JP2013099703A - Header member, membrane module and method for producing membrane module - Google Patents

Abstract

An object of the present invention is to provide a header member, a membrane module, and a method for manufacturing the membrane module that contribute to improving the quality of the membrane module by suppressing the growth of peeling between the sealing material filled in the inside. .
A bottomed tubular header member 9 is attached to an end of a hollow fiber membrane bundle 7 and fixed to the hollow fiber membrane bundle 7 by filling and solidifying a sealing material S therein. An inlet-side cylinder portion 21 provided on the inlet side into which the hollow fiber membrane bundle 7 is inserted, and a bottom-side cylinder having an inner diameter smaller than that of the inlet-side cylinder portion 21 and provided on the bottom side of the inlet-side cylinder portion 21 A step St is formed between the inner surface of the inlet-side tube portion 21 and the inner surface of the bottom-side tube portion 23, and at least one inner surface of the inlet-side tube portion 21 and the bottom-side tube portion 23. Are formed with annular grooves 21 a, 23 a, 23 b along the axis L of the header member 9.
[Selection] Figure 1

Description

  The present invention relates to a header member, a membrane module, and a method for manufacturing a membrane module for manufacturing a membrane module having a hollow fiber membrane bundle.

  A hollow fiber membrane is known as a membrane used in a membrane filtration method using a microfiltration membrane or an ultrafiltration membrane. Membrane modules using hollow fiber membranes are widely used for various membrane separation applications because they have a large membrane area and can be downsized. The hollow fiber membrane module generally includes a hollow fiber membrane bundle composed of a plurality of hollow fiber membranes, and a sealing and fixing portion in which both ends of the hollow fiber membrane bundle are bonded and sealed in a state where both ends of the hollow fiber membrane bundle are open. And a casing that accommodates the hollow fiber membrane bundle sealed by the sealing and fixing portion. On the other hand, a cartridge-type membrane module that is detachably inserted into a case called a housing without a casing is also known (see Patent Document 1). The structure of the cartridge type membrane module is basically the same as the structure of the normal membrane module fixed in the casing, but a protective member called a protective net or a protective cylinder is attached so as to surround the hollow fiber membrane bundle. And is housed in the housing.

  When manufacturing a cartridge type membrane module, for example, it is attached so that the end of the hollow fiber membrane bundle is covered with a bottomed cylindrical header member, and a sealing material is put inside the header member using a centrifugal bonding method. Fill and solidify. Next, when the hollow fiber membrane bundle is fixed to the header member through the sealing material, a part of the bottom side of the header member is cut together with the end of the hollow fiber membrane bundle, and as a result, the hollow fiber membrane bundle is cut. The module end face is formed with an opening communicating with the inside of the module. Manufacturing the membrane module using the header member increases the dimensional stability of the membrane module as a finished product.

Special table 2007-503298 gazette

  However, in the conventional header member, when peeling occurs between the inner surface in contact with the sealing material and the sealing material, the peeling is likely to grow, and as a result, the quality of the membrane module may be deteriorated. there were.

  The present invention has been made in view of such problems, and a header member and a membrane that contribute to improving the quality of a membrane module by suppressing the occurrence or growth of peeling between the sealing material filled inside and the membrane. An object of the present invention is to provide a module and a method for manufacturing a membrane module.

  The present invention relates to a bottomed tubular header member that is attached to an end of a hollow fiber membrane bundle and is fixed to the hollow fiber membrane bundle by filling and solidifying a sealing material therein. An inlet-side cylinder portion provided on the inlet side into which the inlet is inserted, and a bottom-side cylinder portion having an inner diameter smaller than that of the inlet-side cylinder portion and provided on the bottom side of the inlet-side cylinder portion. A step is formed between the inner surface of the tube portion and the inner surface of the bottom tube portion, and at least one inner surface of the inlet tube portion and the bottom tube portion has an annular groove along the axis of the header member. Is formed.

  According to the present invention, even if peeling occurs on the inlet side of the header member, a step is formed between the inner surface of the inlet side cylinder portion and the inner surface of the bottom side cylinder portion. Propagation of delamination from the portion side to the bottom tube portion is prevented, and therefore, delamination growth is suppressed. Further, since the sealing material filled in the header member enters the annular groove and is solidified, the contact surfaces of the header member and the sealing material are fitted in a concave-convex shape and firmly bonded. It is effective for suppressing the occurrence or growth of peeling. As a result, the quality of the membrane module can be improved.

  Further, it is preferable that the groove includes a shallow groove formed in the inlet side cylinder part and a deep groove formed in the bottom side cylinder part and deeper than the shallow groove. When filling the inside of the header member with the sealing material, for example, an inlet for the sealing material is formed on the bottom side of the header member, and the sealing material is filled through the inlet. The deeper the groove formed on the inner surface of the header member, the stronger the bond between the sealing material and the header member, which is advantageous in that it prevents peeling. However, in the method of filling the sealing material from the bottom side of the header member, the inlet side cylindrical portion is less likely to enter the sealing material than the bottom side cylindrical portion, so if the groove of the inlet side cylindrical portion is made too deep, There is a possibility that a gap is generated between the sealing material and the header member without the sealing material entering. On the other hand, since the sealing material easily enters the bottom side cylinder portion as compared with the inlet side cylinder portion, the sealing material can be sufficiently introduced even if the depth of the groove is positively increased. In other words, according to the above configuration, when the sealing material is filled from the bottom side of the header member, a strong coupling between the header member and the sealing material is realized while ensuring the filling of the sealing material. This is effective for suppressing the growth of peeling.

  Further, it is preferable that an annular convex portion along the axis of the header member is formed on the inner surface of the bottom cylindrical portion of the present invention. The sealing material filled in the header member fills the gap formed between the hollow fiber membrane bundle and the header member, and covers the convex portion formed on the inner surface of the bottom side tubular portion. The sealing material filled in the header member heat shrinks in the process of solidification, but in this case, the sealing material that solidifies the convex portion sandwiches the convex portion so that the sealing material solidifies. Delamination in the process is prevented. As a result, it is effective in suppressing the growth of peeling and improving the quality of the membrane module.

  The membrane module according to the present invention includes a cylindrical header portion formed using the header member, a hollow fiber membrane bundle composed of a plurality of hollow fiber membranes inserted into the header portion, and a hollow fiber membrane bundle. And a module end face in which the inside of the hollow fiber membrane is opened.

  According to the present invention, even if separation occurs on the inlet side of the header portion, a step is formed between the inner surface of the inlet side cylindrical portion and the inner surface of the bottom side cylindrical portion. Propagation of peeling from the part to the bottom cylinder part is prevented. Furthermore, since the contact surfaces of the header portion and the sealing material are fitted in a concavo-convex shape and firmly bonded, it is possible to contribute to improving the quality of the membrane module.

  Further, the membrane module further includes a cylindrical protective member that surrounds the hollow fiber membrane bundle in an annular shape and is fixed to the header portion together with the hollow fiber membrane bundle by a sealing portion. The protective member includes a plurality of protective members. It is preferable that a through-hole and a linear protrusion protruding in the axial direction of the protection member from the end fixed to the header portion are provided. The hollow fiber membrane bundle is well held by the protective member and protected from external impacts. Moreover, the linear protrusion part is provided in the edge part of the protection member so that it may protrude in the axial direction of a protection member. For example, when the end portion of the protective member is formed by a flat circumference without a protruding portion, if peeling occurs at the end portion, the peeling easily propagates in the circumferential direction, and the peeling easily grows. However, according to the above configuration, since the protrusion formed at the end of the protective member becomes an obstacle and the propagation of peeling in the circumferential direction is prevented, it is effective in suppressing the growth of peeling.

  Further, it is preferable that the protective member has a net-like shape and has a plurality of meshes that form through holes, and the projecting portion is formed so as to protrude from each of the plurality of meshes that are annularly connected at the end of the protective member. is there. By providing a plurality of protrusions corresponding to each of the plurality of meshes, the protrusions are arranged at substantially equal intervals in the circumferential direction, and the propagation of peeling in the circumferential direction can be effectively suppressed.

  Further, the present invention provides a method of manufacturing a membrane module using the header member described above, a step of bundling a plurality of hollow fiber membranes to form a hollow fiber membrane bundle, and the header member at the end of the hollow fiber membrane bundle. A step of mounting and filling a sealing material in a molten state inside the header member, a step of forming a sealing portion by solidifying the sealing material filled inside the header member, and forming the sealing portion A step of cutting a part of the bottom side of the header member and a part of the sealing part together with an end part of the hollow fiber membrane to form a module end face in which a plurality of hollow fiber membranes are opened; It is characterized by including.

  According to the present invention, in the process of forming the sealing portion, even if peeling occurs on the inlet side of the header member, a step is formed between the inner surface of the inlet side cylindrical portion and the inner surface of the bottom cylindrical portion. Therefore, this step prevents propagation of separation from the inlet side cylinder part side to the bottom side cylinder part, and further, the sealing material filled in the header member enters the annular groove and is solidified. Therefore, since the contact surfaces of the header member and the sealing material are fitted in a concavo-convex shape and firmly bonded, a high quality membrane module can be manufactured.

  ADVANTAGE OF THE INVENTION According to this invention, generation | occurrence | production or growth of peeling between the sealing materials with which it was filled can be suppressed, and the quality of a membrane module can be improved.

It is a disassembled perspective view of the membrane module precursor used for manufacture of the cartridge module which concerns on embodiment of this invention. It is a figure which shows the header member which concerns on this embodiment, (a) is a bottom view, (b) is sectional drawing along the bb line of (a). It is a figure which shows a cylindrical protective member, (a) is a side view, (b) is a fragmentary sectional view along the bb line of (a). It is a figure which shows a module precursor, (a) is a side view, (b) is sectional drawing along the bb line of (a), (c) is along the cc line of (a). FIG. 6 is a sectional view showing a module end face. It is sectional drawing which expands and shows the inlet side of a header member in the state in which the hollow fiber membrane bundle was inserted. It is an expanded sectional view which shows the state in the middle of being filled with the adhesive material inside the header member. It is a disassembled perspective view for demonstrating the aspect which attaches a cartridge module to a housing. It is a flowchart which shows the procedure which manufactures a cartridge module.

  Preferred embodiments of the present invention will be described below with reference to the drawings.

  Various methods are used to remove microbial particles such as yeast and bacterial cells from an aqueous solution. In particular, membrane filtration methods using microfiltration membranes and ultrafiltration membranes can remove all microorganisms. It is possible and can be processed continuously in large quantities, so it is suitable for industrial use. As a membrane filtration device used for such a membrane filtration method, a hollow fiber membrane bundle accommodated in a casing is fixed to the casing and modularized, or a hollow fiber membrane bundle without a casing is provided. There is a type in which a membrane module is integrated and the membrane module is detachably accommodated in a case called a housing. The membrane module according to the present embodiment is a type called the latter cartridge module.

The cartridge module 1 (see FIG. 7) is used by being detachably accommodated in a predetermined housing 3. The cartridge module 1 manufactures a module precursor 5 by fixing header members 9 (see FIG. 1) to both ends of a bundle of hollow fiber membranes (hereinafter referred to as “hollow fiber membrane bundle”) 7, for example. The module precursor 5 is manufactured by cutting a part of both ends of the module precursor 5 to form a module end face 6 in which the end of the hollow fiber membrane 7a is opened. First, the module precursor 5 will be described.
(Module front)

  As shown in FIGS. 1 and 4, the module precursor 5 includes a bottomed tubular header member 9 that is attached to both ends of the hollow fiber membrane bundle 7, and the hollow fiber membrane bundle 7 is inserted through the hollow fiber membrane bundle 7. The cylindrical protective member 11 that protects the bundle 7 and the density variation of the hollow fiber membrane 7a that is inserted into the end of the hollow fiber membrane bundle 7 are corrected. And a sealing portion for bonding (bonding) the hollow fiber membrane bundle 7, the protective member 11, the cross plate 13 and the header member 9 with the sealing material S filled and solidified in the header member 9. 15.

  The header member 9 (see FIG. 2) is made of a heat-resistant polymer material such as polysulfone, and is formed, for example, by cutting a round bar made of a heat-resistant polymer material. The header member 9 has a bottomed cylindrical shape (cup shape), and includes an inlet-side cylinder portion 21 provided on the inlet side into which the hollow fiber membrane bundle 7 is inserted, and a bottom-side cylinder portion 23 provided on the bottom side. Prepare. The inner diameter of the inlet side cylinder part 21 and the bottom side cylinder part 23 is different, and the inner diameter of the bottom side cylinder part 23 is smaller than that of the inlet side cylinder part 21. The ratio (inner diameter ratio of the header member 9) when the inner diameters r1 and r2 of the inlet side cylinder part 21 and the bottom side cylinder part 23 are compared with each other, that is, r2 / r1, is 0.5 or more and 0.99 or less. And preferred. Moreover, from the relationship with the number of hollow fiber membranes (module membrane area) which can be filled, 0.8 or more and 0.98 or less are more preferable.

  The inner surfaces of the inlet side cylinder part 21 and the bottom side cylinder part 23 communicate with each other via an annular seating surface 25 formed on a virtual plane substantially orthogonal to the axis L of the header member 9. The seat surface 25 forms a step St (see FIG. 5) having a height difference between the inner surfaces of the inlet-side cylinder portion 21 and the bottom-side cylinder portion 23.

  A plurality of annular shallow grooves 21 a along the axis L of the header member 9 are formed on the inner surface of the inlet side cylinder portion 21. In the present embodiment, the shape of the shallow groove 21a exemplifies an aspect of a groove (a groove having a shape in which a right triangle is cut out in a cross-sectional view). In addition, groove shapes that can be formed by post-processing can be widely used, including clipper grooves (mountain grooves) and the like.

  Here, regarding the shape of the shallow groove 21a, a supplementary description will be given by taking as an example a case where the centrifugal bonding method is employed as a method of filling the sealing material S in the header member 9. In this case, considering the ease of air bubble removal, the ease of processing, the cost for mass production, etc., the shallow groove 21a is a groove of any one of four types: a square groove, a groove, a round groove, and a clipper groove. An embodiment in which the above four types of groove shapes are appropriately combined with the shape or the plurality of shallow grooves 21a is preferable, and any one of three types of groove shapes, such as a square groove, a groove groove, and a clipper groove, A mode in which the above three types of groove shapes are appropriately combined with the shallow groove 21a is preferable.

  In addition, it is efficient to arbitrarily determine the number of shallow grooves 21a formed in the inlet side cylindrical portion 21 and the processing position depending on the size of the header member 9 or the mutual relationship with the object to be peeled, that is, the sealing material S. I think there is.

  A plurality of annular deep grooves 23 a along the axis L of the header member 9 are formed on the inner surface of the bottom side cylinder portion 23, and a plurality of annular shallow grooves 23 b along the axis L of the header member 9 are formed. ing. The deep grooves 23a are provided at two locations near the inlet side cylinder portion 21, and the shallow grooves 21a are formed in a predetermined region near the bottom portion 9b. The shallow groove 23 b of the bottom side cylinder part 23 has substantially the same shape and depth as the shallow groove 21 a of the inlet side cylinder part 21.

  The deep groove 23a according to the present embodiment exemplifies a form of a square groove (a groove having a shape in which a rectangle is cut out in a cross-sectional view). Groove shapes that can be formed by post-processing can be widely adopted, including (mountain grooves).

  Here, regarding the shape of the deep groove 23a, a case where the centrifugal bonding method is employed as a method of filling the sealing material S in the header member 9 will be described supplementarily. In this case, considering the ease of air bubble removal, the ease of processing, the cost of mass production, etc., the deep groove 23a has any one of four types of groove shapes: a square groove, a groove, a round groove, and a clipper groove. Or an embodiment in which the above-mentioned four types of groove shapes are appropriately combined with the plurality of shallow grooves 21a, and any one of the three types of groove shapes, such as a square groove, a recess groove, and a clipper groove, A mode in which the above three types of groove shapes are appropriately combined with the shallow groove 21a is preferable.

  The deep groove 23a is deeper than the shallow groove 21a formed in the inlet side cylinder portion 21, and the ratio of the average depth d2 of the shallow groove 21a to the average depth d1 of the deep groove 23a, that is, d2 / d1. Is preferably 0.1 or more and 0.9 or less. In the present embodiment, a shallow groove 23b is also formed in the bottom cylindrical portion 23, and the shallow groove 23b has the same depth as the shallow groove 21a. Therefore, the depth of the deep groove 23a is greater than that of the shallow groove 23b as in the case of the shallow groove 21a, and the relationship of comparing the average depth is the same as that of the shallow groove 21a. Yes.

  In the present embodiment, of the two deep grooves 23a, one deep groove 23a on the inlet side is provided so as to be aligned with the seat surface 25 forming the step St, and as a result, the seat surface 25 and the deep groove An annular first convex portion 23 c is formed along the axis L of the header member 9. In addition, an annular second convex portion 23 d is formed between the two deep grooves 23 a arranged adjacent to each other along the axis L of the header member 9.

  Note that the number and processing positions of the deep grooves 23a and the shallow grooves 23b or the convex portions 23c and 23d formed in the bottom side cylinder portion 23 are related to the size of the header member 9 and the cutting position for forming the module end surface 6. However, it is considered efficient to arbitrarily determine the relationship with the object to be peeled, that is, the sealing material S.

  Next, the hollow fiber membrane bundle (porous membrane) 7 will be described. The hollow fiber membrane bundle 7 is formed by bundling a large number of hollow fiber membranes 7a. The material of the hollow fiber membrane 7a is not particularly limited, and examples thereof include polyethylene, polypropylene, polyvinylidene fluoride, polysulfone, polytelsulfone, ethylene-vinyl alcohol copolymer, polytetrafluoroethylene, polyacrylonitrile, polyether ketone, and the like. The hollow fiber membrane 7a may be sterilized by autoclaving. By sterilizing by autoclaving, the hollow fiber membrane 7a can be suitably used for filtration of microbial particles.

  The hollow fiber membrane bundle 7 is inserted into the cylindrical protective member 11 and is protected by the protective member 11. Although the shape of the protection member 11 can be selected according to the use etc., it is usually cylindrical in many cases, and in this embodiment, the cylindrical shape will be described as an example. The material of the protective member 11 can be selected according to the type of fluid to be treated and the separation component, for example, polyethylene, polypropylene, polyvinyl chloride, polycarbonate, acrylic polymer, polysulfone, polyethersulfone, plastic, stainless steel, etc. It may be a metal. Usually, polyethylene, polypropylene, polyvinyl chloride, etc. are often used.

  The protective member (also referred to as “net member” or “net”) 11 has a net shape having a plurality of meshes forming a rectangular through-hole H (see FIG. 3), and a plurality of meshes are regularly arranged. It is cylindrical. Note that the end of the protection member 11 is inserted into the header member 9 and is installed substantially concentrically with the header member 9. Therefore, in the following description, the axis of the protection member 11 is described as the same axis L as the header member 9.

  The protection member 11 includes a plurality of vertical line portions 11a along the axis L direction and a plurality of circle portions 11b along the circumferential direction. A plurality of rectangular through-holes H are formed in the protection member 11 by integrally forming the plurality of vertical line portions 11a and the plurality of circle portions 11b so as to cross each other. At both ends in the direction of the axis L of the protection member 11, tips (projections) 11c of the plurality of vertical line portions 11a are formed so as to protrude from the circle portion 11b. As a result, the protruding portions 11c of the plurality of vertical line portions 11a embody a form that is formed so as to protrude from each of the plurality of meshes that are continuous in a ring shape.

  In addition, although the protection member 11 which concerns on this embodiment illustrates cylindrical shape, this protection member 11 may be polygonal cylinder shape.

  The cross board 13 is formed by using the same material as the sealing material S that actually forms the sealing portion 15, for example, epoxy resin, vinyl ester resin, urethane resin, olefin polymer, silicone resin, fluorine-containing resin. Formed by. The cross plate 13 has a function as an insert for adjusting the number of hollow fiber membranes 7 a so that the density is not biased (variation) in the circumferential direction, and is inserted into the end portion of the hollow fiber membrane bundle 7. It is attached. In the present embodiment, the cross plate 13 will be specifically described as an example of the insert. However, the insert may be formed of one flat plate or five or more partition pieces extending radially. It may be provided.

  The cross plate 13 (see FIG. 4) has two rectangular flat plates fitted so as to be orthogonal to each other, and has a shape having four partition pieces 13a extending radially from the center of the intersecting line. Yes. Moreover, the surface of the partition piece 13a is intentionally roughened, and consideration is given to increasing the bonding (adhesion) strength when the sealing material S is filled and solidified. Moreover, the dimension of the partition piece 13a corresponds to substantially half of the inner diameter of the bottom side cylinder portion 23 of the header member 9, and the inner diameter of the virtual cylinder passing through the outer edges of the four partition pieces 13a and the bottom side cylinder portion 23. The inner diameter of the imaginary cylinder / the inner diameter of the bottom cylindrical portion 23 is 0.5 to 0.99. A large number of the hollow fiber membrane bundles 7 are substantially divided into four equal parts inside the bottom side cylindrical portion 23 by the four partition pieces 13 a.

  A cross plate 13 is inserted into both end portions of the hollow fiber membrane bundle 7 inserted into the protective member 11, and a large number of hollow fiber membrane bundles 7 are visually divided by the cross plate 13. The hollow fiber membrane bundle 7 is inserted into the header member 9 with the cross plate 13 attached, and the front end of the protection member 11 surrounding the hollow fiber membrane bundle 7 forms a step St inside the header member 9. Abut. In this state, the end portion of the hollow fiber membrane bundle 7 to which the cross plate 13 is attached fits in the bottom side tubular portion 23 of the header member 9.

After the header members 9 are mounted on both ends of the hollow fiber membrane bundle 7, the header member 9 is filled with a molten sealing material S (also referred to as "sealing material" or "adhesive"). The end of the hollow fiber membrane bundle 7 is sealed. For the sealing material S, for example, an epoxy resin, a vinyl ester resin, a urethane resin, an olefin polymer, a silicone resin, a fluorine-containing resin, or the like is used. Further, the filling of the sealing material S is performed through an introduction port 9a formed in the bottom portion 9b of the header member 9, and is appropriately executed by, for example, a centrifugal bonding method or a stationary bonding method. The sealing material 15 filled in the header member 9 is solidified to form the sealing portion 15 and the module precursor 5 is formed.
(Cartridge module)

  As shown in FIGS. 1, 4, and 7, the cartridge module (membrane module) 1 is manufactured using a module precursor 5. In the module precursor 5, both ends of the hollow fiber membrane 7 a are closed by the sealing portions 15, and in order to complete the cartridge module 1, a module end face 6 is formed in which both ends of the hollow fiber membrane 7 a are opened. There is a need to. In the present embodiment, a part of the bottom side of the header member 9 is cut and removed to form the module end surface 6 (see FIG. 4C), and the cartridge module 1 is completed.

  The cartridge module 1 includes a cylindrical header portion 1a formed using a header member 9, a hollow fiber membrane bundle 7 including a plurality of hollow fiber membranes 7a inserted into the header portion 1a, and a hollow fiber membrane bundle 7 Is sealed to the header portion 1a, the module end face 6 in which the inside of the hollow fiber membrane 7a is opened, and the hollow fiber membrane bundle 7 are surrounded in an annular shape, and the sealing portion 15 together with the hollow fiber membrane bundle 7 is enclosed. And a cylindrical protective member 11 fixed to the header portion 1a.

  The cartridge module 1 constitutes a filtration membrane unit by being inserted into the housing 3 and detachably attached. The shape of the housing 3 can be selected according to the application and the like, but usually it is often a cylindrical shape. The material of the housing 3 can be selected according to the type of fluid to be treated and the separation component, for example, plastic such as polyvinyl chloride, polycarbonate, acrylic polymer, polysulfone, polyethersulfone, or metal such as stainless steel. Also good. Usually, stainless steel, polyvinyl chloride, polysulfone, etc. are often used.

The structure will be described in detail by taking the cylindrical housing 3 as an example. The housing 3 includes a cylindrical body 3a that houses the cartridge module 1, and a pair of caps 3b that are assembled to both ends of the body 3a by screwing. A seal ring 3c is provided between the body 3a and the cap 3b by tightening the cap 3b. The body 3a is formed with a pipe portion 3d that serves as an outlet for concentrated water, an inlet for raw water, or the like at both ends. The cap 3b has a substantially conical shape, and a pipe portion 3e is formed at the top for serving as an inlet for raw water and discharging filtered water.
(Manufacturing method of cartridge module)

  Next, a manufacturing method of the cartridge module (membrane module) 1 will be described with reference to FIG. First, a process of forming a hollow fiber membrane bundle 7 by bundling a plurality of hollow fiber membranes 7a is executed (step S1). Specifically, a predetermined number of hollow fiber membranes 7a are cut and aligned so that the cutting length is a predetermined length on the basis of the bundle head (bundling), and further, local cleaning of the hollow fiber membrane 7a and processing of the end portions are performed. Implement as appropriate.

  Next, an assembling process for the module precursor element is executed (step S2). Specifically, the bundled hollow fiber membrane bundle 7 is inserted into the protective member 11. Further, the cross plate 13 is attached to the portion protruding from the protective member 11 to correct the variation in the number density of the hollow fiber membranes 7a, and in this state, the header member 9 is attached to both ends of the hollow fiber membrane bundle 7 and the module is installed. Assemble the front frame elements.

  Next, a step of filling the molten sealing material S in the header member 9 is executed (step S3). As a filling method of the sealing material S, there are a centrifugal bonding method in which the sealing material S is filled using centrifugal force, a stationary bonding method in which the sealing material S is filled using gravity, and the like. The centrifugal bonding method and the stationary bonding method will be described as a representative.

  The centrifugal bonding method is performed using a centrifugal bonding machine equipped with a jig called a centrifugal cassette. The structure in which the module precursor element is assembled is attached to the centrifuge cassette in a state of being laid horizontally, and rotates on a horizontal plane with the vertical axis as a rotation axis. Centrifugal force acts on the header member 9 by the rotation of the centrifugal cassette, and the sealing material S is filled in the header member 9 using this centrifugal force. There are two possible filling methods using centrifugal force, for example, depending on the length of the hollow fiber membrane bundle 7. One method is a method in which both ends are centrifugally bonded at the same time, and another method is a method in which centrifugal bonding is performed twice on each side. For example, when performing each one side, it arrange | positions so that one edge part used as adhesion | attachment object may become an outer side of a centrifugal direction, and the other edge part may become an inner side of a centrifugal direction. The molten sealing material S is transferred to the header member 9 side that is outside in the centrifugal direction using centrifugal force, and further, the sealing material S is passed through the inlet 9 a formed in the bottom 9 b of the header member 9. Is filled inside.

  On the other hand, in the static adhesion method, the hollow fiber membrane bundle 7 on which the header member 9 is mounted is arranged in a state where it is erected along the vertical direction. One end of the hollow fiber membrane bundle 7 to be bonded is on the upper side, and the other end is on the lower side. The upper header member 9 is filled with the molten sealing material S through the inlet 9a of the bottom 9b. Here, the sealing material S is filled in the header member 9 without a gap by its own weight, and then, when the sealing material S cools and loses its fluidity, the top and bottom are inverted, and the inside of the header member 9 is on the upper side. The sealing material S is filled with its own weight.

  When comparing the cartridge modules 1 obtained by the two filling methods from the viewpoint of mass productivity and quality, the most notable structural difference is the unevenness of the interface shape around the header portion 1a, that is, the header portion. It is the unevenness | corrugation difference of the sealing part 15 in the entrance side of 1a. However, this difference is not an essential difference in terms of the performance of the cartridge module 1. In addition, the centrifugal bonding method is characterized in that the centrifugal force is set by the manufacturing apparatus, so that the tendency is likely to appear in other condition settings. The stationary bonding method is influenced by the viscosity of the sealing material S, the outside air temperature, and the like. It is easy to be affected. However, if the bonding conditions are properly set, that is, if the desired accuracy can be ensured, it is considered that there is no difference in mass productivity and quality of the cartridge module 1.

  Next, a step of solidifying the sealing material S filled in the header member 9 to form the sealing portion 15 is executed (step S4). Specifically, when the filling of the sealing material S is completed, the hollow fiber membrane bundle 7 is allowed to cool. As a result, the sealing material S is solidified to form the sealing portion 15, and the module precursor 5 is obtained. Next, the module precursor 5 is cured at 50 ° C. for a predetermined time (step S5), and then 90 ° C. curing is performed for a predetermined time (step S6).

  Next, a part of the bottom 9b side of the header member 9 and a part of the sealing part 15 are cut together with the end of the hollow fiber membrane 7a to open the inside of the plurality of hollow fiber membranes 7a. (Step S7), and the cartridge module 1 is completed.

  Next, effects of the header member 9 and the cartridge module 1 will be described. When the module precursor 5 is manufactured, the sealing material S is filled so as to fill the gap inside the header member 9 (see FIGS. 5 and 6), and further cooled and solidified to form the hollow fiber membrane bundle 7 and the cross plate. 13, the protective member 11 and the inner surface of the header member 9 are bonded (bonded). In the header member 9, the inner diameter r1 of the inlet side cylinder portion 21 is larger than the inner diameter r1 of the bottom side cylinder portion 23, and there is a step St between the inner surfaces of the inlet side cylinder portion 21 and the bottom side cylinder portion 23. Is provided. In the process in which the sealing material S is cooled and solidified, the sealing material S slightly heat shrinks. Even if peeling occurs at the contact surface with the sealing material S in the inlet side cylindrical portion 21 due to this heat shrinkage, the propagation of peeling from the inlet side cylindrical portion 21 side to the bottom side cylindrical portion 23 is caused by the step St. Is prevented and, therefore, delamination growth is suppressed.

  Further, deep grooves 23a and shallow grooves 21a and 23b are formed on the inner surface of the header member 9, and the sealing material S enters the deep grooves 23a and the shallow grooves 21a and 23b and is solidified. Therefore, the contact surfaces of the header member 9 and the sealing material S are fitted in a concavo-convex shape and firmly bonded (bonded), which is effective in suppressing the growth of peeling, and is effective in preventing peeling (leakage). For example, it can withstand heat and pressure during sterilization or radiation treatment. As a result, the quality of the cartridge module 1 can be improved.

  Furthermore, a shallow groove 21 a is formed in the inlet side cylinder portion 21 of the header member 9, and a deep groove 23 a is formed in the bottom side cylinder portion 23 in addition to the shallow groove 21 a. For example, since the sealing material S enters and solidifies deeper as the depth of the groove formed on the inner surface of the header member 9 is deeper, the deeper groove is firmly bonded to the header member 9. This is advantageous in terms of suppressing peeling. However, in a method in which the sealing material S is filled from the bottom 9b side of the header member 9 as in the centrifugal bonding method or the stationary bonding method, the inlet-side cylindrical portion 21 is more sealed than the bottom-side cylindrical portion 23. Since it becomes difficult to enter, if the groove of the inlet side cylinder portion 21 is made too deep, there is a possibility that a gap may be generated between the sealing material S and the header member 9 without the sealing material S entering. On the other hand, since the sealing material S is easier to enter in the bottom side cylindrical portion 23 than in the inlet side cylindrical portion 21, the sealing material S can sufficiently enter even if the depth of the groove is positively increased. it can. That is, according to the header member 9, when the sealing material S is filled from the bottom 9 b side, the header member 9 and the sealing material S can be firmly filled while ensuring the filling of the sealing material S. Bonding is easy to realize, and it is effective in suppressing delamination or delamination growth. In addition, although the shallow groove 23b is formed in the bottom side cylinder part 23 which concerns on this embodiment other than the deep groove 23a, it is also possible to form only the deep groove 23a and to omit formation of the shallow groove 23b. .

  In addition, on the inner surface of the bottom side tubular portion 23 of the header member 9, an annular first convex portion 23 c and a second convex portion 23 d are formed along the axis L of the header member 9. When the sealing material S is filled in the header member 9, it covers the first and second protrusions 23 c and 23 d. As described above, the sealing material S is thermally contracted in the process of solidification. In this case, the sealing material S covering the convex portions 23c and 23d contracts so as to sandwich the convex portions 23c and 23d. Peeling in the process in which the stop material S is solidified is prevented. As a result, it is effective in improving the quality of the cartridge module 1 by suppressing the growth of peeling.

  Further, in the cartridge module 1 according to the present embodiment, since the header portion 1a is formed using the header member 9 described above, occurrence of peeling when the sealing portion 15 is formed by solidification of the sealing material S is generated. In addition, propagation is suppressed and high quality can be expected.

  In addition, since the cartridge module 1 includes the cylindrical protective member 11 that surrounds the hollow fiber membrane bundle 7 in an annular shape, the hollow fiber membrane bundle 7 is held together by the protective member 11 and protected from external impacts and the like. Is done.

  Further, the protection member 11 is formed with a linear (line-shaped) protruding portion 11c protruding in the direction of the axis L from both ends fixed to the header portion 1a. For example, when the end portion of the protective member 11 is formed by a flat circumference without the protruding portion 11c, if peeling occurs at this end portion, the peeling easily propagates in the circumferential direction, and the peeling grows. easy. However, according to the protective member 11 according to the present embodiment, since the protrusion 11c becomes an obstacle and propagation of peeling in the circumferential direction is prevented, it is effective in suppressing the growth of peeling. In addition, the effect of the protrusion part 11c can be confirmed by the presence or absence of occurrence of peeling visible from the appearance before and after the curing in the process of manufacturing the cartridge module 1.

  Further, even when membrane filtration is performed using the cartridge module 1, there is a possibility that separation occurs between the header portion 1 a and the sealing portion 15 due to, for example, physical cleaning or chemical cleaning. There is. However, in this embodiment, since the header portion 1a and the sealing portion 15 are firmly bonded (bonded), the occurrence of peeling can be effectively prevented, and the case where peeling occurs temporarily. However, the growth of peeling can be effectively suppressed.

Moreover, according to the manufacturing method of the cartridge module (membrane module) 1 described above, even if peeling occurs on the inlet side of the header member 9 in the process of forming the sealing portion 15, Propagation of peeling from the inlet side cylinder part 21 side to the bottom side cylinder part 23 is prevented by the step St formed between the inner surface of the bottom side cylinder part 23. Further, since the sealing material S filled in the header member 9 enters into the annular shallow grooves 21a and 23b and the deep grooves 23a and is solidified, the contact surfaces of the header member 9 and the sealing material S are in contact with each other. It fits in a concavo-convex shape and is firmly bonded (bonded), which is effective in suppressing the occurrence and growth of peeling. As a result, the cartridge module 1 with high quality can be manufactured.
(Surface treatment of header member)

  Next, the surface treatment applied to the inner surface of the header member 9 constituting the module precursor 5 will be described in detail. The inner surface of the header member 9 is subjected to a predetermined surface treatment for hydrophilization, and by this surface treatment (hydrophilization treatment), excellent adhesive force at the contact portion between the sealing material S and the header member 9 is obtained. Can be expected. The effect of the surface treatment can be confirmed by the presence or absence of occurrence of peeling that can be seen from the appearance before and after the curing in the process of manufacturing the cartridge module 1.

  As this surface treatment method, various methods such as chemical treatment, flame treatment, primer treatment, corona discharge treatment, laser treatment, and plasma treatment can be appropriately employed. Of these surface treatments, plasma treatment or corona discharge treatment is preferred from the viewpoints of workability, safety, and quality stability.

  In addition, as a result of earnestly examining the plasma treatment and the corona discharge treatment as the surface treatment method of the header member 9, the present inventor obtained the following knowledge. One is that there is no great difference in the hydrophilization effect between the plasma treatment and the corona discharge treatment under atmospheric pressure, and either can be used. Further, generally speaking, plasma processing often refers to processing under vacuum (low pressure), but this method is not suitable for mass production due to many limitations on processing equipment. On the other hand, if plasma processing under atmospheric pressure is adopted, it is suitable for complicated shapes and for large amounts of processing. In the case of plasma treatment, it has been found that the continuity of the treatment effect remains the same regardless of whether it is air plasma or inert gas plasma.

  As for the hydrophilization mechanism by such surface treatment, plasma treatment or corona discharge treatment can be used to modify the introduction of oxygen atoms into the outermost surface of the header member 9, cleanability of the reaction surface with the sealing material S, outermost surface, etc. It is considered that it has a strong adhesive force by improving the unevenness (anchor effect), introducing a polar functional group, activating a functional group, a reactive group, or a polar group.

  The hydrophilicity of the material surface can be quantified by various evaluation indexes, but a method of measuring the contact angle (θ) when a specific solvent is allowed to stand on the surface is simple.

  According to said surface treatment method, it can confirm that the water contact angle ((theta)) after a process becomes 60 degrees or less after a process with respect to 90-110 degree | times before a process. Since the treatment effect varies with time, when considering mass productivity, the water contact angle (θ) after treatment is preferably 50 degrees or less. When atmospheric pressure plasma treatment is used as the surface treatment, the following control factors exist as treatment conditions, and the effect naturally varies depending on the treatment conditions. Control factors include the type of gas used, the shape of the plasma irradiation port, the distance from the plasma irradiation port to the processing surface, the gas supply amount, the plasma output (processing power), the moving speed of the irradiation port, the processing time, and the like. These control factors are basically the same in the corona discharge treatment.

  The surface treatment (hydrophilization treatment) effect changes with time, but the water contact angle (θ) increases with time and passage in the measurement results of the present inventors. That is, since the hydrophilizing effect is diminished, it is necessary to proceed to the bonding step immediately after the treatment, but it is preferably within 24 hours, more preferably within 12 hours, and more preferably within 8 hours.

  To confirm the effect of surface hydrophilization treatment, prepare a plate of a predetermined material and perform surface treatment under various conditions (gas flow rate, substrate-irradiation part distance, scanning speed). Was determined by the water contact angle. In addition, with respect to the change over time of the treatment effect, the treatment sample was left in the room and the evaluation was carried out using the numerical value of the contact angle. Furthermore, confirming that the adhesive strength has become stronger and that the treatment effect has changed over time is obtained by applying a sealing material (adhesive) S to the plate material after surface hydrophilization treatment (plate material having a width of 2 cm, a length of 10 cm, and a thickness of 5 mm). It was evaluated by measuring the shear strength with a strength tester after curing and bonding (overlapping state with a length of 1 cm).

  The evaluation device used for measuring the shear strength is a Tensilon universal testing machine (model RTF-1350). The sample is pulled, whether the substrate breaks or the bonded portion peels, and the strength is numerically expressed as the maximum point load at that time. Turned into.

  In addition, the base material used for the confirmation of the treatment effect was based on polysulfone, and the effect under the same conditions was confirmed using PP, PE, ABS as a comparison target. However, the absolute value of the contact angle was different, but the tendency was almost the same.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

(Production example of porous hollow fiber membrane)
Polysulfone (SOLVAY ADVANCED POLYMERS, Udel P3500) 18% by weight and polyvinylpyrrolidone (BASF, Luvitec k80) 15% by weight were dissolved in N-methyl-2-pyrrolidone 62% by weight at 70 ° C. to obtain glycerin 5 Weight% was added and further stirred to prepare a film-forming stock solution. This film-forming stock solution was fed from a double ring spinning nozzle (outer diameter 2.4 mm, intermediate diameter 1.2 mm, inner diameter 0.6 mm, the same was used in the following examples) to 90 wt% NMP of the internal coagulation liquid. The solution was extruded with an aqueous solution at 70 ° C., passed through a free running distance of 50 mm, and coagulated in water at 80 ° C. At this time, the temperature from the spinneret to the coagulation bath was surrounded by a cylinder having a bottom area of 38 cm ² , and the temperature of the free running portion was 75 ° C. and the relative humidity was 100% (absolute humidity 240 g / m ³ ). At this time, after removing the solvent in water, polyvinylpyrrolidone was decomposed in an aqueous 2000 ppm sodium hypochlorite solution for 15 hours and then washed with water at 90 ° C. for 3 hours to obtain a porous hollow fiber membrane. The obtained hollow fiber had an outer diameter of 2.3 mmφ, an inner diameter of 1.4 mmφ, a minimum pore diameter of 0.4 μm, and an initial pure water permeability of 80 L / hr.

[Cartridge module test]
(Examples 1, 2, 3, 4, 5)
A header member of a predetermined structure is manufactured by cutting from a polysulfone round bar (200mmφ * 1000mmL), PP net (protective member), presence / absence of surface treatment (surface hydrophilization treatment) inside the header member, groove processing ( The porous hollow fiber obtained in Production Example 1 so as to have a membrane area of 12 m ² by variously changing the structure of the cross-plate size, the structure inside the header member, and the structure of the axial end of the protective member. The membrane was put in, a module of practical size was produced, and the peeled state was observed and evaluated. The sealing material (adhesive) is filled in the header member using a centrifugal bonding method. The adhesive is an epoxy resin, the centrifugal force is 35 G, the centrifuge atmosphere temperature is 35 ° C., the centrifuge time is 4 hours, and the curing is 50 ° C. For 48 hours, and then at 90 ° C. for 16 hours. After curing, a predetermined position of the header member was cut to form a module end face, and the hollow portion and the cut end face were observed. Observation was conducted mainly on the presence or absence of peeling, including during production. The observation results are shown in Table 1. The “inner diameter ratio of the header member” in Table 1 means (the inner diameter of the bottom cylinder) / (the inner diameter of the inlet cylinder).

  In actual use, the cartridge module may not cause a problem depending on the degree of peeling visible from the appearance. Therefore, it was qualitatively determined whether or not peeling occurred. Even in the module evaluation by the present inventor, it has been confirmed that no problem occurs when there is no peeling occurrence portion.

(Comparative Examples 1 and 2)
Modules were created with a structure similar to that of Examples 1 to 5, and observed in the same manner. All the modularization conditions are matched. The observation results are shown in Table 2. The “inner diameter ratio of the header member” in Table 2 means (inner diameter of the bottom side cylinder part) / (inner diameter of the inlet side cylinder part). Further, in Comparative Example 1, the depth of the groove of the inlet side cylinder part with respect to the groove formed in the bottom side cylinder part is very shallow. Therefore, the groove of the inlet side cylinder part with respect to the groove of the bottom side cylinder part shown in Table 2 is reduced. The ratio of the average depth is “0.01”. Moreover, in the comparative example 2, the substantial groove | channel is not formed in the inner surface of a bottom side cylinder part, and the substantial groove | channel is not formed also in the inner surface of an entrance side cylinder part. Therefore, the groove of the bottom side cylinder part and the groove of the inlet side cylinder part shown in Table 2 are considered to have substantially the same depth, and the average depth of the groove of the inlet side cylinder part with respect to the groove of the bottom side cylinder part is The ratio is “1.0”.

  DESCRIPTION OF SYMBOLS 1 ... Cartridge module (membrane module), 1a ... Header part, 6 ... Module end surface, 7 ... Hollow fiber membrane bundle, 7a ... Hollow fiber membrane, 9 ... Header member, 21 ... Inlet side cylinder part, 21a ... Shallow groove, 23 ... bottom side cylinder part, 23a ... deep groove, 23b ... shallow groove, 23c ... 1st convex part, 23d ... 2nd convex part, 11 ... protection member, 11c ... protrusion part, 15 ... sealing part, H ... protection Through hole of member, L ... axis, S ... sealing material, r1 ... inner diameter of inlet side cylinder part, r2 ... inner diameter of bottom side cylinder part, St ... step.

Claims (7)

In the bottomed cylindrical header member attached to the end of the hollow fiber membrane bundle and fixed to the hollow fiber membrane bundle by filling and solidifying the sealing material inside,
An inlet side cylinder part provided on the inlet side into which the hollow fiber membrane bundle is inserted, and a bottom cylinder part having an inner diameter smaller than that of the inlet side cylinder part and provided on the bottom side of the inlet side cylinder part And comprising
A step is formed between the inner surface of the inlet-side tube portion and the inner surface of the bottom-side tube portion, and at least one inner surface of the inlet-side tube portion and the bottom-side tube portion has an axis of the header member A header member characterized in that an annular groove is formed along the circumference.   2. The header member according to claim 1, wherein the groove includes a shallow groove formed in the inlet-side cylinder portion and a deep groove formed in the bottom-side cylinder portion and deeper than the shallow groove. .   3. The header member according to claim 1, wherein an annular convex portion is formed on an inner surface of the bottom-side cylinder portion along an axis of the header member.   The cylindrical header part formed using the said header member as described in any one of Claims 1-3, The hollow fiber membrane bundle which consists of several hollow fiber membranes inserted in the said header part, The said hollow A membrane module comprising: a sealing portion for fixing the yarn membrane bundle to the header portion; and a module end face in which the inside of the hollow fiber membrane is opened. Further comprising a cylindrical protective member that annularly surrounds the hollow fiber membrane bundle and is fixed to the header portion by the sealing portion together with the hollow fiber membrane bundle;
The protective member is provided with a plurality of through-holes and a linear protrusion protruding in an axial direction of the protective member from an end fixed to the header portion. Item 5. The membrane module according to Item 4.   The protection member has a mesh shape and has a plurality of meshes that form the through-holes, and the protruding portions are formed so as to protrude from the plurality of meshes that are continuously connected to each other at the end of the protection member. The membrane module according to claim 5. In the method of manufacturing a membrane module using the header member according to any one of claims 1 to 3,
Bundling a plurality of hollow fiber membranes to form a hollow fiber membrane bundle;
Attaching the header member to an end of the hollow fiber membrane bundle, and filling the molten sealing material in the header member;
A step of solidifying the sealing material filled in the header member to form a sealing portion;
After forming the sealing portion, a part of the bottom side of the header member and a part of the sealing portion are cut together with an end portion of the hollow fiber membrane to open the inside of the plurality of hollow fiber membranes. Forming a module module end face, and a method for manufacturing a membrane module.

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