JP2009297642A - Hollow fiber membrane for charge into hollow fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hollow fiber membrane for charge into a hollow fiber separating a mixed liquid as a constitution substance by charging the high temperature and high pressure mixed liquid into the hollow of the hollow fiber membrane, fundamentally preventing a channeling phenomenon of a feed liquid occurring when charging the mixed liquid for separation to the outside of the hollow fiber membrane, and enhancing the permeation separation efficiency by increasing a contact ratio of the mixed liquid with the membrane surface per unit volume. <P>SOLUTION: In the hollow fiber membrane for charge into the hollow fiber, the mixed liquid to be separated is charged into the hollow of the hollow fiber membrane to pass through porous membranes containing an activated layer. The tubular activated layer having hollow is formed, polymer fiber braid, metallic wire braid or mixed braid of the polymer fiber braid with the metallic wire is braided directly on the outer surface of the activated layer, to suppress expansion of the activated layer when charging the mixed liquid of high temperature and high pressure. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hollow fiber membrane, and more specifically, a porous membrane (hereinafter simply referred to as “active layer membrane”) containing an active layer by introducing a mixed liquid to be separated into the hollow of the hollow fiber membrane. The present invention relates to a hollow fiber membrane for making a hollow fiber to be permeated.

  In general, when a mixed liquid is separated by a hollow fiber membrane, the separated liquid (hereinafter also referred to as “feed mixed liquid”) is introduced into the outside of the hollow fiber membrane, and pressure is applied to permeate the hollow fiber membrane. To be discharged into the hollow. This is because when a mixed liquid to be separated is introduced into the hollow and pressure is applied, the strength of the membrane is weak and the membrane is broken at 5-10 atmospheres.

  Conventionally, blade reinforced hollow fiber membranes in which an active layer membrane is formed on the outer surface of a braided blade made of polymer fibers or the like have been used. However, there are the following disadvantages in separating the mixed solution by introducing the mixed solution that also separates the blade-reinforced hollow fiber membrane into the hollow.

  In other words, in the case of the active layer membrane applied to the outer surface of the polymer fiber blade, the blade can act as a reinforcing material to some extent against the pressure applied to the outside of the hollow fiber (external pressure). When the pressure is applied by introducing the mixed solution supplied to the inside of the inside, the applied internal pressure works directly on the active layer applied to the outer surface through the gap of the blade, so that the active layer film is easily destroyed. There are disadvantages. In this way, due to the vulnerability of the hollow fiber membrane to the internal pressure, it is possible to throw the supplied mixed liquid into the outside of the hollow fiber membrane and collect the permeated substance from the hollow inside of the hollow fiber membrane. It is a general method of separation.

  However, such a method of collecting the mixed liquid from the externally charged permeate into the hollow interior generates an unnecessary space in the membrane module, and requires a large amount of the supplied mixed liquid. The contact ratio with the film surface is lowered and the required film area is increased. In particular, when the supply mixed liquid flows along the length of the hollow fiber between the hollow fibers inside the hollow fiber membrane bundle, a channeling phenomenon that forms a supply mixed liquid film occurs, and various supply mixed liquids are charged. In this case, the mixing between the supplied mixed liquids is not performed well, and as a result, the separation efficiency is lowered.

  The blades constituting the blade-reinforced hollow fiber membrane are mainly knitted from polymer fibers, but polyester, nylon, aramid, polypropylene, polyethylene, etc. are used, and in the case of hollow fiber membranes used in high-temperature separation membrane processes, glass Fiber may be used as a material for the blade. The thickness of the blade depending on the fiber used when weaving into the shape of a blade using polymer fibers, the thickness of the filaments that make up the yarn (denier), the number of filaments, and the number of yarn streaks used for weaving And the inner diameter is determined. Although an appropriate polymer fiber material is selected according to the intended use, the blade-reinforced hollow fiber membrane is mainly used in a membrane separation process for treating a non-solvent solution mainly at room temperature. Although it shows excellent properties in the tensile strength of the membrane by the blade reinforcement, that is, the load in the longitudinal direction of the membrane, it works on the load acting perpendicular to the surface of the membrane, especially the pressure applied from the inside to the outside of the hollow fiber membrane. This is because it shows poor characteristics. For example, when a supply mixed solution is introduced into a hollow in a reverse osmosis membrane separation process at a pressure of 20 atm or higher in a polymer fiber blade reinforced hollow fiber membrane, the blade is expanded in the radial direction by the pressure, and as a result, the blade The active layer film applied thereon is damaged and causes the film performance to deteriorate. For this reason, when supplying the mixture to be separated into the hollow interior of the hollow fiber membrane at a high temperature and high pressure, it is not easy to braid the blade outside the hollow fiber membrane in order to increase the pressure resistance of the hollow fiber membrane. It is not useful.

  The present invention, which was made to improve the above-mentioned problems of the conventional hollow fiber membranes, is a hollow fiber interior in which a high-temperature, high-pressure mixed liquid is introduced into the hollow interior of the hollow fiber membrane and the mixed liquid can be separated as a constituent substance. The purpose is to provide a hollow fiber membrane for injection.

  Another object of the present invention is to provide a hollow fiber membrane for introduction into a hollow fiber that can fundamentally prevent the channeling phenomenon of the supply liquid that may occur when the mixed liquid is introduced outside the hollow fiber membrane and separated. There is to offer.

  Still another object of the present invention is to provide a hollow fiber membrane for introduction into a hollow fiber, which can enhance the permeation separation efficiency by increasing the contact rate with the membrane surface per unit volume of the mixed solution.

  In order to solve the above problems, according to an aspect of the present invention, a hollow active layer film having a hollow shape is formed, and a polymer fiber and a metal wire are directly mixed on the outer surface of the active layer film. Provided is a hollow fiber membrane for hollow fiber insertion, in which a braid is braided to suppress expansion of the active layer membrane when a high-temperature, high-pressure mixed liquid is introduced into the hollow inside of the active layer membrane. .

  The active layer film may be a composite film having a porous layer located outside and an active layer located inside and denser than the porous layer.

  The polymer fiber used for blade knitting is preferably one or more fibers selected from polyester, nylon, aramid, polypropylene, and polyethylene.

  The metal wire used for braiding the blade is preferably one or more metal wires selected from copper wire, nickel wire, stainless steel wire, tin wire and nichrome wire.

  In order to maintain tightness between the tubular active layer membrane and the blade, the outer diameter of the hollow fiber membrane of the active layer before the knitting is the inner diameter of the blade knitted without the hollow fiber membrane of the active layer It is preferable to have a diameter of 1.1 to 3.0 times.

  The polymer fiber is preferably a yarn obtained by focusing 10 to 400 fiber filaments having a thickness of 100 to 500 denier into a single muscle.

  The metal wire is preferably a single metal wire having a diameter of 0.05 to 0.40 mm, or an aggregate metal wire in which 2 to 5 thin metal wires are combined into a single line.

  The polymer fiber or the metal wire used for knitting the blade preferably has 10 to 80 total bars.

  The blade is formed by knitting polymer fibers, metal wires, or both polymer fibers and metal wires to the outside while supplying the tubular active layer film formed in advance to a knitting machine to the core. preferable.

  The metal wire is preferably combined with the polymer fiber in advance to form a single line before knitting, or a single line is formed only with the metal wire.

  It is preferable that the thickness of the metal wire that forms a single line only with the metal wire is thicker than the thickness of the metal wire combined with the polymer fiber.

  In the mixed blade of the polymer fiber and the metal wire, the number of streaks of the metal wire or the number of streaks of the metal wire combined with the polymer fiber is 5 to 30% of the total number of knitting yarn streaks. Is preferred.

  Each metal wire in the blade is preferably knitted while maintaining an equal interval with the adjacent metal wire.

  The active layer membrane is preferably a nano-permeable membrane, a reverse osmosis membrane, a vapor permeable membrane, a permeable evaporation membrane or a gas permeable membrane.

  According to the present invention having the above-described configuration, a high-temperature, high-pressure supply mixture can be introduced into the hollow interior of the hollow fiber membrane to separate the mixture as a constituent material, and the supply mixture can be contained inside the hollow fiber membrane. As a result, the unnecessary space in the membrane module is minimized, and as a result, the contact ratio with the membrane surface per unit volume of the supply liquid mixture becomes high, the area of the required membrane is reduced, and the supply liquid is external to the hollow fiber membrane. In addition to fundamentally eliminating the channeling phenomenon that occurs when charging, the external blade layer acts as a spacer for the permeate flow, minimizing the pressure drop phenomenon, thus reducing the length of the module. There is an effect that heat loss to the outside can be minimized by flowing the supply mixed solution into the hollow fiber.

  Exemplary embodiments of the present invention will be described below in detail with reference to the accompanying drawings. In addition, in this specification and drawing, about the component which has the substantially same function structure, duplication description is abbreviate | omitted by attaching | subjecting the same code | symbol.

  A hollow fiber membrane for hollow fiber insertion according to the present invention is formed by forming a tubular active layer membrane having a hollow, directly on the outer surface thereof, a polymer fiber blade, a metal wire blade or a mixture of polymer fiber and metal wire. This is characterized by the fact that the active layer film is prevented from expanding when the blade is knitted and a high-temperature, high-pressure mixed liquid is introduced into the hollow interior. That is, the hollow fiber membrane for hollow fiber insertion according to the present invention is formed by braiding a polymer fiber directly on the outer surface of a tubular active layer membrane having a hollow, and braiding a metal wire. Or a blade formed by braiding polymer fibers and metal wires together.

  Due to the inherent pressure resistance limitation of the hollow fiber membrane made of a polymer material, it is sufficient to withstand the pressure of the supply mixture in order to separate it after the high-pressure supply mixture is introduced into the hollow fiber membrane. The mechanical strength of the hollow fiber membrane must be ensured. In order to ensure mechanical strength with the blade in the hollow fiber membrane in which the mixture is introduced into the hollow interior, the blade must be located outside the active layer membrane. For this purpose, the present invention forms a tubular active layer film and braids the blade directly on the outside thereof. In this case, the blade having excellent mechanical properties can be supported over the entire surface by using the pressure applied to the inside of the hollow fiber membrane as a reinforcing material. At this time, an active layer denser than the external porous layer may be formed in the form of a composite film inside the active layer film. When the outer layer of the active layer film is formed from a porous material and an active layer that is denser (for example, having a lower porosity) is formed inside the active layer film, even if a high-pressure supply mixture is injected, the supply mixture It will have sufficient mechanical strength to withstand this pressure.

  The allowable pressure and allowable temperature are determined according to the blade material, but blades knitted from molecular fibers are vulnerable to pressure, high temperature and contact with organic solvents. In this case, it is necessary to supplement the physical properties of the blade. is there. Not only the mechanical properties of metal materials are much better than polymer fibers, but also heat resistance and lack of compatibility with organic solvents when contacted with organic solvents (low wettability), so dimensional stability Also excellent. For this reason, at the time of blade knitting according to the present invention, the polymer fiber and the metal wire can be mixed and knitted, or the metal fiber can be knitted only.

  When braided with metal wires alone, the mechanical properties and dimensional stability of the blade are excellent, but the blade itself is stiff, especially in the high pressure process, the active layer film located inside is damaged by the rough blade surface In addition, the handling at the time of manufacturing the module is deteriorated. For this reason, in hollow fiber membranes used under conditions of high temperature and high pressure, it is possible to replace a part of the polymer fiber as the blade constituent element with a metal wire, that is, to mix the polymer fiber and the metal wire. preferable. In this case, not only the fluidity of the blade can be increased, but also the stability of the manufactured blade against pressure, temperature and organic solvent contact is mainly determined by the metal wire as the reinforcing material. As a result, blades made by mixing metal wires and polymer fibers are extremely stable under conditions of high temperature, high pressure, or contact with organic solvents, and the film reinforced by such blades is also stable. I have to be. The mechanical properties and dimensional stability of the blades become better as the proportion of metal wires increases during the manufacture of blades made of metal wires and polymer fibers, but the blades themselves are stiff and the Handling becomes worse. Conversely, when the proportion of the metal wire is reduced, the fluidity of the blade is increased and the handleability is good, but the mechanical properties and dimensional stability are weakened. Therefore, in the mixed blade of the polymer fiber and the metal wire, the number of the metal wire or the number of the metal wire combined with the polymer fiber is 5 to 30% of the total number of the knitting yarns. preferable. Moreover, it is preferable that each metal wire in the blade is knitted while maintaining an equal interval with an adjacent metal wire. Various metal materials such as copper, nickel, stainless steel, tin, and nichrome can be used for the metal wire used here, and the thickness of each metal wire is 0.05 depending on the size of the hollow fiber membrane to be manufactured. Use a diameter of ˜0.4 mm.

  The polymer fiber used for knitting the blade is a fiber such as polyester, nylon, aramid, polypropylene, or polyethylene, and a yarn-like polymer fiber can be used. A yarn is a collection of a plurality of filaments having a constant thickness in a single line, and the filament has a thickness of 100 to 500 denier and the number of filaments is 10 to 400.

  The thickness of each of the polymer fiber and the metal wire is determined according to the thickness and diameter of the blade to be manufactured, and the thickness of the metal wire and the polymer fiber used to manufacture a blade having a uniform appearance. Choose the same thing as much as possible.

  The polymer fiber or metal wire used for knitting the blade preferably has 10 to 80 bars in total.

  Examples of the active layer membrane include a nano-permeable membrane, a reverse osmotic pressure membrane, a vapor permeable membrane, a permeable evaporation membrane, and a gas permeable membrane. Hereinafter, more specific description will be given with reference to the drawings.

  1A is a partially cut perspective view of the blade-reinforced hollow fiber membrane according to the first embodiment of the present invention, FIG. 1B is a cross-sectional view of the blade-reinforced hollow fiber membrane shown in FIG. 1A, and FIG. 1C is FIG. FIG. 2A is a partially cut perspective view of the blade-reinforced hollow fiber membrane according to the second embodiment of the present invention, and FIG. 2B is FIG. 2A. 2C is a cross-sectional view of the blade-reinforced hollow fiber membrane shown in FIG. 2, FIG. 2C is a layout diagram of the metal wire bobbin and polymer fiber bobbin during blade braiding shown in FIG. 2A, and FIG. FIG. 3B is a cross-sectional view of the blade-reinforced hollow fiber membrane shown in FIG. 3A, and FIG. 3C is a perspective view of the metal wire bobbin and the height at the time of blade braiding shown in FIG. 3A. It shows a layout diagram of the fiber bobbins, respectively.

  In the first embodiment shown in FIGS. 1A and 1B, the blade is directly knitted with only polymer fibers outside the active layer film 1, and the second embodiment shown in FIGS. 2A and 2B is When the braid is directly knitted by mixing two bars of the metal wire 3 and 34 bars of the polymer fiber 5 outside the active layer film 1, the third embodiment shown in FIGS. The case where the braid is directly knitted by mixing 4 bars of the metal wire 3 and 32 bars of the polymer fiber 5 outside the layer film 1 is shown.

  Referring to FIG. 1C, FIG. 2C, or FIG. 3C, the blade feeds the core active layer film 1 formed in advance in the knitting machine to the core while the polymer fiber 5, the metal wire 3 or the polymer fiber are provided outside thereof. 5 and the metal wire 3 are knitted and formed.

  After the polymer fiber 5 or the metal wire 3 is wound around the bobbins 7 and 9, it is provided on the annular carrier 11 of the knitting machine. At this time, the number of bobbins to be attached is the same as the number of streaks used in the knitting described above. 10 to 80.

  When using a metal wire for knitting, as shown in FIGS. 2A and 3A, only the metal wire can be wound around a bobbin and used for knitting, but before knitting, the metal wire is combined with polymer fibers for knitting. It can also be used. However, when only the metal wire is wound around the bobbin, a metal wire having a thickness larger than that of the wire wound with the polymer fiber must be used. 2A and 3A exemplify the case where a single metal wire is used as the metal wire, but if necessary, an aggregate metal wire obtained by combining these 2 to 5 thin metal wires may be used. It may be used.

  When the braid is knitted by mixing polymer fibers and metal wires as in the second and third embodiments, as described above, the number of metal wire bars is 5 to 30% of the total number of bars. In order to achieve this, 5 to 30% of the number of metal wire bobbins 7 or the number of metal wire bobbins 7 combined with polymer fibers is attached to the carrier 11 of the knitting machine with respect to the total number of bobbins attached. . At this time, when the metal wire bobbins 7 are attached to the carrier 11 in order to make the interval between the metal wires uniform, they must be arranged symmetrically with respect to the circular center of the carrier 11 according to the number. If the metal bobbins are arranged out of symmetry, the surface of the braided blade is neither smooth nor uniform.

  When the tubular active layer film 1 is supplied into the center of the annular carrier 11 and a certain number of knitting yarn bobbins 7 and 9 are rotated along the annular carrier 11, the outside of the active layer film 1 to which the blade is supplied is provided. Knitted to. At this time, in order to maintain the tightness between the active layer membrane 1 and the blade, the outer diameter of the hollow fiber membrane 1 of the active layer before knitting is 1. It preferably has a diameter of 1 to 3.0 times. This is because the outer diameter of the active layer film 1 must be larger than the inner diameter of the blade knitted without the active layer in order to maintain tightness between the active layer film 1 and the blade knitted outside thereof. This is because it must be done.

  In the following, examples according to the present invention will be described more specifically, and the properties will be compared with those of a conventional polymer fiber blade reinforced hollow fiber membrane.

<Example 1>
Polysulfone (500 g) and polyvinylpyrrolidone (PVP) (130 g) were dissolved in dimethylacetamide (1370 g) to produce a uniform solution, which was irradiated to water as a coagulating liquid at 35 ° C. to completely remove residual solvent and additive PVP. Thereafter, a tubular porous membrane having an inner diameter of 1.1 mm and an outer diameter of 1.9 mm was manufactured. A 2 μm-thick polyvinyl alcohol layer was applied to the inner surface of the produced porous membrane to form a tubular active layer membrane. In this way, the active layer film is formed with a porous layer outside, and an active layer denser than the outside is formed inside. A braid was produced by knitting 36 300/150 polyester yarns outside the active layer membrane to produce a hollow fiber membrane for introduction into a hollow fiber having an outer diameter of 2.9 mm.

<Example 2>
Polysulfone (500 g) and polyvinylpyrrolidone (PVP) (130 g) were dissolved in dimethylacetamide (1370 g) to produce a uniform solution, which was irradiated to water as a coagulating liquid at 35 ° C. to completely remove residual solvent and additive PVP. Thereafter, a porous membrane having an inner diameter of 1.1 mm and an outer diameter of 1.9 mm was manufactured. A 2 μm-thick polyvinyl alcohol layer was applied to the inner surface of the produced porous membrane to form a tubular active layer membrane. In this way, the active layer film is formed with a porous layer outside, and an active layer denser than the outside is formed inside. A hollow fiber membrane for insertion into a hollow fiber having an outer diameter of 2.9 mm was manufactured by knitting a blade with 34 300/150 polyester yarns and two 0.2 mm diameter stainless steel wires outside the active layer membrane. .

<Example 3>
Polysulfone (500 g) and polyvinylpyrrolidone (PVP) (130 g) were dissolved in dimethylacetamide (1370 g) to produce a uniform solution, which was irradiated to water as a coagulating liquid at 35 ° C. to completely remove residual solvent and additive PVP. Thereafter, a porous membrane having an inner diameter of 1.1 mm and an outer diameter of 1.9 mm was manufactured. A 2 μm-thick polyvinyl alcohol layer was applied to the inner surface of the manufactured hollow fiber membrane to form a tubular active layer membrane. In this way, the active layer film is formed with a porous layer outside, and an active layer denser than the outside is formed inside. A hollow fiber membrane for introduction into a hollow fiber having an outer diameter of 2.9 mm was manufactured by braiding a blade with 32 300/150 polyester yarns and 4 stainless steel wires with a diameter of 0.2 mm outside the active layer membrane. .

<Comparative Example 1>
The blade was knitted with 36 300/150 polyester yarns, but the outer diameter was 2 mm and the inner diameter was 1 mm. A conventional blade-reinforced hollow fiber having a porous membrane prepared by dissolving 500 g of polysulfone and 130 g of polyvinyl pyrrolidone in 1370 g of dimethylacetamide, producing a uniform solution, uniformly coating the outer surface of the blade, and coagulating it in water. A membrane was produced. It applied so that the thickness of polyvinyl alcohol might be set to 2 micrometers on the porous membrane surface.

<Comparative Example 2>
The blade was knitted with 34 300/150 polyester yarns and two 0.2 mm diameter stainless steel wires, but the outer diameter was 2.0 mm and the inner diameter was 1.0 mm. A homogeneous solution is prepared by dissolving 500 g of polysulfone and 130 g of polyvinyl pyrrolidone in 1370 g of dimethylacetamide, and this is uniformly coated on the outer surface of the blade, and then coagulated in water to form a blade-reinforced hollow fiber membrane having a porous membrane. Manufactured. It applied so that the thickness of polyvinyl alcohol might be set to 2 micrometers on the porous membrane surface.

<Comparative Example 3>
The blade was knitted with 32 300/150 polyester yarns and 4 0.2 mm diameter stainless steel wires, but the outer diameter was 2.0 mm and the inner diameter was 1.0 mm. A homogeneous solution is prepared by dissolving 500 g of polysulfone and 130 g of polyvinyl pyrrolidone in 1370 g of dimethylacetamide, and this is uniformly coated on the outer surface of the blade, and then coagulated in water to form a blade-reinforced hollow fiber membrane having a porous membrane. Manufactured. It applied so that the thickness of polyvinyl alcohol might be set to 2 micrometers on the porous membrane surface.

In order to manufacture the hollow fiber membranes manufactured in the above examples and comparative examples in the form of a module, a C-PVC pipe having a length of 1 meter and an inner diameter of 1 inch is packed with 130 strands of hollow fiber membrane bundles, respectively. Was ported with epoxy resin. In a pressure test for a hollow fiber membrane manufactured under each condition, air at 2, 10, 20, and 40 atmospheres was added to the inside of the hollow fiber membrane, and the stability of the membrane was observed. A pervaporation experiment was conducted on the hollow fiber membranes produced under each condition, and the mixed feed solution used was composed of 95% by mass of ethanol and 5% by mass of water. The mixed supply liquid is inside the hollow fiber membrane for the hollow fiber membrane modules of Examples 1, 2, and 3, and the outside of the hollow fiber membrane for the hollow fiber membrane modules of Comparative Examples 1, 2, and 3. At the same time, a permeation separation experiment was performed by applying a vacuum of 5 torr to the opposite side. The temperature of the used mixed feed liquid was 60 ° C., and the initial flow rate of the supplied mixed liquid was 100 cm ³ / min. Under each operating condition, the permeation rate through the membrane, the permeate water content, the temperature of the feed mixture at the inlet and outlet of the module were measured.

  Table 1 shows the pressure test results of Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3. All hollow fiber membranes (Comparative Examples 1, 2, and 3) coated with an active layer membrane on the outside of the blade are shown. 3), it is observed that the lower coating layer is destroyed at a pressure of 10 atm or higher, whereas the hollow fiber membrane knitted with a blade outside the active layer membrane according to the present invention exhibits stability even at 40 atm. ing. However, in the hollow fiber membrane for feeding into the hollow fiber according to the present invention, in the case of the blade knitted only with the polymer fiber (Example 1), the hollow fiber membrane is caused by the pressure applied to the inside of the hollow fiber membrane over time. The blade expands in the radial direction and the thickness of the active layer of the hollow fiber membrane gradually decreases, and the empty fiber membrane is not destroyed, but leakage of solute through the active layer occurs. However, when the blade is knitted by mixing metal wires and polymer fibers (Examples 2 and 3), the hollow fiber membrane shows excellent stability against pressure.

  From the above results, it can be seen that when the blade is knitted outside the hollow fiber membrane, the hollow fiber membrane shows excellent pressure resistance against charging into the hollow inside of the mixture, and the metal wire is mixed with the polymer fiber. When the blade is knitted, it can be seen that the blade reinforcing effect appears more remarkably.

  Table 2 shows the separation performance of the pervaporation membrane with respect to the hollow fiber membrane for introduction into the hollow fiber according to the present invention, together with a comparative example. In the case of a hollow fiber membrane (Examples 1, 2, and 3) in which a blade is knitted outside the hollow fiber membrane according to the present invention, the supply mixed solution can be poured into the hollow fiber membrane. In the case of hollow fiber membranes applied to the outside (Comparative Examples 1, 2, and 3), the supply mixture must flow outside the hollow fiber membranes due to weak pressure resistance. The generated channeling phenomenon of the supply liquid not only lowers the permeation speed but also causes a phenomenon of separation efficiency. In the case of a hollow fiber membrane in which the blade is knitted outside the hollow fiber membrane according to the present invention, such a channeling phenomenon of the supply liquid does not occur, and the membrane contact rate of the supply liquid per unit volume is larger. It can be confirmed that the permeation rate is faster and the separation efficiency is more excellent. It can be seen that the hollow fiber membrane for introducing into the hollow fiber according to the present invention has a much smaller temperature difference between the supply liquid at the module inlet and the module outlet than the hollow fiber membrane of the comparative example and less heat loss of the supply liquid in the module. .

  In the above comparison, it has been proved that the hollow fiber membrane for introducing into the hollow fiber according to the present invention not only has excellent membrane stability at high temperature and high pressure, but also has excellent membrane permeation separation performance. Yes.

  The hollow fiber membrane for internal insertion of the hollow fiber according to the present invention is a membrane separation process under high temperature or high pressure due to the pressure resistance of the hollow fiber membrane which is improved by support by a blade having high mechanical strength, that is, nano, reverse osmotic pressure, gas It is extremely suitable for membrane separation processes such as separation, pervaporation, and vapor permeation, and high permeation separation efficiency can be obtained.

  As mentioned above, although preferred embodiment of this invention was described referring an accompanying drawing, it cannot be overemphasized that this invention is not limited to this example. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the claims, and these are naturally within the technical scope of the present invention. Understood.

1 is a partially cut perspective view of a blade-reinforced hollow fiber membrane according to a first embodiment of the present invention. 1B is a cross-sectional view of the blade-reinforced hollow fiber membrane shown in FIG. 1A. FIG. 1B is a layout diagram of a metal wire bobbin and a polymer fiber bobbin during blade braiding shown in FIG. 1A. FIG. It is a partial cutaway perspective view with respect to 2nd Embodiment of the braid | blade reinforcement | strengthening hollow fiber membrane by this invention. It is sectional drawing of the braid | blade reinforcement | strengthening hollow fiber membrane shown to FIG. 2A. FIG. 2B is a layout diagram of the metal wire bobbin and the polymer fiber bobbin during blade braiding shown in FIG. 2A. It is a partial cutaway perspective view with respect to 3rd Embodiment of the braid | blade reinforcement | strengthening hollow fiber membrane by this invention. It is sectional drawing of the braid | blade reinforcement | strengthening hollow fiber membrane shown to FIG. 3A. FIG. 3B is a layout diagram of a metal wire bobbin and a polymer fiber bobbin during blade braiding shown in FIG. 3A.

Explanation of symbols

1: active layer film,
3: Metal wire,
5: polymer fiber,
7: Metal wire bobbin,
9: polymer fiber bobbin,
11: Bobbin carrier

Claims (14)

  Forming a tubular active layer membrane having a hollow, knitting a mixed blade of polymer fiber and metal wire directly on the outer surface of the active layer membrane, and high temperature inside the hollow of the active layer membrane, A hollow fiber membrane for hollow fiber insertion, wherein the active layer membrane is prevented from expanding when a high-pressure mixed liquid is introduced.   2. The composite film according to claim 1, wherein the active layer film is a composite film having a porous layer located outside and an active layer located inside and denser than the porous layer. Hollow fiber membrane for hollow fiber inside loading.   2. The hollow fiber internal injection according to claim 1, wherein the polymer fiber used for blade knitting is one or more fibers selected from polyester, nylon, aramid, polypropylene and polyethylene. Hollow fiber membrane.   The metal wire used in the blade knitting is one or more metal wires selected from copper wire, nickel wire, stainless steel wire, tin wire and nichrome wire. A hollow fiber membrane for filling the hollow fiber as described.   In order to maintain tightness between the tubular active layer membrane and the blade, the outer diameter of the hollow fiber membrane of the active layer before the knitting is the inner diameter of the blade knitted without the hollow fiber membrane of the active layer The hollow fiber membrane for introducing into hollow fibers according to claim 1, wherein the hollow fiber membrane has a diameter 1.1 to 3.0 times greater than that of the hollow fiber.   2. The hollow fiber internal feed according to claim 1, wherein the polymer fiber is a yarn obtained by converging 10 to 400 fiber filaments having a thickness of 100 to 500 denier into a single muscle. Hollow fiber membrane.   The metal wire is a single metal wire having a diameter of 0.05 to 0.40 mm, or an aggregate metal wire in which 2 to 5 thin metal wires are combined into a single line. The hollow fiber membrane for hollow fiber insertion according to claim 1.   The hollow fiber membrane for hollow fiber insertion according to claim 1, wherein the polymer fiber or the metal wire used for knitting the blade has 10 to 80 total bars. .   The blade is formed by knitting polymer fibers, metal wires, or both polymer fibers and metal wires to the outside while supplying the tubular active layer film formed in advance to a knitting machine to the core. The hollow fiber membrane for hollow fiber insertion according to claim 1, characterized in that   2. The hollow fiber according to claim 1, wherein the metal wire is combined with the polymer fiber in advance to form a single line before knitting, or a single line is formed with only the metal wire. Hollow fiber membrane for internal loading.   The thickness of the metal wire that forms a single line only with a metal wire is thicker than the thickness of the metal wire that is combined with the polymer fiber. Hollow fiber membrane.   In the mixed blade of the polymer fiber and the metal wire, the number of streaks of the metal wire or the number of streaks of the metal wire combined with the polymer fiber is 5 to 30% of the total number of knitting yarn streaks. The hollow fiber membrane for hollow fiber internal injection according to claim 1 or 11, characterized in that:   13. The hollow fiber membrane for introducing into hollow fibers according to claim 12, wherein each metal wire in the blade is knitted while maintaining equal intervals with adjacent metal wires. The hollow fiber membrane for hollow fiber insertion according to claim 1, wherein the active layer membrane is a nano-permeable membrane, a reverse osmosis membrane, a vapor permeable membrane, a permeable evaporation membrane or a gas permeable membrane.

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