JP3886373B2 - Polymer permeable membrane assembly - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polymer permeable membrane assembly, and more particularly to a polymer permeable membrane assembly used for a dehumidifier, a humidifier, a concentrator, a separator, a filter, a fuel cell, and the like.
[0002]
[Prior art]
This type of polymer permeable membrane can be divided into reverse osmosis membranes, ultrafiltration membranes, microfiltration membranes, gas separation membranes, dialysis membranes, etc., depending on their functions. Although it is used for processing, it needs to be modularized when incorporated into the housing. Further, the shape of the osmotic membrane includes a flat membrane shape, a hollow fiber shape, a spiral shape, a laminated shape, a composite membrane shape, and the like, and the form of the module varies depending on the form of the membrane.
[0003]
As a specific example of modularizing the polymer permeable membrane, for example, Japanese Patent Application Laid-Open No. 62-74434 discloses that both ends of a yarn bundle formed by bundling a plurality of hollow fibers for gas separation are thermosetting. A yarn bundle element is formed by embedding and fixing integrally in a resin wall centrifugally molded with an epoxy resin, and this yarn bundle element is incorporated in a housing by the resin wall.
[0004]
In JP-A-1-254209, a plurality of hollow fiber membranes are loaded into a housing made of heat-resistant engineering plastics, and both ends of the hollow fiber membranes are mixed with a polyamide-based curing agent and an epoxy resin. A hollow fiber type module structure is disclosed which is fixed in a flow-tight manner to the housing by a potting material formed as described above. It is stated that this module structure is excellent in heat resistance and chemical resistance and has high strength and can be used in various fields.
[0005]
Further, JP-A-63-224714 discloses that a potting material made of epoxy resin is fixed to an end portion of a yarn bundle made of hollow fibers, and a ceramic is formed on the surface layer surface of the potting material on the side in contact with the seal member. A gas separation device in which powder is blended and a metal elastic member is disposed on the opposite surface is shown. It is stated that this gas separation device can isolate the raw material gas passage chamber and the permeate gas in a dense state even when used under severe conditions of high temperature and high pressure.
[0006]
As described above, in the conventional polymer permeable membrane assembly in which the polymer permeable membrane is modularized, both ends of the polymer permeable membrane are directly embedded and fixed inside the resin wall, that is, the potting material as it is. However, since there is a difference in expansion rate and shrinkage rate between these polymer permeable membranes and potting materials due to the difference in materials, the device is severely subjected to repeated high temperature wet state and low temperature dry state. When used under conditions, the polymer osmotic membrane and the potting material may be repeatedly deformed with different adhesion surfaces, or the potting material may be raised or depressed at the fixed portion to cause deformation or fineness. As a result, there is a problem that the sealing property between the polymer permeable membrane and the potting material tends to be incomplete.
[0007]
[Problems to be solved by the invention]
The technical problem of the present invention is that the polymer permeable membrane and the potting material are securely and firmly fixed so that they do not peel or deform even if there is a difference in properties such as expansion coefficient or contraction ratio. It is an object of the present invention to provide a polymer permeable membrane assembly that is excellent in durability and sealability.
[0008]
[Means for Solving the Problems]
In order to solve the above problems, according to the present invention, a mounting portion whose surface is coated with a metal plating layer is formed on at least one end of a polymer permeable membrane having selective permeability, and the metal plating is formed on the mounting portion. A polymer permeable membrane assembly is provided, wherein a resin potting material is fixed through a layer.
At this time, it is desirable that the polymer permeable membrane is made of an ion exchange resin, and the metal plating layer is provided after an ion cross-linking treatment for substituting the ion exchange groups with metal ions on the surface of the attachment portion. .
[0009]
In the polymer permeable membrane assembly of the present invention having the above configuration, since the potting material is fixed to the end of the polymer permeable membrane via the metal plating layer, the adhesion is enhanced by the metal plating layer and the sealing property is improved. In addition to the improvement, the mechanical strength of the end portion of the polymer permeable membrane is also increased. For this reason, when the polymer permeable membrane assembly is incorporated in the housing of the apparatus and used for various fluid treatments, the polymer permeable membrane swells with water other than the portion where the polymer permeable membrane is fixed to the potting material, or is dried. Even when contracted, in the attachment portion fixed to the potting material of the polymer permeable membrane, swelling and contraction are reliably suppressed by the metal plating layer, and peeling and cracking due to deformation of the potting material are unlikely to occur. Moreover, since heat resistance is also improved by the said metal plating layer, it can also be used in combination with a potting material with high self-reaction heat.
[0010]
That is, according to the present invention, the expansion / contraction coefficient of the polymer permeable membrane is greatly different from that of the potting material, the heat resistant temperature is low, the flexibility is large, or the adhesiveness is poor. In addition, the polymer permeable membrane can be securely and firmly fixed to the potting material by interposing the metal plating layer, and a polymer permeable membrane assembly excellent in durability and sealing performance can be obtained.
[0011]
Further, according to the present invention, the surface of the polymer permeable membrane made of an ion exchange resin and selectively permeable is subjected to ion cross-linking treatment for substituting ion exchange groups with metal ions, and the surface is subjected to etching treatment . Thus, a polymer permeable membrane assembly is provided, in which a mounting portion having a hardened and improved adhesion surface is formed, and a resin potting material is fixed to the mounting portion. Is done.
[0012]
In such a polymer permeable membrane assembly, since the adhesion and mechanical strength at the attachment portion of the polymer permeable membrane are enhanced, this polymer permeable membrane is formed in the same manner as when the metal plating layer is formed. The membrane can be securely and firmly fixed to the potting material, and a polymer permeable membrane assembly excellent in durability and sealing performance can be obtained.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows a fluid treatment apparatus using a polymer permeable membrane assembly of the present invention. This fluid treatment apparatus is constructed by incorporating the polymer permeable membrane assembly 2A in a cylindrical housing 1. It is configured.
[0014]
The housing 1 includes a cylindrical outer cylinder 10 and head caps 11 and 12 attached to both axial ends of the outer cylinder 10 by means such as screwing. One head cap 11 is provided with a first supply port 13 a for supplying a humidifying fluid 14 such as hydrogen gas, and the other head cap 12 takes out the humidified humidifying fluid 14. A first discharge port 13b is provided, and the outer cylinder 10 is provided with a second supply port 15a for supplying a humidifying fluid 16 such as water vapor, and for taking out the humidifying fluid 16. The second discharge port 15b is provided.
[0015]
In the polymer permeable membrane assembly 2A, a plurality of polymer permeable membranes (hollow fiber membranes) 18 each having a hollow fiber shape are bundled in a cylindrical shape, and thermosetting properties such as epoxy resin and urethane resin are provided at both ends of the membrane bundle. A potting material 19 made of resin is fixed in a short columnar shape, and the potting material 19 is closely fitted and held in a cylindrical potting case 20, and the potting case 20 is held at the end of the outer cylinder 10. It is accommodated in the housing 1 by being closely fitted and fixed to the part.
[0016]
The polymer permeable membrane, that is, the hollow fiber membrane 18 may be made of any material as long as it can selectively permeate fluid such as gas, water vapor, or liquid. Polymer materials such as polypropylene, polyacrylonitrile, aromatic polyamide, aromatic polyimide, and fluorine ion exchange resin are used.
[0017]
In fixing the potting material 19 to the end portion of the hollow fiber membrane 18, as can be seen from FIG. 2, by performing metal plating on the end portion of each hollow fiber membrane 18, both the inner and outer surfaces are made of nickel or the like. A mounting portion 18 a covered with the metal plating layer 22 is formed, and the potting material 19 is fixed to the mounting portion 18 a via the metal plating layer 22.
[0018]
The plating method is preferably an electroless plating method, but may be an electrolytic plating method or another plating method. Such metal plating is performed as follows. First, the attachment portion 18a of the hollow fiber membrane 18 is immersed in an aqueous solution containing a metal complex so that the metal complex is adsorbed on the surface of the membrane, and then the adsorbed metal complex is reduced with a reducing agent to reduce the attachment portion 18a. By depositing a metal layer on the inner surface and the outer surface of the substrate, and then washing, drying and high-temperature treatment, the adhesion between the metal plating layer 22 and the hollow fiber membrane 18 is enhanced. When the metal plating layer 22 is further grown, the metal complex adsorption step and the reducing agent precipitation step may be repeated a plurality of times. Moreover, after performing a metal plating process, the adhesiveness of the hollow fiber membrane 18 and the metal plating layer 22 can be remarkably improved, for example, by performing a heat treatment of about 60 to 200 and drying.
[0019]
Further, as a method for fixing the potting material 19 to both ends of the membrane bundle in which the hollow fiber membranes 18 are bundled, for example, the following method is available. That is, the metal bundle-treated mounting portion 18a of the membrane bundle is accommodated in a mold, and the mold is rotated to apply a centrifugal force in the direction of the end of the membrane bundle while liquid thermosetting is performed in the mold. This is a method of fixing the potting material 19 having a short columnar shape to the end of the membrane bundle by injecting resin and heating to a temperature of 60 to 100 ° C. to cure. However, the potting material can also be fixed by immersing the end of the membrane bundle in a liquid thermosetting resin and thermosetting it without applying centrifugal force. Alternatively, it is possible to fix the mounting portion 18a of the hollow fiber membrane 18 with an adhesive to a potting material formed in advance in a required shape with a resin.
[0020]
In the fluid processing apparatus having the above-described configuration, when the humidifying fluid 14 is supplied from the first supply port 13a and the humidifying fluid 16 is supplied from the second supply port 15a, the humidifying fluid 14 is connected to each hollow fiber. One of the humidification fluids 16 flows between the hollow fiber membranes 18 and is discharged from the second discharge port 15b through the membrane 18 and is discharged from the first discharge port 13b. Since a part of the fluid 16 passes through the hollow fiber membrane 18 and is mixed into the humidified fluid 14, the humidified humidified fluid 14 is taken out from the first outlet 13b. The second supply port 15a is provided on the first discharge port 13b side so that the humidifying fluid 14 and the humidifying fluid 16 are in countercurrent contact with each other via the hollow fiber membrane 18, and a second The discharge port 15b is provided on the first supply port 13 side.
[0021]
Here, in the case where the hollow fiber membrane 18 has a low heat-resistant temperature and a property that easily swells, the hollow fiber membrane 18 tends to deform in the radial direction and the longitudinal direction due to swelling, and if the use temperature is high, Softens and tries to further deform in the inner diameter direction. Therefore, if the mounting portion 18a of the hollow fiber membrane 18, that is, the portion embedded and fixed in the potting material 19 is in a deformable state due to swelling or the like, if the heat resistant temperature of the potting material 19 is low, The potting material 19 can no longer suppress the swelling force of the hollow fiber membrane 18 and rises, leading to the occurrence of cracks. Further, when the hollow fiber membrane 18 is changed from a wet state to a dry state, the hollow fiber membrane 18 is contracted and peeled off from the potting material 19 or the potting material 19 is easily depressed.
[0022]
However, in the above embodiment, since the hollow fiber membrane 18 is fixed to the potting material 19 via the metal plating layer 22 provided on the mounting portion 18a, the metal plating layer 22 adheres to the potting material 19. Not only improves the sealing performance but also increases the mechanical strength of the mounting portion 18a. Therefore, when this polymer permeable membrane assembly 2A is incorporated into the housing 1 of the apparatus and used for various fluid treatments, the hollow fiber membrane 18 swells with water other than the portion fixed to the potting material 19, Even if it shrinks due to drying, the metal plating layer 22 reliably suppresses swelling and shrinkage at the portion fixed to the potting material 19, and it is difficult for mutual peeling and cracking due to deformation of the potting material 19 to occur.
[0023]
Further, when the potting material 19 is fixed to the attachment portion 18a of the hollow fiber membrane 18 in the production of the polymer permeable membrane assembly 2A, for example, an epoxy resin is used as the potting material, and the heat resistance temperature of the hollow fiber membrane 18 is increased. In low cases, the epoxy resin has a property of self-heating during curing, and the self-heating temperature tends to increase if the epoxy resin has heat resistance. When the membrane 18 is directly embedded in the epoxy resin, the end of the hollow fiber membrane 18 is thermally decomposed by the self-heating temperature of the epoxy resin and foams, and the epoxy resin is cured in a state where a nest is formed inside. As a result, the sealing property is significantly reduced.
[0024]
However, in the above embodiment, since the metal plating layer 22 is formed at the end of the hollow fiber membrane 18 and the heat resistance of the hollow fiber membrane 18 is enhanced by the metal plating layer 22, the potting material having a high self-reaction heat. Even so, it can be used in combination with it.
[0025]
The hollow fiber membrane 18 (polymer permeable membrane) can also be formed of a fluorine-containing ion exchange resin. In this case, since the fluorine-containing ion exchange membrane has excellent moisture permeability and swelling / shrinkability, the attachment portion 18a of the hollow fiber membrane 18 is subjected to ion cross-linking treatment for the purpose of increasing membrane strength, and then metal plating is performed. It is desirable to apply a treatment to cover the metal plating layer 22. Thus, by replacing the exchange group of the fluorine-containing ion exchange membrane with metal ions, the membrane strength of the attachment portion 18a can be increased and the above-described swelling and shrinkage can be suppressed. In addition, although the adhesiveness with respect to the potting material 19 of the hollow fiber membrane 18 falls by substitution with the said metal ion, the said adhesiveness can be maintained or improved reliably by coat | covering the said metal plating layer 22 on the surface. it can.
[0026]
The metal ion may be of any kind, but the most effective metal ion is potassium ion. In this case, the mounting portion 18a of the hollow fiber membrane 18 is immersed in an aqueous solution of potassium hydroxide to replace the ion exchange groups with potassium ions, washed with water and dried, and then subjected to a metal plating process to obtain nickel or the like. The metal plating layer 22 is formed. And the said potting material adheres to the said attaching part 18a of the bundled hollow fiber.
[0027]
In the above embodiment, the attachment portion 18a of the hollow fiber membrane 18 (polymer permeable membrane) is coated with the metal plating layer 22, but instead of coating such a metal plating layer 22, FIG. As shown in the second embodiment, the mounting portion 18a of the hollow fiber membrane 18 is subjected to the metal ion cross-linking treatment as described above , and the surface thereof is subjected to an etching treatment with a solvent so as to be hardened and adhesive. The polymer treated membrane assembly 2B can be obtained by forming the treated surface 23 having an increased thickness and attaching the resin potting material 19 to the mounting portion 18a.
[0028]
The fluid treatment apparatus incorporating the polymer permeable membrane assemblies 2A and 2B described above can be suitably applied to, for example, a solid polymer fuel cell main body, a solid polymer fuel cell humidifier, and the like. This solid polymer fuel cell uses a proton-conducting solid polymer electrolyte membrane, and this solid polymer electrolyte membrane has physical properties similar to those of the above-described fluorine-containing ion exchange membrane. In order to maintain the nature, it is necessary to replenish moisture from the outside, and it is always wet. Further, since the operating temperature is 100 ° C. or lower, the stability and heat resistance of the seal against the swelling and shrinkage behavior of the electrolyte membrane are required. Therefore, the adhesion and adhesion to the potting material can be improved by applying the surface treatment as described above to the mounting portion 18a.
However, the polymer permeable membrane assembly 2A can be used for other dehumidifiers, humidifiers, concentrators, separators, filters, and the like.
[0029]
In each of the above embodiments, the polymer permeable membrane assemblies 2A and 2B use the hollow fiber-shaped polymer permeable membrane 18, and the potting material 19 is attached to both ends of the bundled hollow fiber membranes 18, and the hollow fiber membrane 18 However, the form of the polymer permeable membrane assembly is not limited to this, and varies depending on the application. For example, the number of the hollow fiber membrane 18 may be one. In some cases, the mounting portion 18a is formed only on one end side of the hollow fiber membrane 18, and the potting material 19 is fixed thereto. Alternatively, for example, when used for gas separation, the potting material 19 on one end side is fixed so that the end of the hollow fiber membrane 18 is open to the outside, and the potting material 19 on the other end side is attached to the hollow fiber membrane 18. It may be fixed so as to close the end.
[0030]
Furthermore, instead of using the hollow fiber polymer permeable membrane as described above, a polymer permeable membrane assembly can be formed using a flat membrane polymer permeable membrane. The polymer permeable membrane assembly 2C of the third embodiment shown in FIG. 4 has an attachment having a metal plating layer 22 or a treated surface 23 obtained by the above-described method at the end of a flat polymer permeable membrane 30. A portion 30a is formed, and the potting material 19 is fixed to the mounting portion 30a. The shape of the polymer permeable membrane 30 in this case can be circular, rectangular, or any other appropriate shape, and the mounting portion 30a and the potting material 19 can be used depending on the application of the polymer permeable membrane assembly 2C. It is provided on the entire periphery of the polymer permeable membrane 30 or partially on only a part of the outer periphery. Further, the polymer permeable membrane 30 may be used in a plurality of layers. In this case, the adjacent polymer permeable membranes 30 and 30 may be arranged in close contact with each other depending on the use. In some cases, they are arranged at regular intervals.
[0031]
A polymer permeable membrane assembly 2D of the fourth embodiment shown in FIG. 5 is formed by laminating a plurality of flat polymer permeable membranes 30 to form a laminated body 33, and at the end of the laminated body 33, A mounting portion 33a having the metal plating layer 22 or the processing surface 23 is formed, and the potting material 19 is fixed to the mounting portion 33a. Also in this case, the mounting portion 33a and the potting material 19 may be provided on the entire circumference of the laminated body 33 or may be provided partially.
[0032]
The polymer permeable membrane assembly 2E of the fifth embodiment shown in FIGS. 6 and 7 is formed by winding a polymer permeable membrane 35 in a spiral shape. The polymer permeable membrane 35 is formed in a flattened shape. As shown in FIG. 8, the polymer permeable membrane 35 is wound in a spiral shape with the opening 36 of the cylinder facing the axial direction, and at least the axial direction A mounting portion 35a having the metal plating layer 22 or the processing surface 23 described above is formed at one end, and the potting material 19 is fixed.
The polymer permeable membrane 35 may be formed of a single membrane material into a cylindrical shape, but as shown in FIG. 8, two rectangular membrane materials 37a and 37b are stacked to face each other. May be formed in a flat cylindrical shape by bonding and integrating each other.
[0033]
【The invention's effect】
As described above, according to the present invention, even if there is a difference in properties such as expansion coefficient and contraction ratio between the polymer permeable membrane and the polymer permeable membrane, they are securely and firmly fixed so as not to cause peeling or deformation. In this way, a polymer permeable membrane assembly having excellent durability and sealing performance can be obtained.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a dehumidifying device using a polymer permeable membrane assembly according to the present invention.
FIG. 2 is an enlarged cross-sectional view of a main part of the polymer permeable membrane assembly.
FIG. 3 is an enlarged cross-sectional view of a main part showing a second embodiment of the polymer permeable membrane assembly.
FIG. 4 is an enlarged cross-sectional view of a main part showing a third embodiment of the polymer permeable membrane assembly.
FIG. 5 is an enlarged cross-sectional view of a main part showing a fourth embodiment of the polymer permeable membrane assembly.
FIG. 6 is an enlarged cross-sectional view of a main part showing a fifth embodiment of the polymer permeable membrane assembly.
7 is a cross-sectional view taken along line AA in FIG.
8 is a developed perspective view of FIG. 7. FIG.
[Explanation of symbols]
2A, 2B, 2C, 2D, 2E Polymer permeable membrane assembly 18, 30, 35 Polymer permeable membrane 18a, 30a, 33a, 35a Mounting portion 19 Potting material 22 Plating layer 23 Treatment surface

Claims (3)

  A mounting portion whose surface is covered with a metal plating layer is formed at the end of the polymer permeable membrane having permselectivity, and a resin potting material is fixed to the mounting portion via the metal plating layer. A polymer permeable membrane assembly characterized by that. The end of the polymer permeable membrane made of ion exchange resin and selectively permeable is subjected to ion cross-linking treatment to replace the ion exchange group with metal ions, and the surface is etched to make it hard and adhere. A polymer permeable membrane assembly comprising: a mounting portion having a treated surface with improved properties; and a resin potting material fixed to the mounting portion. The polymer permeable membrane is made of an ion exchange resin,
2. The polymer permeable membrane assembly according to claim 1, wherein the metal plating layer is provided on the surface of the end portion subjected to ion crosslinking treatment for substituting ion exchange groups with metal ions . 3.

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