to solvent phase exchange with the coating layer and is solidified, the outer surface material liquid enters a coagulating bath to be exchanged and formed into a membrane, the average pore diameter of the membrane is 0.01 micrometer, the inner diameter of the membrane is 4mm, the outer diameter of the membrane is 6mm, and the pure water internal pressure flux under the conditions of 0.2MPa and 25 ℃ is 580L/m2 .h。
Example 3:
adding 17 wt% of polyether sulfone resin (Veradel 3000P of Suwei corporation, Belgium), 62 wt% of N, N-dimethylformamide, 10 wt% of polyethylene glycol 200, 10 wt% of polyvinylpyrrolidone K-30 and 1 wt% of sulfonated polyether sulfone into a stirring tank, stirring at 80 ℃ for 12 hours, filtering and defoaming in vacuum to obtain the coating material liquid. The 16-denier 1000 polyester composite yarns are respectively guided by a rotating mandrel to be flatly and crossly wound on a stainless steel hollow mandrel with the outer diameter of 8mm, and the cross points are ultrasonically welded and bonded to form a network tubular base material. The web-like substrate is continuously fed into the coating head under the action of a traction force, while the coating liquid is fed to the coating head by means of a metering pump. The coating liquid permeates into the yarns and completely infiltrates the coated network tubular base material, the coated network tubular base material continuously leaves the coating head, the rotating core rod is used as a scraper to scrape a coating layer with a certain thickness on the inner surface of the tubular base material, core liquid formed by mixing 15% of N, N-dimethylformamide and 85% of water is subjected to solvent phase exchange with the coating layer and is solidified, the outer surface material liquid enters a coagulating bath to be exchanged and formed into a film, the average pore diameter of the film is 0.08 micrometer, and the inner diameter of the film is equal to8mm, 12mm in outer diameter, and 2150L/m in pure water at 25 deg.C under 0.2MPa2 .h。
Example 4:
adding 18 weight percent of polyether sulfone resin (BASF 6020P), 70 weight percent of N, N-dimethylformamide, 5 weight percent of polyethylene glycol 200, 6 weight percent of polyvinylpyrrolidone K-30 and 1 weight percent of sulfonated polyether sulfone into a stirring tank, stirring for 12 hours at 80 ℃, filtering and defoaming in vacuum to obtain coating liquid. The polyester composite yarns with the denier of 16 being 900 are respectively guided by a rotating mandrel to be flatly and crossly wound on a stainless steel hollow mandrel with the outer diameter of 8mm, and the cross points are ultrasonically welded and bonded to form a network tubular base material. The web-like substrate is continuously fed into the coating head under the action of a traction force, while the coating liquid is fed to the coating head by means of a metering pump. The coating liquid permeates into the yarns and completely infiltrates the coated network tubular base material, the coated network tubular base material continuously leaves the coating head, the rotating core rod is used as a scraper to scrape a coating layer with a certain thickness on the inner surface of the tubular base material, core liquid formed by mixing 30% of triethyl phosphate and 70% of water is subjected to solvent phase exchange with the coating layer and is solidified, the outer surface material liquid enters a coagulating bath for exchange film forming, the average pore diameter of the prepared film is 0.06 micrometer, the inner diameter is 4mm, the outer diameter is 6mm, and the pure water internal pressure flux under the conditions of 0.2MPa and 25 ℃ is 1670L/m2 .h。
Example 5:
adding 15 wt% of polyether sulfone resin (Veradel 3000P of Suwei corporation, Belgium), 60 wt% of N, N-dimethylacetamide, 10 wt% of polyethylene glycol 200, 10 wt% of polyvinylpyrrolidone K-30 and 5 wt% of sulfonated polyether sulfone into a stirring tank, stirring at 80 ℃ for 12 hours, filtering and defoaming in vacuum to obtain the coating material liquid. The 16-denier-300 polyester composite yarns are respectively guided by a rotating mandrel to be flatly and crossly wound on a stainless steel hollow mandrel with the outer diameter of 8mm, and the cross points are ultrasonically welded and bonded to form a network tubular base material. Under the action of traction forceThe lower web tubular substrate continuously enters the coating head while coating solution is delivered to the coating head by a metering pump. The coating liquid permeates into the yarns and completely infiltrates the coated network tubular base material, the coated network tubular base material continuously leaves the coating head, the rotating core rod is used as a scraper to scrape a coating layer with a certain thickness on the inner surface of the tubular base material, the core liquid (water) and the coating layer are subjected to solvent phase exchange and solidification, the outer surface liquid enters a coagulating bath to be exchanged and formed into a film, the average pore diameter of the film is 0.03 micron, the inner diameter is 8mm, the outer diameter is 12mm, and the pure water internal pressure flux under the conditions of 0.2MPa and 25 ℃ is 1160L/m2 .h。
Example 6:
adding 17 wt% of polyvinylidene fluoride resin (Solvay Solexis 1015, Solvay Suwei, Belgium), 55 wt% of N-methyl pyrrolidone, 10 wt% of dimethyl sulfoxide, 7 wt% of polyethylene glycol 600, 9 wt% of polyvinylpyrrolidone K-30 and 2 wt% of polyoxyethylene-polyoxypropylene segmented copolymer into a stirring tank, stirring at 80 ℃ for 12 hours, filtering and defoaming in vacuum to obtain coating liquid. The 4 polyester composite yarns with the denier of 200 are respectively guided by a rotating mandrel to be flatly and crossly wound on a stainless steel mandrel with the outer diameter of 1.5mm, and the cross points are ultrasonically welded and bonded to form the network tubular base material. The web-like substrate is continuously fed into the coating head under the action of a traction force, while the coating liquid is fed to the coating head by means of a metering pump. The coating liquid permeates into the yarns and completely infiltrates the coated network tubular base material, the network tubular base material coated by the coating liquid continuously leaves the coating head, the base material of the coating liquid enters a coagulating bath for exchange film formation, the average pore diameter of the film is 0.05 micron, the inner diameter of the film is 1.5mm, the outer diameter of the film is 2.5mm, and the external pressure flux of pure water under the conditions of 0.1MPa and 25 ℃ is 760L/m2 .h。
Example 7:
17 percent of modified polyether sulfone, 62 percent of N, N-dimethylacetamide, 10 percent of polyethylene glycol 600, 9 percent of polyvinylpyrrolidone K-30 andadding 2% polyoxyethylene-polyoxypropylene segmented copolymer into a stirring tank, stirring for 12 hours at 80 ℃, filtering, and defoaming in vacuum to obtain coating liquid. The 4 polyester composite yarns with the denier of 200 are respectively guided by a rotating mandrel to be flatly and crossly wound on a stainless steel mandrel with the outer diameter of 1.5mm, and the cross points are ultrasonically welded and bonded to form the network tubular base material. The web-like substrate is continuously fed into the coating head under the action of a traction force, while the coating liquid is fed to the coating head by means of a metering pump. The coating liquid permeates into the yarns and completely infiltrates the coated network tubular base material, the network tubular base material coated by the coating liquid continuously leaves the coating head, the base material of the coating liquid enters a coagulating bath for exchange film formation, the average pore diameter of the prepared film is 0.04 micron, the inner diameter is 1.5mm, the outer diameter is 2.4mm, and the external pressure flux of pure water under the conditions of 0.1MPa and 25 ℃ is 930L/m2 .h。
Example 8:
adding 15 wt% of polyvinylidene fluoride resin (Solvay Solexis 6020 of Solvay Suwei company, Belgium), 50 wt% of N, N-dimethylformamide, 29 wt% of triethyl phosphate, 4 wt% of polyethylene glycol 600, 1 wt% of polyvinylpyrrolidone K-30 and 1 wt% of polymethyl methacrylate into a stirring tank, stirring for 12 hours at 80 ℃, filtering and defoaming in vacuum to obtain the coating liquid. The 4-denier 250 polyester composite yarns are respectively guided by a rotating mandrel to be flatly and crossly wound on a stainless steel mandrel with the outer diameter of 1.5mm, and the cross points are ultrasonically welded and bonded to form a network tubular base material. The web-like substrate is continuously fed into the coating head under the action of a traction force, while the coating liquid is fed to the coating head by means of a metering pump. The coating liquid permeates into the yarns and completely infiltrates the coated network tubular base material, the network tubular base material coated by the coating liquid continuously leaves the coating head, the base material of the coating liquid enters a coagulating bath for exchange film formation, the average pore diameter of the film is 0.1 micron, the inner diameter is 1.5mm, the outer diameter is 2.4mm, and the external pressure flux of pure water under the conditions of 0.1MPa and 25 ℃ is 1420L/m2·h。
Claims (8)
1. The preparation method of the in-situ embedded reinforced hollow composite membrane is characterized by comprising the following steps of:
(1) mixing polymer resin, a pore-forming agent, a hydrophilic agent and a solvent according to the weight ratio of 15-20: 5-20: 1-5: 55-79, then stirring, filtering and defoaming in vacuum to obtain a coating material liquid;
(2) flatly and crossly winding a plurality of strands of yarns on a rotating mandrel, and bonding the cross points of the yarns by ultrasonic welding to form a network tubular reinforcing base material wrapped on the mandrel;
(3) continuously conveying the coating liquid to the hollow coating head by using a metering pump, and enabling the network tubular reinforcing base material to move downwards along the core rod by using traction force and continuously enter the coating head; the coating liquid permeates into the yarns and completely coats the network tubular reinforced base material, and meanwhile, the rotating core rod is used as a scraper to scrape a coating layer on the inner surface of the network tubular reinforced base material;
(5) under the action of traction force, the network tubular reinforced base material coated by the coating liquid continuously leaves the coating head and enters a coagulating bath, the surface liquid of the network tubular reinforced base material exchanges with water in the coagulating bath to form a film, and finally the in-situ embedded reinforced hollow composite film is prepared;
the polymer resin is one or two of polyether sulfone, modified polyether sulfone, polyvinylidene fluoride, polysulfone, polyvinyl chloride, polyacrylonitrile or cellulose acetate;
when the outer diameter of the core rod is larger than 3mm, the core rod adopts a hollow tubular structure; the core liquid is introduced from the upper end part of the core rod, so that the core liquid flows downwards along the inner part of the core rod; after the coating of the network tubular reinforced substrate in the coating head is finished, the network tubular reinforced substrate is pulled to be separated from the tail end of the core rod; the core liquid flows out from the lower end part of the core rod and exchanges solvent with the surface of the coating layer on the inner side of the network tubular reinforced base material to realize solidification;
the core solution is one or two mixed solution of water, N-dimethylacetamide, N-dimethylformamide or triethyl phosphate;
when the outer diameter of the core rod is less than 3mm, the core liquid is not introduced, and the coating material is only used for wrapping the network tubular reinforcing base material.
2. The method of claim 1, wherein the porogen is two or three of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, ethylene glycol, diethylene glycol, or triethylene glycol.
3. The method of claim 1, wherein the hydrophilic agent is one of sulfonated polyethersulfone, polymethylmethacrylate, polyoxyethylene-polyoxypropylene block copolymer, or polyether siloxane.
4. The method according to claim 1, wherein the solvent is one or two of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, trimethyl phosphate, or triethyl phosphate.
5. The method according to claim 1, wherein the yarn is a composite filament with a denier of 200-1000, and the material is one of polypropylene, polyester or nylon.
6. The method according to claim 1, wherein the network tubular reinforcing base material is formed by cross-winding and welding 4 to 32 yarns, and has an inner diameter of 1 to 12mm and an outer diameter of 1.6 to 20mm, and a mesh aperture between the yarns is 0.1 to 2 mm.
7. The method of claim 1, wherein the reinforcing network structure of the prepared in-situ embedded reinforced hollow composite membrane is formed in situ during the preparation of the composite membrane; the in-situ embedded reinforced hollow composite membrane has the inner diameter of 1-12 mm, the outer diameter of 1.6-20 mm and the average pore diameter of 0.01-1 micron.
8. The method according to claim 1, wherein the stirring in step (1) is continued at 80 ℃ for 12 hours.
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| CN101543731B (en) * | 2009-03-23 | 2013-07-31 | 杭州洁弗膜技术有限公司 | Method for preparing fiber braided tube embedded enhanced type polymer hollow fiber microporous membrane |
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