CN103041717B - Yarn fiber reinforced double-layer tubular filtering membrane and method for preparing same - Google Patents
Yarn fiber reinforced double-layer tubular filtering membrane and method for preparing same Download PDFInfo
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- CN103041717B CN103041717B CN201310012882.9A CN201310012882A CN103041717B CN 103041717 B CN103041717 B CN 103041717B CN 201310012882 A CN201310012882 A CN 201310012882A CN 103041717 B CN103041717 B CN 103041717B
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Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a yarn fiber reinforced double-layer tubular filtering membrane. The tubular filtering membrane has a double-layer structure, wherein the inner layer is a first polymer membrane, while the outer layer is a second polymer membrane; and yarn fibers distributed in parallel are arranged in the inner layer or the outer layer for mechanically reinforcing the tubular filtering membrane. The tubular filtering membrane provided by the invention is obviously improved in transverse compression resistance and blast resistance as well as membrane safety while having excellent axial mechanical properties; and the tubular filtering membrane with excellent overall performance for external-compression type filtering or internal-compression type filtering by adjusting the distribution positions of the yarn fibers and the double-layer structure and the properties of the membrane. The invention also discloses a method for preparing the tubular filtering membrane; and the two-layer synchronous coextrusion technique is employed, so that the production efficiency of the membrane can be effectively improved and the preparation cost of the tubular filtering membrane can be reduced.
Description
Technical Field
The invention belongs to the technical field of membranes, and particularly relates to a yarn fiber reinforced tubular filtering membrane with a double-layer structure and a preparation method thereof.
Background
The membrane separation process is a novel high-efficiency separation technology which takes a selective permeation membrane as a separation medium and separates, purifies and concentrates a mixture under the pushing of an external force. The tubular filtering membrane has the characteristics of large effective separation area, simple component structure, easy operation and the like, and is widely applied to the fields of water treatment, biological medicine, food chemical industry and the like. However, compared with inorganic membranes such as ceramics and metals, the mechanical strength of the polymer tubular filtration membrane is relatively poor, and the problems of filament breakage, flattening, cracking and the like are easy to occur in the using and cleaning processes. In order to improve the mechanical property of the tubular filter membrane, the fiber and the braided tube thereof are widely applied to the production and manufacture of the filter membrane.
The fiber braided tube is applied to the preparation of a tubular filter membrane, and the technology of coating a casting solution on the outer layer of the braided tube is usually adopted, so that the filter membrane has good tensile and compressive properties. Patents US 4061821 and US 5472607 disclose a method for preparing a PAN hollow fiber membrane and a PVDF hollow fiber membrane, respectively, having a braided tube as an inner layer, the mechanical properties of the membranes being significantly improved. In addition, in the preparation of the reinforced tubular membrane, preparation technologies such as coating a double-layer membrane casting solution (CN 102160967a) outside a weaving tube, synchronously weaving fibers and coating the membrane casting solution (CN 101543731a), and arranging a polymer separation membrane layer (CN 1864828A) inside and outside the weaving tube are also seen. However, the tubular membrane reinforced with the braided tube has the following problems: the bonding performance between the braided tube and the polymer film is poor, and the phenomena of falling and peeling exist in the using process; the braided tube reinforced tubular membrane prepared by the conventional method is generally only suitable for external pressure type filtration; the tubular membrane is relatively costly, subject to the efficiency and cost of existing fiber weaving.
In addition, the unwoven fibers can also be used directly to increase the strength of the tubular membrane. Patent WO 03/097221 proposes the simultaneous introduction of fibers and dope solution into a spinneret to produce a fiber reinforced composite membrane having a homogeneous hollow fiber membrane-like inner/outer layer structure. However, the fiber reinforced membrane only axially distributes fibers in the membrane, so that the tensile resistance of the membrane is improved only axially, and the compression resistance and the explosion resistance are not obviously improved; meanwhile, the fiber and the membrane liquid have certain bonding problem inevitably, and the membrane yarn has certain potential safety hazard in the long-term use process.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the yarn fiber reinforced double-layer tubular filtering membrane which has high flux, excellent comprehensive performances of mechanics, pressure resistance, interception, pollution resistance and the like and is suitable for external pressure type filtering or internal pressure type filtering. The tubular filter membrane is of a double-layer structure, the inner layer is a first polymer membrane, the outer layer is a second polymer membrane, and the inner layer and/or the outer layer contain yarn fibers distributed in parallel for mechanical reinforcement of the tubular filter membrane. The tubular filtering membrane has high flux and excellent comprehensive performance and has wide applicability in different application fields by adjusting the double-layer structure and performance of the membrane and the distribution position of the yarn fibers.
The technical scheme adopted by the invention is as follows:
the utility model provides a yarn fibre reinforcing double-deck tubular filtration membrane which characterized in that: the tubular filtering membrane is of a double-layer structure, the inner layer is a first polymer membrane, the outer layer is a second polymer membrane, yarn fibers used for reinforcing are distributed on the tubular filtering membrane, the outer diameter of the tubular filtering membrane is 0.8-5.0 mm, and the inner diameter of the tubular filtering membrane is 0.4-3.0 mm.
Wherein,
the polymer materials of the first polymer film and the second polymer film are the same polymer or different polymers; the homogeneous polymer of the present invention includes homogeneous polymers of various specifications having different physical property parameters such as molecular weight and molecular weight distribution.
Preferably, the polymer material is selected from any one of polyvinylidene fluoride, polyvinyl chloride, polyether sulfone, polysulfone, polyacrylonitrile and cellulose acetate; for example, the polymer material of the first polymer film may be polyvinylidene fluoride, and the polymer material of the second polymer film may be polyvinylidene fluoride of other specifications having different physical property parameters such as molecular weight and molecular weight distribution; the first polymer film and the second polymer film may be made of polyvinylidene fluoride having the same physical properties such as molecular weight and molecular weight distribution.
Preferably, the yarn fibers may be distributed only within the first polymer film (fig. 1-1), only within the second polymer film (fig. 1-2), or both within the first polymer film and within the second polymer film (fig. 1-3).
More preferably, the yarn fibers are symmetrically distributed within the first polymer film or within the second polymer film.
More preferably, the number of the yarn fibers is 3-12.
Preferably, the yarn fiber material is selected from one or more than two blended yarn fibers of cellulose, polyester, polyamide, polyvinyl alcohol, polypropylene, polyacrylonitrile, polyvinyl chloride, carbon fiber and glass fiber, and the yarn fibers distributed in the first polymer film or the second polymer film can be the same or different; the yarn is long yarn formed by lengthening and twisting short fiber, the short fiber materials are not blended yarn at the same time, and the short fiber materials are pure yarn at the same time; the fiber is a long silk thread formed by gathering a plurality of long fibers, the long fibers are not blended fibers at the same time, and the long fibers are pure fibers at the same time. The yarn fiber comprises yarn and fiber, and specifically comprises blended yarn, pure yarn, blended fiber and pure fiber; the pure yarn fibers include, but are not limited to, pure cellulose yarn fibers (including cellulose yarn and cellulose fiber), polyester yarn fibers (including polyester yarn and polyester fiber), polyamide yarn fibers (including polyamide yarn and polyamide fiber), polyvinyl alcohol yarn fibers (including polyvinyl alcohol yarn and polyvinyl alcohol fiber), polypropylene yarn fibers (including polypropylene yarn and polypropylene fiber), polyacrylonitrile yarn fibers (including polyacrylonitrile yarn and polyacrylonitrile fiber), polyvinyl chloride yarn fibers (including polyvinyl chloride yarn and polyvinyl chloride fiber), carbon fiber yarn fibers (including carbon fiber yarn and carbon fiber), glass fiber yarn fibers (including glass fiber yarn and glass fiber) and the like; the blended yarn fibers include, but are not limited to, polyester-cotton blended yarn fibers (polyester and cellulose blended yarns), polyamide-cotton blended yarn fibers (polyamide and cellulose blended yarns), polyester-nitrile blended yarn fibers (polyester and polyacrylonitrile blended yarns), and the like.
The tubular filtering membrane has a double-layer structure, the yarn fibers are distributed in the membrane, the yarn fibers ensure the tensile strength of the membrane in the axial direction, and the double-layer structure enables the transverse compression resistance and the transverse explosion resistance of the membrane and the safety of the membrane to be obviously improved. And the tubular filtering membrane with excellent comprehensive performance suitable for external pressure type filtering or internal pressure type filtering can be obtained by adjusting the distribution position of the yarn fibers, the double-layer structure of the membrane and the performance. When the yarns for reinforcing are distributed in the first polymer membrane, the first polymer membrane mainly plays a role of a supporting layer, the second polymer membrane outer skin layer is of a denser structure and mainly plays a role of a functional layer (figure 1-1), and the tubular filter membrane is more suitable for an external pressure type filter system; when the yarn fibers for reinforcement are distributed in the second polymer membrane, the second polymer membrane mainly plays a role of a supporting layer, the inner skin layer of the first polymer membrane is of a compact structure and mainly plays a role of a functional layer (figure 1-2), and the tubular filter membrane is more suitable for an internal pressure type filter system; when the yarns for reinforcement are distributed in the first polymer membrane and the second polymer membrane, the inner layer of the first polymer membrane and the outer layer of the second polymer membrane are both of a compact structure, so that the two polymer membranes have good strength and separation effect (shown in figures 1-3).
The second purpose of the invention is to provide the application of the yarn fiber reinforced double-layer tubular filter membrane in an external pressure type filter system or an internal pressure type filter system, wherein the external pressure type filter system and the internal pressure type filter system comprise but are not limited to the pharmaceutical industry (traditional Chinese medicine concentration, pesticide production, biological fermentation liquor filtration and the like), the food industry (fructose separation and purification, food additive concentration, dairy product production, wine refining, natural pigment extraction and the like), dye chemical industry and auxiliaries, the biotechnology (protein, polypeptide and the like clarification and refining), the environmental protection and water treatment fields (spinning, printing and dyeing and other industrial wastewater treatment and recycling, municipal wastewater treatment, preparation of various water required by industry and life and the like).
The third purpose of the invention is to provide a preparation method of the yarn fiber reinforced double-layer tubular filter membrane, which adopts a double-layer synchronous coextrusion technology to realize one-step membrane forming and comprises the following steps:
(1) preparing casting solution of a first polymer film and a second polymer film, defoaming and standing for later use;
(2) respectively injecting the casting solution of the first polymer film and the casting solution of the second polymer film into a casting solution runner of the first polymer film and a casting solution runner of the second polymer film in a spinning nozzle, enabling the reinforced yarns to be arranged in parallel and penetrate through the casting solution runners, and carrying out double-layer synchronous co-extrusion to form the yarn-reinforced double-layer tubular filtering membrane by a solution phase conversion method under the combined action of core liquid and a coagulating bath; the spinning nozzle is of a three-flow-channel structure and sequentially comprises a core liquid flow channel (A), a membrane casting liquid flow channel (B) of a first polymer membrane and a membrane casting liquid flow channel (C) of a second polymer membrane from inside to outside;
(3) and (3) rolling, cleaning and airing the co-extruded double-layer tubular filtering membrane to obtain the yarn fiber reinforced double-layer tubular filtering membrane with stable structure and performance.
The casting solution of the first polymer film and the casting solution of the second polymer film respectively comprise a polymer material, a modifier, a pore-forming agent and a solvent. The formula and preparation conditions of the casting solution can be adjusted according to actual needs. The two kinds of casting solution may have the same or different recipe and compounding condition, and the polymer material, modifier, pore forming agent and solvent may be the same or different matter, and each matter may have the same or different content. Meanwhile, the ingredients and the standing temperature of the two casting solution can be the same or different.
Preferably, the polymer material is selected from any one of polyvinylidene fluoride, polyvinyl chloride, polyether sulfone, polysulfone, polyacrylonitrile and cellulose acetate, and the mass percentage of the polymer material is 8-30%; the modifier is selected from the group consisting of compounds having a molecular weight of 1X 104～1×106One or more of polyvinylpyrrolidone, silicon dioxide, titanium oxide and aluminum oxide, wherein the mass percentage of the polyvinylpyrrolidone, the silicon dioxide, the titanium oxide and the aluminum oxide is 0.5-6%; the pore-forming agent is selected from water, ethanol, glycerol, glycol and polyethylene with molecular weight of 400-1000Any one or more of diols, the mass percentage of which is 0.5-8%; the solvent is selected from any one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide, and the mass percentage of the solvent is 56-91%; and preparing the casting solution and standing at the temperature of 60-90 ℃. For example, the pore former of the first polymer film may be selected from polyethylene glycol having a molecular weight of 400, and the pore former of the second polymer film may be selected from polyethylene glycol having a molecular weight of 1000; alternatively, the pore-forming agent of each of the first polymer film and the second polymer film may be polyethylene glycol having a molecular weight of 400.
Wherein, the core liquid flow channel, the casting solution flow channel of the first polymer film and the casting solution flow channel of the second polymer film can adopt different shapes; the core liquid, the casting solution of the first polymer film and the casting solution of the second polymer film can be injected into the spinning nozzle in different sequences, but the effect of synchronous coextrusion is finally achieved.
Preferably, the core liquid flow channel is a circular flow channel, and the casting solution flow channel of the first polymer film and the casting solution flow channel of the second polymer film are both annular flow channels.
Preferably, the core solution is injected first, and then the casting solution of the first polymer film and the casting solution of the second polymer film are injected simultaneously; or simultaneously injecting the core liquid, the casting solution of the first polymer film and the casting solution of the second polymer film.
Preferably, the yarn passes through only the dope solution flow path of the first polymer film (fig. 2-1), or only the dope solution flow path of the second polymer film (fig. 2-2), or both the dope solution flow path of the first polymer film and the dope solution flow path of the second polymer film (fig. 2-3); the passing means that the yarn fiber passes through the flow channel of the spinning nozzle and is fixed on the film yarn collecting device along the spinning line. In this manner, the yarns may be distributed only within the first polymer membrane of the double-layer tubular filtration membrane (FIGS. 1-1), only within the second polymer membrane of the double-layer tubular filtration membrane (FIGS. 1-2), or both within the first polymer membrane and within the second polymer membrane of the double-layer tubular filtration membrane (FIGS. 1-3).
More preferably, the yarn fibers are symmetrically distributed within the first polymer film or within the second polymer film;
more preferably, the number of the yarn fibers is 3-12.
Preferably, the yarn fiber material is selected from one or more than two blended yarn fibers of cellulose, polyester, polyamide, polyvinyl alcohol, polypropylene, polyacrylonitrile, polyvinyl chloride, carbon fiber and glass fiber, and the yarn fibers distributed in the first polymer film or the second polymer film can be the same or different; the yarn is long yarn formed by lengthening and twisting short fiber, the short fiber materials are not blended yarn at the same time, and the short fiber materials are pure yarn at the same time; the fiber is a long silk thread formed by gathering a plurality of long fibers, the long fibers are not blended fibers at the same time, and the long fibers are pure fibers at the same time. The yarn fiber comprises yarn and fiber, and specifically comprises blended yarn, pure yarn, blended fiber and pure fiber. The pure yarn fibers include, but are not limited to, pure cellulose yarn fibers (including cellulose yarn and cellulose fiber), polyester yarn fibers (including polyester yarn and polyester fiber), polyamide yarn fibers (including polyamide yarn and polyamide fiber), polyvinyl alcohol yarn fibers (including polyvinyl alcohol yarn and polyvinyl alcohol fiber), polypropylene yarn fibers (including polypropylene yarn and polypropylene fiber), polyacrylonitrile yarn fibers (including polyacrylonitrile yarn and polyacrylonitrile fiber), polyvinyl chloride yarn fibers (including polyvinyl chloride yarn and polyvinyl chloride fiber), carbon fiber yarn fibers (including carbon fiber yarn and carbon fiber), glass fiber yarn fibers (including glass fiber yarn and glass fiber) and the like; the blended yarn fibers include, but are not limited to, polyester-cotton blended yarn fibers (blended by cellulose and polyester), polyamide-cotton blended yarn fibers (blended by polyamide and cellulose), polyester-nitrile blended yarn fibers (blended by polyester and polyacrylonitrile), and the like.
The core solution is water or a water/solvent mixed solution, the temperature is 20-60 ℃, and the solvent in the mixed solution is any one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide, and the mass percentage of the solvent is 5-30%; the solidification liquid is water or a water/solvent mixed liquid, the temperature is 20-60 ℃, and the solvent in the mixed liquid is any one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide, and the mass percentage of the solvent is 5-30%.
According to the preparation method of the yarn fiber reinforced double-layer tubular filtering membrane, the yarn fiber and the casting solution of the first polymer membrane and the second polymer membrane are finally extruded out of the spinning jet synchronously, namely the discharging speed of the casting solution is consistent with the unwinding speed of the yarn fiber and is 5-30 m/min, and continuous one-step membrane forming is realized, so that the production efficiency of the membrane is effectively improved, and the preparation cost is reduced.
The invention has the beneficial effects that:
(1) the yarn fiber is adopted to improve the mechanical property of the membrane so as to avoid or reduce the phenomenon of filament breakage of the tubular filtering membrane in the using and cleaning processes.
(2) The tubular filtering membrane is of a double-layer structure, so that the transverse compression resistance and the transverse explosion resistance of the membrane and the safety performance of the membrane are obviously improved by the double-layer structure while the axial tensile strength of the membrane is guaranteed by the yarn fiber.
(3) Tubular filtering membranes with different structures and performances can be prepared by adjusting the quantity and distribution positions of the yarns and controlling the formula of the casting solution and the film forming conditions, so that the tubular filtering membranes are suitable for external pressure type filtering or internal pressure type filtering systems.
(4) The yarn fiber reinforced double-layer tubular filter membrane has the advantages of high flux, excellent interception, hydrophilicity, pollution resistance and the like.
(5) The invention directly applies the unwoven yarn fiber to improve the mechanical property of the membrane, and adopts the technology of synchronous coextrusion of the yarn fiber and the double-layer membrane casting solution, thereby effectively improving the production efficiency of the membrane and reducing the preparation cost.
Drawings
FIG. 1 is a schematic cross-sectional structure of a yarn fiber reinforced double-layer tubular filter membrane of the present invention:
wherein, fig. 1-1 shows a double-layer tubular filtration membrane in which the yarn fiber is distributed only in the first polymer membrane, fig. 1-2 shows a double-layer tubular filtration membrane in which the yarn fiber is distributed only in the second polymer membrane, and fig. 1-3 shows a double-layer tubular filtration membrane in which both the yarn fiber is distributed in the first polymer membrane and the second polymer membrane;
in the figure, 1 is a first polymer film, 2 is a second polymer film, and 3 is a yarn.
FIG. 2 is a cross-sectional view of the discharge port of the spinneret of the present invention:
wherein FIG. 2-1 shows a dope solution flow path through which a yarn passes only through a first polymer film of a spinneret, FIG. 2-2 shows a dope solution flow path through which a yarn passes only through a second polymer film of a spinneret, and FIG. 2-3 shows a dope solution flow path through which a yarn passes through a first polymer film of a spinneret and a dope solution flow path through which a second polymer film passes;
in the figure, A is a core liquid flow channel, B is a casting solution flow channel of a first polymer film, C is a casting solution flow channel of a second polymer film, and 3 is a yarn.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and examples.
The cross-sectional structure of the yarn fiber reinforced double-layer tubular filter membrane is schematically shown in figure 1. The tubular filtering membrane is of a double-layer structure, the inner layer is a first polymer membrane, the outer layer is a second polymer membrane, yarn fibers used for reinforcing are distributed on the tubular filtering membrane, the outer diameter of the tubular filtering membrane is 0.8-5.0 mm, and the inner diameter of the tubular filtering membrane is 0.4-3.0 mm. The tubular filtration membrane has 3 structures, i.e., the yarn is distributed only in the first polymer membrane (fig. 1-1), the yarn is distributed only in the second polymer membrane (fig. 1-2), and both the yarn is distributed in the first polymer membrane and the second polymer membrane (fig. 1-3), depending on the position of the yarn inside.
Wherein, the polymer materials of the first polymer film and the second polymer film are the same polymer or different polymers.
Preferably, the polymer material is selected from any one of polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), Polyethersulfone (PES), Polysulfone (PSF), Polyacrylonitrile (PAN), and Cellulose Acetate (CA);
preferably, the yarn fibers are symmetrically distributed within the first polymer film or within the second polymer film.
More preferably, the number of the yarn fibers is 3-12.
Preferably, the yarn fiber material is selected from one or more than two blended yarn fibers of cellulose, polyester, polyamide, polyvinyl alcohol, polypropylene, polyacrylonitrile, polyvinyl chloride, carbon fiber and glass fiber, and the yarn fibers distributed in the first polymer film or the second polymer film can be the same or different; the yarn is long yarn formed by lengthening and twisting short fiber, the short fiber materials are not blended yarn at the same time, and the short fiber materials are pure yarn at the same time; the fiber is a long silk thread formed by gathering a plurality of long fibers, the long fibers are not blended fibers at the same time, and the long fibers are pure fibers at the same time. The yarn fiber comprises yarn and fiber, and specifically comprises blended yarn, pure yarn, blended fiber and pure fiber. The pure yarn fibers include, but are not limited to, pure cellulose yarn fibers (including cellulose yarn and cellulose fiber), polyester yarn fibers (including polyester yarn and polyester fiber), polyamide yarn fibers (including polyamide yarn and polyamide fiber), polyvinyl alcohol yarn fibers (including polyvinyl alcohol yarn and polyvinyl alcohol fiber), polypropylene yarn fibers (including polypropylene yarn and polypropylene fiber), polyacrylonitrile yarn fibers (including polyacrylonitrile yarn and polyacrylonitrile fiber), polyvinyl chloride yarn fibers (including polyvinyl chloride yarn and polyvinyl chloride fiber), carbon fiber yarn fibers (including carbon fiber yarn and carbon fiber), glass fiber yarn fibers (including glass fiber yarn and glass fiber) and the like; the blended yarn fibers include, but are not limited to, polyester-cotton blended yarn fibers (blended by cellulose and polyester), polyamide-cotton blended yarn fibers (blended by polyamide and cellulose), polyester-nitrile blended yarn fibers (blended by polyester and polyacrylonitrile), and the like.
The specific implementation mode of the yarn fiber reinforced double-layer tubular filter membrane prepared by the invention is as follows:
(1) preparing casting solution of a first polymer film and a second polymer film: and blending the polymer material, the modifier, the pore-forming agent and the solvent, defoaming and standing for later use.
Wherein, the formulation and the preparation conditions of the two casting solution can be the same or different. Preferably, the polymer material is selected from any one of polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), polyether sulfone (PES), Polysulfone (PSF), Polyacrylonitrile (PAN) and Cellulose Acetate (CA), and the mass percentage of the polymer material is 8-30%; the modifier is selected from the group consisting of compounds having a molecular weight of 1X 104～1×106Polyvinylpyrrolidone (PVP) and Silica (SiO)2) Titanium oxide (TiO)2) Alumina (Al)2O3) Any one or more of the above components, the mass percentage of which is 0.5-6%; the pore former is selected from water (H)2O), ethanol, glycerol, glycol and polyethylene glycol (PEG) with the molecular weight of 400-1000, wherein the mass percentage of the one or more polyethylene glycols is 0.5-8%; the solvent is selected from any one of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO), and the mass percentage of the solvent is 56-91%.
(2) Double-layer coextrusion integrated film forming: the spinning head is of a three-flow-channel structure, namely a core liquid flow channel (A), a casting solution flow channel (B) of a first polymer film and a casting solution flow channel (C) of a second polymer film in sequence from inside to outside, the section structure of a discharge port of the spinning head is shown in figure 2, yarns are arranged in parallel and penetrate through the casting solution flow channel of the spinning head, the casting solutions of the first polymer film and the second polymer film are respectively injected into the casting solution flow channel of the first polymer film and the casting solution flow channel of the second polymer film in the spinning head, the yarns for reinforcement are arranged in parallel and penetrate through the casting solution flow channels, double-layer synchronous co-extrusion is carried out under the combined action of core liquid and a coagulating bath, and then the integrated yarn reinforced double-layer tubular filtering membrane is wound up through the coagulating. During the manufacturing process, the yarn may pass through only the dope solution flow channel of the first polymer film of the spinneret (fig. 2-1), the yarn may pass through only the dope solution flow channel of the second polymer film of the spinneret (fig. 2-2), and both the dope solution flow channel of the first polymer film of the spinneret and the dope solution flow channel of the second polymer film of the spinneret (fig. 2-3) may be formed, thereby respectively manufacturing the double-layer tubular filtration membranes represented by fig. 1-1, fig. 1-2, and fig. 1-3.
Preferably, the yarns are symmetrically distributed in the first polymer film or the second polymer film, and the preferable number is 3-12. The yarn fiber material is selected from any one or more than two blended yarn fibers of cellulose, polyester, polyamide, polyvinyl alcohol, polypropylene, polyacrylonitrile, polyvinyl chloride, carbon fiber and glass fiber, and the yarn fibers distributed in the first polymer film or the second polymer film can be the same or different. The core solution is water or a water/solvent mixed solution, the temperature is 20-60 ℃, and the solvent in the mixed solution is any one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide, and the mass percentage of the solvent is 5-30%; the solidification liquid is water or a water/solvent mixed liquid, the temperature is 20-60 ℃, and the solvent in the mixed liquid is any one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide, and the mass percentage of the solvent is 5-30%.
And finally, the yarn and the casting solution of the first polymer film and the second polymer film are synchronously co-extruded from a spinning nozzle, namely the discharging speed of the casting solution is consistent with the unwinding speed of the yarn, and is 5-30 m/min, so that continuous one-step film forming is realized.
(3) Post-treatment of the double-layer tubular filter membrane: and (3) after the membrane is unwound and collected, soaking and cleaning the membrane in water at the temperature of 5-80 ℃ for 24 hours, then soaking the membrane in a glycerol/water mixed solution (the glycerol content is 1-50 wt%) at the temperature of 5-80 ℃ for 24 hours, and airing the membrane at the temperature of 30 ℃ to obtain the yarn fiber reinforced double-layer tubular filtering membrane with stable structure and performance.
And (3) performance measurement of the yarn fiber reinforced double-layer tubular filter membrane: the membrane size and surface/cross-sectional structure were determined by field emission scanning electron microscopy SIRION-100 (SEM); the water flux is measured by a self-made flux testing device, namely the internal pressure or external pressure pure water permeability of a unit membrane area in a unit time at 25 ℃ and under the pressure of 0.1MPa is measured; the mechanical properties were measured by an electronic stretcher REGER RWT 10; burst resistance is characterized by the pressure at which the membrane ruptures during water pressurization.
The following examples illustrate the present invention in detail, but are not to be construed as limiting the invention.
Example 1
The method comprises the following specific steps:
(1) preparing a casting solution of the first polymer film: PVC (PVC 1300, 12wt%) with polymerization degree of 1300 and molecular weight of 4 multiplied by 104PVP (PVP K30, 1.2wt%), PEG400(4wt%), H2Stirring O (0.5wt%) and DMAC (82.3wt%) at 70 deg.C for 24 hr, filtering, defoaming at 70 deg.C and standing; preparing a casting solution of a second polymer film: PVC (PVC 1300, 18wt%) with polymerization degree of 1300 and molecular weight of 4X 104PVP (PVP K30, 1.8wt%), PEG400(4wt%), H2O (0.5wt%), DMAC (75.7wt%) were stirred at 70 ℃ for 24 hours, filtered, defoamed at 70 ℃ and left to stand for further use.
(2) Double-layer coextrusion integrated film forming: the polyester fibers (6) were passed through the dope solution flow channel (B) of the first polymer film of the spinneret and fixed in advance to the film yarn collecting device along the spinning line. Bore fluid (40 ℃ H)2O), the casting solution of the first polymer film and the casting solution of the second polymer film are respectively and simultaneously injected into a core solution flow channel (A) in a spinning nozzle, a casting solution flow channel (B) of the first polymer film and a casting solution flow channel (C) of the second polymer film under the action of pressure, and then are co-extruded with polyester fibers to enter a coagulating bath (H at 40℃)2O), the spinning speed was 20 m/min.
(3) Post-treatment of the double-layer tubular filter membrane: after the membrane is unwound and collected, the membrane is placed in water at 40 ℃ for soaking and cleaning for 24 hours, then placed in glycerol/water mixed liquor (the content of the glycerol is 20wt%) at 40 ℃ for soaking for 24 hours, and dried at 30 ℃ to obtain the yarn fiber reinforced double-layer tubular filtering membrane, and then the performance test is carried out.
The specific film-forming parameters are as follows:
example 2
The specific steps are the same as example 1, and the specific film-making parameters are as follows:
example 3
The specific steps are the same as example 1, and the specific film-making parameters are as follows:
example 4
The specific steps are the same as example 1, and the specific film-making parameters are as follows:
example 5
The specific steps are the same as example 1, and the specific film-making parameters are as follows:
example 6
The specific steps are the same as example 1, and the specific film-making parameters are as follows:
example 7
The specific steps are the same as example 1, and the specific film-making parameters are as follows:
example 8
The specific steps are the same as example 1, and the specific film-making parameters are as follows:
example 9
The specific steps are the same as example 1, and the specific film-making parameters are as follows:
example 10
The specific steps are the same as example 1, and the specific film-making parameters are as follows:
the performance parameters of the yarn fiber reinforced double-layer tubular filtering membrane prepared in the embodiment 1-10 are as follows:
the above examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Claims (8)
1. The utility model provides a yarn fibre reinforcing double-deck tubular filtration membrane which characterized in that: the tubular filtering membrane is of a double-layer structure, the inner layer is a first polymer membrane, the outer layer is a second polymer membrane, yarn fibers for reinforcement are distributed in the tubular filtering membrane, the outer diameter of the tubular filtering membrane is 0.8-5.0 mm, and the inner diameter of the tubular filtering membrane is 0.4-3.0 mm; the yarn fibers are distributed only in the first polymer film, or only in the second polymer film, or in the first polymer film and the second polymer film.
2. The yarn fiber reinforced double-layer tubular filtration membrane according to claim 1, characterized in that: the polymer materials of the first polymer film and the second polymer film are the same polymer or different polymers.
3. The yarn fiber reinforced double-layer tubular filtration membrane according to claim 2, characterized in that: the polymer material is selected from any one of polyvinylidene fluoride, polyvinyl chloride, polyether sulfone, polysulfone, polyacrylonitrile and cellulose acetate.
4. The yarn fiber reinforced double-layer tubular filtration membrane according to claim 1, characterized in that: the yarn fibers are symmetrically distributed in the first polymer film or the second polymer film.
5. The yarn fiber reinforced double-layer tubular filtration membrane according to claim 1, characterized in that: the number of the yarn fibers is 3-12.
6. The yarn fiber-reinforced double-layer tubular filtration membrane according to any one of claims 1 to 5, characterized in that: the yarn fiber material is selected from any one or more than two blended yarn fibers of cellulose, polyester, polyamide, polyvinyl alcohol, polypropylene, polyacrylonitrile, polyvinyl chloride, carbon fiber and glass fiber, and the yarn fibers distributed in the first polymer film or the second polymer film can be the same or different.
7. A preparation method of a yarn fiber reinforced double-layer tubular filter membrane is characterized by comprising the following steps:
(1) preparing casting solution of a first polymer film and a second polymer film, defoaming and standing for later use;
(2) respectively injecting the casting solution of the first polymer film and the casting solution of the second polymer film into a casting solution runner of the first polymer film and a casting solution runner of the second polymer film in a spinning nozzle, enabling the reinforced yarns to be arranged in parallel and penetrate through the casting solution runners, and carrying out double-layer synchronous co-extrusion to form the yarn-reinforced double-layer tubular filtering membrane by a solution phase conversion method under the combined action of core liquid and a coagulating bath; the spinning nozzle is of a three-flow-channel structure and sequentially comprises a core liquid flow channel, a casting film liquid flow channel of a first polymer film and a casting film liquid flow channel of a second polymer film from inside to outside;
(3) the co-extruded double-layer tubular filtering membrane is rolled, cleaned and dried to obtain a yarn fiber reinforced double-layer tubular filtering membrane with stable structure and performance;
the yarn in the step 2) only passes through the casting solution runner of the first polymer film, or only passes through the casting solution runner of the second polymer film, or both the casting solution runner of the first polymer film and the casting solution runner of the second polymer film pass through the yarn.
8. Use of the yarn fiber reinforced double tube filtration membrane of any one of claims 1 to 6 in an external pressure filtration system or an internal pressure filtration system.
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| CN103263807A (en) * | 2013-05-21 | 2013-08-28 | 张永安 | Strong water-absorbing composite filtering strip used for filter |
| CN104815563A (en) * | 2015-04-20 | 2015-08-05 | 天津工业大学 | Reinforced hollow fibrous membrane and preparation method thereof |
| CN107961681A (en) * | 2016-10-18 | 2018-04-27 | 浙江省化工研究院有限公司 | A kind of method for improving Pvdf Microporous Hollow Fiber Membrane intensity |
| CN111356513A (en) * | 2017-09-07 | 2020-06-30 | 博滤克斯公司 | Small diameter tubular porous fiber filter |
| CN108211815A (en) * | 2017-12-29 | 2018-06-29 | 盐城海普润膜科技有限公司 | A kind of composite enhanced hollow-fibre membrane and its preparation method and application |
| CN108355499B (en) * | 2018-03-23 | 2020-04-24 | 海南立昇净水科技实业有限公司 | Double-separation-layer hollow fiber ultrafiltration membrane containing tubular support net and preparation method thereof |
| CN108715801B (en) * | 2018-06-01 | 2021-12-03 | 苏州凯虹高分子科技有限公司 | Cell separation filter element and manufacturing method thereof |
| CN110732246A (en) * | 2019-09-10 | 2020-01-31 | 梧州中科鼎新工业技术研究院(有限合伙) | acid-resistant hollow fiber nanofiltration membrane and preparation method thereof |
| CN111013249B (en) * | 2019-12-26 | 2022-01-28 | 山东国大黄金股份有限公司 | Carbon fiber composite fiber filter screen |
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