CN101138706A - Bunchiness hollow fiber film and method of preparing the same - Google Patents
Bunchiness hollow fiber film and method of preparing the same Download PDFInfo
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- CN101138706A CN101138706A CNA2006100155756A CN200610015575A CN101138706A CN 101138706 A CN101138706 A CN 101138706A CN A2006100155756 A CNA2006100155756 A CN A2006100155756A CN 200610015575 A CN200610015575 A CN 200610015575A CN 101138706 A CN101138706 A CN 101138706A
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Abstract
A bunchy hollow fiber membrane is characterized with the high flexibility and strong tension resistance. An external diameter of a fiber bundle of the fiber membrane is 0.3 to 3 mm. An internal diameter of a single fiber is 0.1 to 1.0 mm, a fiber wall is 0.05 to 1mm, the porosity is 50 t0 90 percent, and a membrane separation pore diameter is 0.01 to 1um. The breaking tension of each hollow fiber membrane bundle is 0.2-25.0kg, and the purified water penetration flux is 600-10000l/m<SUP>2</SUP> per hour at 0.1MPa and 25 centigrade degrees. A multi-pore membrane made with the present invention is provided with the advantage that a narrow-tube membrane is provided with a large external area; compared with a hollow fiber membrane, packing density within a volume unit is not greatly changed; the production efficiency is high; and so on.
Description
Technical Field
The invention relates to a high-strength porous membrane, namely a bundle-shaped hollow fiber membrane and a preparation method thereof, which can be used for manufacturing an external pressure type polymer hollow fiber ultrafiltration membrane or a polymer hollow fiber microporous membrane.
Background
The hollow fiber membrane is mainly used for filtration and separation in various fields.
The formation mechanism of the solution phase transfer film-forming hollow fiber membrane is that the film-forming polymer, the organic solvent and the pore-forming agent are mixed according to a certain proportion, and the mixture is dissolved uniformly and then enters a coagulating bath through a spinning nozzle. The solvent and the pore-forming agent in the polymer solution enter the coagulant phase, and the polymer is precipitated into a polymer hollow fiber membrane due to phase transfer. The hollow fiber separation membrane with a certain aperture can be obtained by controlling the formula of the spinning solution, the parameters of the spinning process and the post-treatment conditions of the hollow fiber.
The radial section structure of the hollow fiber porous membrane formed by solution phase transfer film formation is generally an asymmetric structure, namely, the hollow fiber porous membrane consists of a separation skin layer and a porous supporting layer, and the water permeability of the membrane can be improved by a method of adding various pore-forming agents and auxiliary agents into spinning stock solution:
japanese Kokoku publication Sho-62-017614 describes a method of mixing polyvinylidene fluoride, a high-molecular weight pore-forming agent polyethylene glycol, and a surfactant Tween-80, and then forming a film by phase transfer. The product obtained by the method has insufficient rupture strength, and the permeation speed of pure water is slow, so that the requirement cannot be met;
japanese examined patent publication No. Hei 3-71168 describes a method for producing a porous membrane by adding 7.2wt% of polyethylene glycol as a pore-forming agent, but a membrane having a high permeation flux is not obtained;
CN1128176A describes a method of forming a film by mixing polyvinylidene fluoride, a solvent, a polymer pore-forming agent, a non-solvent, a surfactant, and the like. Wherein, the macromolecule pore-forming agent, the non-solvent, the surfactant and even the cosolvent which are added in proper proportion interact and coordinate with each other to obtain the hollow membrane with high permeation flux;
CN1265048A describes a hollow fiber membrane having a large inner diameter and suitable for a high viscosity liquid, which is obtained by blending polyvinylidene fluoride, an organic liquid and inorganic pellets and then melt-spinning the blend.
The contents of the above-mentioned documents are incorporated herein by reference. However, the external pressure type hollow fiber membrane obtained by the technology has weak strength, especially weak tensile strength and breaking strength, and is easy to have the problems of filament breakage and the like when used in a separation system with serious pollution, especially when an air oscillation cleaning method is used.
In the prior art, in order to improve the strength of the membrane, the external pressure type thin-tube membrane is prepared by coating feed liquid on the periphery of a weaving support tube. This creates new disadvantages: 1. the outer diameter of the thin-tube type membrane is larger, and the filling density in unit volume is reduced compared with that of a hollow fiber membrane; 2. because the combination firmness of the braided supporting tube and the porous membrane material is not high, the braided supporting tube and the porous membrane material are easy to peel off and damage during backwashing after membrane pollution; 3. when the air oscillation cleaning method is adopted, the phenomenon of fatigue, breakage and peeling of the membrane material is easy to occur at the joint part of the root part of the thin-tube membrane and the casting resin; 4. low production efficiency and the like.
The inventor of the patent improves the structure of the spinning nozzle, can perform cluster spinning on 2-8 hollow fiber membranes, and can greatly improve the tensile strength and the breaking strength of the hollow fiber membranes. FIG. 5 is a schematic view of a spinning nozzle structure for bundle spinning of 3 hollow fiber membranes. In order to further improve the tensile strength and the breaking strength of the hollow fiber membrane, during spinning, a continuous and uninterrupted rib wire and 2-8 holes of membrane-making liquid can enter a coagulating bath through a spinning nozzle to prepare a high-strength hollow fiber membrane bundle with continuous reinforcing ribs inside the membrane bundle, so that the hollow fiber membrane with stable performance, proper aperture, high water permeability and high strength is prepared. Or one reinforcing tube and the membrane-making liquid with 2-8 holes enter a coagulating bath through a spinning nozzle to prepare the high-strength hollow fiber membrane bundle with the reinforcing tube inside. The reinforcing tube may be a braided tube or a homogeneous non-braided tube.
Disclosure of Invention
An object of the present invention is to provide a reinforced bundle-like hollow fiber membrane product, and a method of manufacturing the hollow fiber membrane product.
The invention particularly relates to a cluster type external pressure hollow fiber membrane, which is characterized in that: the external diameter of the filament bundle is 0.3-3 mm, the internal diameter of the monofilament is 0.1-1.0 mm, the wall thickness is 0.05-1 mm, the porosity is 50-90%, the membrane separation aperture is 0.01-1 micron, the breaking tension of the hollow fiber membrane bundle is 0.2-25.0 kg/root, the water permeability of pure water is 600-10000L/m 2 ·[email protected]，25℃。
The bundle-shaped hollow fiber membrane of the present invention is characterized in that one bundle-shaped hollow fiber membrane is formed by integrating 2 to 8 single hollow fibers into one bundle.
The invention relates to a bundle-shaped hollow fiber membrane, which is characterized in that continuous reinforced fiber reinforcement is arranged at the center of a hollow fiber membrane bundle.
The invention relates to a bundle-shaped hollow fiber membrane, which is characterized in that the center of a hollow fiber membrane bundle is reinforced by a ribbed pipe.
The invention also relates to a method for preparing the bundle-shaped hollow fiber membrane, which is characterized in that a dry-wet spinning process is adopted, polymer membrane casting liquid and spinning core liquid simultaneously pass through a spinning nozzle to form nascent hollow fibers, 2-8 single nascent state hollow fibers are integrated into a bundle before entering a coagulation bath water tank, and then enter the coagulation bath water tank to form the bundle-shaped hollow fiber membrane.
The invention also provides a preparation method of the bunched hollow fiber membrane, which adopts a dry-wet spinning process, wherein a polymer membrane casting solution, a spinning core solution and a rib wire simultaneously pass through a spinning spray head, the polymer membrane casting solution and the spinning core solution form nascent hollow fibers, 2-8 single nascent state hollow fibers and the rib wire are integrated into a bunch before entering a coagulation bath water tank, the rib wire is positioned at the center of the 2-8 single nascent state hollow fibers, and then the two bunch hollow fibers and the rib wire enter the coagulation bath water tank together to form a bunched hollow fiber membrane with a reinforced center.
Another method for producing a bundle-like hollow fiber membrane of the present invention is characterized by comprising: the method comprises the steps of adopting a dry-wet spinning process, enabling a polymer membrane casting solution, a spinning core solution and a braided tube to simultaneously pass through a spinning nozzle, enabling the polymer membrane casting solution and the spinning core solution to form nascent hollow fibers, integrating 2-8 single nascent hollow fibers and the braided tube into a bundle before entering a coagulation bath water tank, distributing the 2-8 single nascent hollow fibers on the outer wall of the braided tube, and then enabling the hollow fibers and the braided tube to enter the coagulation bath water tank together to form a bundled hollow fiber membrane with the braided tube at the center.
The porous membrane prepared by the invention has the following advantages: 1. the effective external surface area of the thin-tube membrane is larger, and compared with a hollow fiber membrane, the filling density in unit volume is not changed greatly; 2. the reinforcing material and the porous membrane material have high bonding firmness, and the phenomenon of peeling and damaging the reinforcing material and the porous membrane material is not easy to occur during backwashing after membrane pollution; 3. when the air oscillation cleaning method is adopted, the fatigue, damage and peeling phenomena of the membrane material are not easy to occur at the joint of the root part of the thin-tube membrane and the casting resin; 4. high production efficiency and the like.
Drawings
FIG. 1 is a schematic cross-sectional structure of a self-reinforced membrane tow;
FIG. 2 is a schematic cross-sectional structure of a woven rib reinforced membrane tow;
FIG. 3 is a schematic cross-sectional view of a reinforced membrane tow for a support tube;
FIG. 4 is a schematic cross-sectional structure of a reinforced membrane tow for a support tube;
FIG. 5 is a schematic view of the discharge end face of the spinning nozzle;
fig. 6 is a schematic view of a bundled hollow fiber membrane spinning machine.
Detailed Description
As shown in figure 1, during spinning, after passing through a spinning nozzle, 2-8 holes of membrane-making liquid can be directly combined into a strand, and then the strand enters a coagulating bath to prepare a high-strength hollow fiber membrane bundle, so that the hollow fiber membrane with stable performance, proper hole diameter, high water flux and high strength is prepared. The cluster fusion roundness of the hollow fiber membrane bundle can be adjusted by adjusting the water inlet distance of the spinning membrane-making liquid from the nozzle outlet to the outer coagulation bath liquid level and selecting the center distance between the spinning membrane-making liquid outlets on the processing nozzle. The water inlet distance from the nozzle outlet to the outer coagulation bath liquid surface can be 1-1000mm, and the center distance between the film-forming liquid outlets on the spinning nozzle can be 1-20mm. The outer diameter of the single hollow fiber membrane before the strand is not combined can be 0.2mm-3.0mm, and the wall thickness of the single hollow fiber membrane before the strand is not combined can be 0.05mm-1.0mm.
As shown in FIG. 2, during spinning, a rib thread and 2-8 holes of membrane-forming liquid are fed into a coagulating bath through a spinning nozzle to form a high-strength hollow fiber membrane bundle with reinforcing ribs 41 inside the membrane bundle, thereby obtaining a hollow fiber membrane with stable performance, proper aperture, high water flux and high strength. The cluster fusion roundness of the hollow fiber membrane bundle can be adjusted by adjusting the water inlet distance of the spinning membrane-forming liquid from the nozzle outlet to the outer coagulation bath liquid level and selecting the center distance between the spinning membrane-forming liquid outlets on the processing nozzle. By selecting the tensile strength and the softness of the rib wires, the hollow fiber membrane bundle with high tensile strength and high breaking strength can be obtained. The material of the rib wire can be organic polymer fibers such as thread rope, woven nylon, polyimide, aromatic polyamide, polypropylene, polyethylene, etc., or inorganic fibers such as carbon fiber, glass fiber, etc., or woven fabrics thereof. The bonding strength of the rib lines and the membrane material is improved, and the stripping resistance of the rib lines and the membrane material can be improved.
As shown in FIG. 3, during spinning, a woven reinforced tube and 2-8 holes of membrane-forming liquid are fed into a coagulating bath through a spinning nozzle to form a high-strength hollow fiber membrane bundle with reinforced tubes in the membrane bundle, so as to obtain a hollow fiber membrane with stable performance, proper aperture, high water flux and high strength. The cluster fusing roundness of the hollow fiber membrane bundle can be adjusted by adjusting the water inlet distance of the spinning membrane-forming liquid from the nozzle outlet to the outer coagulation bath liquid level and selecting the center distance between the spinning membrane-forming liquid outlets on the processing nozzle. By selecting the tensile strength and the flexibility of the reinforced pipe, the hollow fiber membrane bundle with high tensile strength and breaking strength can be obtained. The reinforcing pipe material can be thread-woven nylon, terylene, polypropylene fiber, viscose fiber and the like, so that the bonding strength between the reinforcing pipe and the film material is improved, and the stripping resistance between the reinforcing pipe and the film material can be improved.
As shown in FIG. 4, during spinning, a support tube and 2-20 holes of membrane-forming liquid are fed into a coagulating bath through a spinning nozzle to form a high-strength hollow fiber membrane bundle with reinforcing tubes inside the membrane bundle, so as to obtain a hollow fiber membrane with stable performance, proper hole diameter, high water flux and high strength. The cluster fusion roundness of the hollow fiber membrane bundle can be adjusted by adjusting the water inlet distance of the spinning membrane-forming liquid from the nozzle outlet to the outer coagulation bath liquid level and selecting the center distance between the spinning membrane-forming liquid outlets on the processing nozzle. By selecting the tensile strength and the flexibility of the supporting tube, the hollow fiber membrane bundle with high tensile strength and breaking strength can be obtained. The material of the support tube may be woven nylon, polyimide, aramid, polypropylene, polyethylene, or other organic polymer fibers, or woven carbon fiber, glass fiber, or other inorganic fiber. The adhesive strength between the supporting tube and the membrane material is improved, and the stripping resistance between the supporting tube and the membrane material can be improved.
The reinforcing rib thread adopted by the invention is a continuous thread with the diameter of 0.01-3mm, the rib thread material can be chemical fiber filament or short fiber such as nylon, terylene, polypropylene, polyimide, aromatic polyamide, polyethylene and the like, and the linear density is 50-500dtex/10-500f; the twisted yarn may be the chemical fiber twisted yarn; a woven or knitted braided rope of the above twisted yarn; the sewing thread can also be made of the fiber material, and the specification is 20-100S/2-4 ply. Or inorganic fiber such as cotton thread rope or carbon fiber, glass fiber, etc. or braided rope thereof, or fishing line made of nylon, polyvinylidene fluoride, etc. The preferable materials are polyester fiber and polyvinylidene fluoride, and the preferable fiber forms are sewing thread and fish thread.
D is the outer diameter of the hollow fiber before bundling, the number of N fibers bundled, S0 and S are the membrane areas before and after the hollow fiber bundling respectively, and D is the outer diameter of the hollow fiber membrane after the hollow fiber bundling into a round shape. S/S0 is the ratio of the area of the hollow fiber membrane after bundling into a round shape to the area of the hollow fiber membrane before bundling. Then there are:
as shown in table 1, after the bundling, the effective area of the hollow fiber membranes is decreased, and the more the bundling number is, the more the effective area of the hollow fiber membranes is decreased, so it is necessary to control the water inlet distance and the center distance between the discharging holes of the spinning nozzle, so that the bundled hollow fiber membranes do not fuse into a circle in appearance, and the outer surface area of the hollow fiber membrane bundle whose appearance is not fused into a circle is larger than the outer surface area of the hollow fiber membrane bundle which is completely fused into a circle. Meanwhile, the number of the hollow fiber membranes is generally 2 to 8, preferably 3 to 6.
TABLE 1 completely fused round bundled hollow fiber membrane external diameter and effective area
| N (root of Number) | d(mm) | S/S0 | ||
| 1.0 | 1.1 | 1.2 | ||
| D(mm) | ||||
| 2 | 1.41 | 1.56 | 1.70 | 0.71 |
| 3 | 1.73 | 1.91 | 2.08 | 0.58 |
| 4 | 2.00 | 2.20 | 2.40 | 0.50 |
| 5 | 2.24 | 2.46 | 2.68 | 0.45 |
| 6 | 2.45 | 2.69 | 2.94 | 0.41 |
When the diameter of the hollow fiber membrane wire is thin, the tensile breaking force of the hollow fiber membrane is small, and when the diameter of the hollow fiber membrane wire is thick, the wall thickness of the hollow fiber membrane must be increased to keep certain crush resistance because the hollow fiber is self-supporting, so that the production cost of the hollow fiber membrane is increased, and the strength improvement degree of the hollow fiber membrane is limited. By adopting the novel method, the hollow fiber membrane tows can be thickened, so that the tensile strength of the hollow fiber membrane is improved, but the wall thickness of a single hollow fiber membrane can still be thinner, so that the membrane resistance is reduced, and the production cost is kept low.
Compared with a solid bar as the reinforcing rib, the reinforcing rib adopts soft ropes or plied chemical fiber yarns. The rope is soft, thereby being beneficial to the swing of the hollow fiber membrane and improving the cleaning effect, thereby reducing the air consumption during cleaning. The polyvinylidene fluoride hollow fiber membrane is soft, and has the advantage that polyvinylidene fluoride is superior to polyether sulfone, but the tensile breaking force of the polyvinylidene fluoride hollow fiber membrane is small.
Compared with the method of adding the chemical fiber short fibers into the spinning membrane casting solution, the strength of the hollow fiber membrane obtained by adopting the method of bundling and ribbing is completely determined by the strength of the ribbing, and the strength of the obtained hollow fiber membrane is easily far greater than that of the hollow fiber membrane obtained by adding the chemical fiber short fibers into the spinning membrane casting solution by selecting continuous and uninterrupted high-strength rib wires.
FIG. 5 is a schematic view of the end face structure of the discharge port of the triple-tow single-rib spinning nozzle. Other spinning nozzle structures with multi-filament bundles and multi-rib structures can be analogized.
Fig. 6 is a schematic view of a cluster type hollow fiber membrane spinning machine. And (3) keeping a certain tension force of the rib thread shaft, enabling the rib thread to pass through a spinning nozzle, then enabling the rib thread and the stranded hollow fiber membrane to enter a solidification water bath 27, passing through a yarn guide wheel 22, and drawing and winding the rib thread on a wire winding wheel 23 to obtain the reinforced rib type reinforced hollow fiber porous membrane. If no reinforcing rib thread is provided, a twisted reinforced hollow fiber porous membrane is obtained. If the reinforced pipe is used, a reinforced pipe type reinforced hollow fiber porous membrane is obtained. The continuous production can be realized by adopting a plurality of spinning kettles, and as shown in the figure, the continuous production can be realized, the continuous production is characterized in that a group of feed liquid tanks 1 and 2 are designed, the feed ports and the discharge ports of the feed liquid tanks are respectively connected by three-way valves 10 and 11, and when one tank works, the other tank defoams, repeatedly alternates and can continuously spin; a group of core liquid tanks 3, 4 which are connected by an upper communicating pipe 5 and a lower communicating pipe 5 and switch valves 17, 18, one tank works, and the other tank is replenished with liquid for the working tank; the coagulation bath water tank 21 is provided with a liquid supplementing pipe 7 and an overflow pipe 6, when a spinning solution 26 enters a coagulation liquid 27 in the coagulation bath water tank 21 through a spinning nozzle 9, a local spinning solvent and additive high-concentration area is formed, and the spinning solution is discharged out of the coagulation bath water tank through the adjacent overflow pipe 6, so that the adverse effect on the performance stability of the hollow fiber membrane due to the overhigh concentration of the spinning solvent and the spinning additives in the coagulation bath water tank 27 can be effectively prevented, meanwhile, the liquid supplementing pipe 7 is arranged at the filament outlet position of the coagulation bath water tank, so that the exchange and extraction of the spinning solvent and the additives in the coagulation bath water tank can be completed as much as possible, and the quality of the spun hollow fiber membrane is stable. The technology can be applied to the mass continuous spinning of the porous spinning nozzle, and has high production efficiency, low cost and good product quality.
The rib material can be nylon, terylene, polypropylene, polyimide, aramid, polyethylene and other fiber filament or short fiber, can also be the twisted yarn of the chemical fiber, and can also be the braided rope of the twisted yarn. Or cotton thread rope or inorganic fiber knitting rope such as carbon fiber and glass fiber, or fishing line made of nylon, polyvinylidene fluoride and other materials. Chemical fiber filaments or staple fibers can be used directly as the rib as shown in fig. 6. Or the chemical fiber filament or short fiber can be directly fed into a nozzle of a spinning machine after being twisted by a twisting machine. The chemical fiber twisted yarn can be made into a braided rope after being knitted or woven and directly enters a nozzle of a spinning machine.
The formation mechanism of the solution phase transfer film-forming hollow fiber film is that the film-forming polymer, the organic solvent and the pore-forming agent are mixed according to a certain proportion, and the mixture is dissolved uniformly and then enters a coagulating bath through a spinning nozzle. The solvent and the pore-forming agent in the polymer solution enter the coagulant phase, and the polymer is precipitated into a polymer hollow fiber membrane due to phase transfer. The hollow fiber separation membrane with a certain aperture can be obtained by controlling the formula of the spinning solution, the parameters of the spinning process and the post-treatment conditions of the hollow fiber. The organic polymer pore-forming agent has the effects of improving the fluidity and the pore-forming property of a polymer solution and the hydrophilicity of the formed polymer solution, and has small permeation and emulsification effects and the like due to low surface tension of the polymer, so that the polymer pore-forming agent mainly plays roles in dispersing, thickening and the like, but cannot fully wet the interface of the spinning solution and the coagulating solution so as to be beneficial to the bidirectional diffusion and permeation of the solvent and the coagulating agent; the organic polymer pore-forming agent is dissolved in a solvent and is molecularly dispersed in the casting solution, a large number of through membrane separation holes are not easy to form during film solidification, and a large amount of polymer pore-forming agent is required to form large membrane separation holes, so that the obtained hollow fiber membrane has high porosity and weak membrane strength.
The inorganic pore-forming agent is dispersed in the casting solution as heterogeneous phase, and is dissolved and extracted by acid, alkali or organic solvent after film forming, even if the added amount is less, larger holes can be formed on the hollow fiber wall, and polymer agglomerate clearance holes formed by the high molecular pore-forming agent during phase transfer can be communicated, so that more effective through membrane separation holes are obtained under the condition of lower separation membrane porosity, and the hollow fiber membrane with high strength and high water permeability can be obtained. However, the excessive addition of the inorganic pore-forming agent can cause the deterioration of the stability of the membrane casting solution, which is not favorable for realizing the stable spinning of the hollow fiber porous membrane.
The dispersing and thickening effects of the low molecular surfactant are weak, and the polymer resin in the casting solution is difficult to be properly dispersed by independently adding the low molecular surfactant into the casting solution, so that the polymer hollow fiber porous membrane with high permeation flux is difficult to obtain. But the low molecular surfactant has strong permeation and emulsification effects, can make up the defects of a high molecular pore-forming agent and an inorganic pore-forming agent in a casting solution, improve the compatibility of an interface of an organic phase and an interface of an inorganic phase, adjust a metastable state structure of a high molecular continuous phase and an inorganic pore-forming agent dispersed phase in the casting solution, uniformly distribute and stably exist the inorganic pore-forming agent dispersed phase in the casting solution, uniformly disperse a micro-phase polymer woven state structure, and simultaneously adjust the interface material exchange speed of a spinning solution and a solidifying solution, so that when the casting solution is transferred into a film, the pores of the hollow fiber are uniform. Therefore, the polymer pore-forming agent, the inorganic pore-forming agent and the surfactant are added in a proper proportion, the dispersion and thickening effects of the polymer pore-forming agent, the interface wetting effect of the surfactant and the differential phase effect of the inorganic pore-forming agent are fully utilized, the pore-forming mechanisms of the three additives are organically matched and have synergistic effect, the casting solution has proper dispersibility and stability, the interface wetting property of the casting solution and the solidification solution is effectively controlled, the bidirectional diffusion and permeation of the coagulant and the casting solution at the interface are facilitated, the precipitation and solidification speed of the polymer in the solidification solution is influenced, and the phase transfer film forming is controlled, so that the hollow fiber separation film with stable performance, proper aperture, high water permeability and high strength can be spun.
In the invention, the film-making additive mainly comprises one or more of inorganic pore-forming agent, organic polymer pore-forming agent and surfactant, and can also comprise other additives. The following weight percentages of the various materials are based on the total weight of the polymer spinning solution and the sum of the weight percentages of the various materials in the spinning solution is 100wt%.
The polymer is one of polyvinylidene fluoride or polyvinylidene fluoride copolymer, or a mixture of one of the polyvinylidene fluoride or polyvinylidene fluoride copolymer and one of the following polymers: polymethyl methacrylate, polyvinyl alcohol, polyvinyl acetate, polyacrylonitrile, polyvinyl acetal and the like, and the polyvinylidene fluoride copolymer is a copolymer with vinylidene fluoride repeating units of not less than 60 percent. The polymer may be a conventional film-forming polymer such as polysulfone, polyethersulfone, polyacrylonitrile, polyvinyl chloride, or the like. The polymer content is generally from 10 to 40% by weight, preferably from 15 to 30% by weight.
The solvent used in the spinning solution is preferably a strongly polar solvent, which may be a mixture of one or more of the following: dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone, triethyl phosphate, sulfolane, dimethyl sulfoxide, and the like. The amount of the solvent is 50 to 90 wt%, preferably 60 to 80wt%.
Cosolvent such as dioxane and butanone can also be added, and the content is 1-5 wt%.
The inorganic pore-forming agent is a mixture of one or more of the following: lithium nitrate, sodium chloride, calcium carbonate, calcium nitrate, silicon dioxide, aluminum oxide, kaolin, and the like. The total amount of the inorganic pore-forming agent is 0.5-20 wt%, preferably 1-10 wt%, the particle size of the inorganic pore-forming agent is less than 10 μm, and the inorganic pore-forming agent is preferably nano-scale particles.
The organic polymer pore-forming agent is a mixture of one or more of the following components: water-soluble polymers such as polyethylene glycol, polyoxyethylene, polyvinylpyrrolidone, polyvinyl alcohol, methylcellulose and the like, wherein the molecular weight of the polyethylene glycol is preferably 200 to 20000 daltons, the molecular weight of the polyoxyethylene is preferably 10 ten thousand daltons or more, and the molecular weight of the polyvinylpyrrolidone is preferably 1 ten thousand to 120 ten thousand daltons. The content of the organic polymer pore-forming agent is 2 to 30 weight percent, preferably 5 to 20 weight percent.
The surfactant is a mixture of one or more of the following: cationic surfactants, anionic surfactants, amphoteric surfactants, nonionic surfactants. Such as sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, hexadecyl trimethyl ammonium bromide, sec-octyl alcohol polyoxyethylene ether, sodium dodecyl amino sulfonate, fluorine-containing surfactant, tween-20, tween-80, etc. The total content of the surfactant is 0.01-5 wt%, and the addition amount is different according to the kind of the surfactant, for example, the addition amount of the nonionic surfactant is preferably 1-2 wt% and the addition amount of the fluorine-containing surfactant is preferably 0.05-0.5 wt%.
The method comprises the steps of adopting conventional dissolution, uniformly mixing a polymer, an inorganic pore-forming agent, an organic high-molecular pore-forming agent, a surfactant and the like in a strong polar solvent, carrying out wet spinning or dry-wet spinning, dissolving out the pore-forming agent by alkali, acid, water or an organic solvent and the like after spinning, and preparing the high-strength and high-flux hydrophilic hollow fiber porous membrane through phase transfer.
By adopting the porous membrane preparation method, the reinforced polymer hollow fiber membrane bundle can be obtained. The outer diameter of a single hollow fiber membrane before being bundled into a strand can be 0.2mm-3.0mm, the wall thickness of the single hollow fiber membrane before being bundled into a strand can be 0.05mm-1.0mm, the porosity is 50-90%, the membrane separation aperture is 0.01-1 micron, the rupture strength is 0.3-2 MPa, the tensile strength of the hollow fiber membrane bundle is 0.2-10.0 kg/strand, and the water permeation flux of pure water is 300-10000L/m 2 ·[email protected]，25℃。
By adopting the preparation method of the porous hollow fiber membrane, the tensile strength of the hollow fiber membrane is mainly enhanced by bundling or even reinforced bundling, and the requirement on the strength of the hollow fiber membrane body is reduced, so a large amount of pore-forming additives can be added according to the requirement, and the hollow fiber membrane with higher membrane flux can be obtained.
The present invention will be described in further detail with reference to examples. The examples are only to explain the invention further and do not limit the scope of protection of the invention.
The spinning conditions commonly used in the prior art are adopted for preparing the membrane. The polyvinylidene fluoride resin is conventional general-purpose commercial polyvinylidene fluoride resin.
Heating, stirring and dissolving the polymer, the spinning solvent and the spinning additive uniformly, and defoaming to obtain the spinning solution. And extruding the spinning stock solution and the spinning core solution together through a spinning nozzle, and solidifying and forming in a solidification bath tank to obtain the hollow fiber separation membrane. Through the structural improvement of the spinning nozzle and the adjustment of spinning process equipment, 2-8 hollow fiber membranes can be subjected to cluster spinning, and the tensile strength and the breaking strength of the hollow fiber membranes can be greatly improved. In order to further improve the tensile strength and the breaking strength of the hollow fiber membrane, during spinning, a rib thread and 2-8 holes of membrane-making liquid can enter a coagulating bath through a spinning nozzle to prepare a high-strength hollow fiber membrane bundle with reinforcing ribs in the membrane bundle, thereby preparing the hollow fiber membrane with stable performance, proper aperture, high water permeability and high strength. Or a reinforced pipe and the membrane-making liquid with 2-8 holes enter a coagulating bath through a spinning nozzle to prepare the high-strength hollow fiber membrane bundle with the reinforced pipe inside. The reinforcing tube may be a braided tube or a homogeneous non-braided tube.
Example 1: uniformly dispersing 500 g of calcium carbonate 2 micron particles in 5 kg of dimethylacetamide solvent under high-speed stirring, adding 2kg of dimethylacetamide, 2kg of polyvinylidene fluoride resin, 500 g of polyethylene glycol and 100 g of Tween-20, uniformly stirring and dissolving, defoaming and spinning. And (3) enabling the spinning solution to pass through a three-tow six-rib nozzle as shown in figure 5, and enabling the spinning solution and six strands of polyester rib yarns to enter a coagulating bath to prepare the bunched hollow fiber membrane. The coagulant is water, the initial modulus of the polyester filament yarn is 20-300cN/dtex, and the filament density of the polyester filament yarn is 100-500 dtex. Calcium carbonate in the polyvinylidene fluoride hollow fiber is removed by hydrochloric acid solution, the inner diameter of the obtained external pressure polyvinylidene fluoride hollow fiber porous membrane is 0.5mm, the wall thickness is 0.15mm, the appearance is not completely dissolved into a round shape, and the shape is petal-shaped. The breaking tension of a single hollow fiber membrane bundle is 10.1kg, and the pure water permeation speed is 970L/m 2 H @0.1MPa20 ℃, membrane separation pore diameter 0.10 μm, porosity 72%.
Comparative example 1: uniformly dispersing 500 g of calcium carbonate 2 micron particles in 5 kg of dimethylacetamide solvent under high-speed stirring, adding 2kg of dimethylacetamide, 2kg of polyvinylidene fluoride resin, 500 g of polyethylene glycol and 100 g of Tween-20, uniformly stirring and dissolving, defoaming and spinning. The coagulant is water. Calcium carbonate in the polyvinylidene fluoride hollow fiber is removed by hydrochloric acid solution, and the inner diameter of the obtained external pressure polyvinylidene fluoride hollow fiber porous membrane is 0.5mm, and the wall thickness is 0.15mm. The breaking tension of the hollow fiber membrane wire is 0.11kg and the pure waterPenetration speed 970L/m 2 H @0.1MPa20 ℃, membrane separation pore diameter 0.10 μm, porosity 72%.
Example 2: 500 g of aluminum oxide 20-80 nano particles are evenly dispersed in 7kg of N-methyl pyrrolidone solvent under high-speed stirring, and then 2kg of polyvinylidene fluoride resin and 500 kg of polyvinylidene fluoride resin are addedPolyvinyl pyrrolidone in 100 g and Tween-80 in 100 g through stirring, defoaming and spinning. The spinning solution passes through a five-tow five-rib nozzle similar to that shown in figure 5, and enters a coagulating bath together with five strands of polypropylene fiber ribs to prepare the bundling type hollow fiber membrane. The density of the polypropylene yarn is 100-500 dtex. The coagulant in the coagulation bath is water. Removing aluminum oxide in polyvinylidene fluoride hollow fibers by using NaOH aqueous solution to obtain an external pressure polyvinylidene fluoride hollow fiber porous membrane with the inner diameter of 0.6mm, the wall thickness of 0.15mm, the tensile strength of a single membrane bundle of the hollow fibers of 11.7kg and the pure water permeation speed of 870L/m 2 H @0.1MPa20 ℃, membrane separation pore diameter 0.20 μm, porosity 78%.
Comparative example 2: uniformly dispersing 500 g of aluminum oxide 20-80 nano particles in 7kg of N-methyl pyrrolidone solvent under high-speed stirring, adding 2kg of polyvinylidene fluoride resin, 500 g of polyvinylpyrrolidone and 100 g of Tween-80, uniformly stirring and dissolving, defoaming, spinning, and feeding into a coagulating bath to prepare the hollow fiber membrane. The coagulant in the coagulation bath is water. Removing aluminum oxide in polyvinylidene fluoride hollow fiber by NaOH aqueous solution to obtain external pressure polyvinylidene fluoride hollow fiber porous membrane with inner diameter of 0.6mm, wall thickness of 0.15mm, single membrane wire breaking tension of 0.07kg of hollow fiber and pure water permeation speed of 870L/m 2 H @0.1MPa20 ℃, membrane separation pore diameter 0.20 μm, porosity 78%.
Example 3: uniformly dispersing 800 g of calcium carbonate 2 micron particles in 5 kg of dimethylacetamide solvent under high-speed stirring, then adding 1.8 kg of dimethylacetamide, 1.8 kg of polyvinylidene fluoride resin, 780 g of polyvinylpyrrolidone and 20 g of fluorinated surfactant FC-4, uniformly stirring and dissolving, spinning after defoaming, and using water as a coagulant in a coagulating bath. Mixing six hollow fibersBundling to obtain the bundled hollow fiber membrane. Removing calcium carbonate in the polyvinylidene fluoride hollow fiber by hydrochloric acid solution to obtain an external pressure polyvinylidene fluoride hollow fiber porous membrane with the inner diameter of 0.6mm, the wall thickness of 0.15mm, the rupture strength of 0.43MPa, the tensile strength of a single membrane bundle of the hollow fiber of 1.7kg and the pure water permeation speed of 1210L/m 2 H @0.1MPa20 ℃ and a membrane separation pore size of 0.50. Mu.m.
Comparative example 3: uniformly dispersing 800 g of calcium carbonate 2 micron particles in 5 kg of dimethylacetamide solvent under high-speed stirring, then adding 1.8 kg of dimethylacetamide, 1.8 kg of polyvinylidene fluoride resin, 780 g of polyvinylpyrrolidone and 20 g of fluorinated surfactant FC-4, uniformly stirring and dissolving, spinning after defoaming, and using water as a coagulant in a coagulating bath. Removing calcium carbonate in the polyvinylidene fluoride hollow fibers by using a hydrochloric acid solution to obtain an external pressure polyvinylidene fluoride hollow fiber porous membrane with the inner diameter of 0.6mm, the wall thickness of 0.15mm, the rupture strength of 0.44MPa, the tensile strength of a single membrane wire of the hollow fibers of 0.2kg and the pure water permeation speed of 1190L/m 2 H @0.1MPa20 ℃ and a membrane separation pore size of 0.50. Mu.m.
Example 4: 500 g of calcium carbonate 2 micron particles are uniformly dispersed in 5 cm under high-speed stirringAdding 2kg of dimethylacetamide, 2kg of polyvinylidene fluoride resin, 500 g of polyethylene glycol and 100 g of Tween-20 into kilogram of dimethylacetamide solvent, stirring and dissolving uniformly, defoaming and spinning. And (3) passing the spinning solution through a four-strand six-rib nozzle similar to that shown in figure 5, and entering the spinning solution and six strands of PVDF (polyvinylidene fluoride) fish wires into a coagulating bath to prepare the bunched hollow fiber membrane. The coagulant is water, and the diameter of the fishing line is 0.3mm. Calcium carbonate in the polyvinylidene fluoride hollow fiber is removed by hydrochloric acid solution, and the obtained external pressure polyvinylidene fluoride hollow fiber porous membrane has the inner diameter of 0.5mm, the wall thickness of 0.15mm, and the appearance which is not completely dissolved into a round shape is in a petal shape. The breaking tension of a single hollow fiber membrane bundle is 15.1kg, and the pure water permeation speed is 940L/m 2 H @0.1MPa20 ℃, membrane separation pore diameter 0.10 μm, porosity 72%.
Example 5: 500 g of calcium carbonate 2 micron particles are uniformly dispersed in 5 kilograms of dimethyl under high-speed stirringAnd adding 2kg of dimethylacetamide, 2kg of polyvinylidene fluoride resin, 500 g of polyethylene glycol and 100 g of Tween-20 into the acetamide solvent, stirring and dissolving uniformly, defoaming and spinning. The spinning solution passes through a four-tow six-rib nozzle similar to that shown in figure 5, and enters a coagulating bath together with six strands of polypropylene braided wires to prepare the bunched hollow fiber membrane. The coagulant is water, and the diameter of the polypropylene braided wire is 0.5mm. Calcium carbonate in the polyvinylidene fluoride hollow fiber is removed by hydrochloric acid solution, and the obtained external pressure polyvinylidene fluoride hollow fiber porous membrane has the inner diameter of 0.5mm, the wall thickness of 0.15mm, and the appearance which is not completely dissolved into a round shape is in a petal shape. The tension of the single hollow fiber membrane bundle at break is 13.8kg, and the pure water penetration speed is 930L/m 2 H @0.1MPa20 ℃, membrane separation pore diameter 0.10 μm, porosity 72%.
Example 6: uniformly dispersing 500 g of calcium carbonate 2 micron particles in 5 kg of dimethylacetamide solvent under high-speed stirring, adding 2kg of dimethylacetamide, 2kg of polyvinylidene fluoride resin, 500 g of polyethylene glycol and 100 g of Tween-20, uniformly stirring and dissolving, defoaming and spinning. The spinning solution passes through a six-strand six-rib nozzle similar to that shown in figure 5, and enters a coagulating bath together with six strands of polypropylene braided tubes to prepare the bunched hollow fiber membrane. The coagulant is water, and the diameter of the outside of the polypropylene braided tube is 1.5mm. Calcium carbonate in the polyvinylidene fluoride hollow fiber is removed by hydrochloric acid solution, and the obtained external pressure polyvinylidene fluoride hollow fiber porous membrane has the inner diameter of 0.5mm, the wall thickness of 0.15mm, and the shape which is not completely dissolved into a round shape is petal-shaped. The breaking tension of a single hollow fiber membrane bundle is 23.1kg, and the pure water permeation speed is 980L/m 2 H @0.1MPa20 ℃, membrane separation pore size 0.10 μm, porosity 72%.
Example 7: uniformly dispersing 500 g of calcium carbonate 2 micron particles in 5 kg of dimethylacetamide solvent under high-speed stirring, adding 2kg of dimethylacetamide, 2kg of polyvinylidene fluoride resin, 500 g of polyethylene glycol and 100 g of Tween-20, uniformly stirring and dissolving, defoaming and spinning. The spinning solution passes through a six-tow single-rib nozzle similar to that shown in figure 5, and enters a polypropylene fiber braided tube into a coagulating bath to prepare the polypropylene fiber composite materialA tube bundle type hollow fiber membrane. The coagulant is water, and the polypropylene braided tube is straightThe diameter is 2.5mm. Removing calcium carbonate in the polyvinylidene fluoride hollow fiber by hydrochloric acid solution to obtain an external pressure polyvinylidene fluoride hollow fiber porous membrane with an inner diameter of 0.4mm and a wall thickness of 0.1mm as shown in figure 4, wherein the external shape is not completely dissolved into a round shape and is in a petal shape. The breaking tension of a single hollow fiber membrane bundle is 19.1kg, and the pure water permeation speed is 960L/m 2 H @0.1MPa20 ℃, membrane separation pore diameter 0.10 μm, porosity 72%.
Claims (7)
1. A cluster type external pressure hollow fiber membrane is characterized in that: the external diameter of the filament bundle is 0.3-3 mm, the internal diameter of the monofilament is 0.1-1.0 mm, the wall thickness is 0.05-1 mm, the porosity is 50-90%, the aperture of the membrane separation is 0.01-1 micron, the tensile force of the hollow fiber membrane bundle is 0.2-25.0 kg/fiber, the water flux of pure water is 600-10000L/m 2 ·[email protected]，25℃。
2. The bundled hollow fiber membrane according to claim 1, wherein: 2-8 single hollow fibers are integrated into one bundle to form a bundle-shaped hollow fiber membrane,
3. the bundled hollow fiber membrane according to claim 1, wherein: 2-8 single hollow fibers are integrated into one bundle to form a bundle-shaped hollow fiber membrane, and continuous reinforced fibers are arranged in the center of the hollow fiber membrane bundle for reinforcement.
4. The bundled hollow fiber membrane according to claim 1, wherein: 2-8 single hollow fibers are integrated into a bundle to form a bundle-shaped hollow fiber membrane, and the center of the hollow fiber membrane bundle is provided with a ribbed tube for reinforcement.
5. A method for producing the bundle-like hollow fiber membrane of claim 2, characterized in that: the method comprises the steps of adopting a dry-wet spinning process, enabling polymer membrane casting liquid and spinning core liquid to pass through a spinning nozzle simultaneously to form nascent hollow fibers, integrating 2-8 single nascent hollow fibers into one bundle before entering a coagulation bath water tank, and then entering the coagulation bath water tank to form a bundle-shaped hollow fiber membrane.
6. A method for producing the bundle-shaped hollow fiber membrane of claim 3, characterized in that: the method comprises the steps of adopting a dry-wet spinning process, enabling polymer membrane casting liquid, spinning core liquid and rib wires to pass through a spinning nozzle at the same time, enabling the polymer membrane casting liquid and the spinning core liquid to form nascent hollow fibers, integrating 2-8 single nascent state hollow fibers and the rib wires into a bundle before entering a coagulation bath water tank, enabling the rib wires to be located in the centers of the 2-8 single nascent state hollow fibers, and then enabling the bundle hollow fiber membrane with the reinforced center to enter the coagulation bath water tank together to form the bundle-shaped hollow fiber membrane with the reinforced center.
7. A method for producing the bundle-like hollow fiber membrane of claim 4, characterized in that: the method comprises the steps of adopting a dry-wet spinning process, enabling a polymer membrane casting solution, a spinning core solution and a braided tube to simultaneously pass through a spinning nozzle, enabling the polymer membrane casting solution and the spinning core solution to form nascent hollow fibers, integrating 2-8 single nascent state hollow fibers and the braided tube into a bundle before entering a coagulation bath water tank, distributing the 2-8 single nascent state hollow fibers on the outer wall of the braided tube, and then enabling the hollow fibers and the braided tube to enter the coagulation bath water tank together to form a bundled hollow fiber membrane with the braided tube at the center.
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