TW201819034A - Filtering membrane module and manufacturing method thereof, and mounting method of the same capable of maintaining filtering performance of filtering membrane and suppressing microorganism reproduction without affecting water quality - Google Patents

Abstract

The subject of this invention is to provide a filtering membrane module that may maintain the filtering performance of filtering membrane, suppress the microorganism reproduction, and not affect the water quality once starting usage, and a manufacturing method thereof. The filtering membrane module of this invention comprises a hollow fiber membrane (3a) used for liquid filtering, and a hollow fiber member module (1) for accommodating a shell (5) of the hollow fiber membrane (3a), wherein the shell (5) is filled with sterilized pure water as the preservation solution for maintaining the filtering performance of the hollow fiber membrane (3a).

Description

Filter membrane module, manufacturing method thereof, and method for setting filter membrane module

The invention relates to a filter membrane module suitable for use as a terminal filter for removing fine particles in treated water in an ultrapure water manufacturing process, a method for manufacturing the same, and a method for setting the filter membrane module.

In the production line of ultrapure water used in the manufacture of semiconductors, display elements and other electronic and electrical parts, the ultrapure water produced using microfiltration membranes, ion exchange resins, and reverse osmosis filtration membranes is immediately supplied to the use. Before the point, a filter membrane module was used as a final filter to remove particles from ultrapure water. As the filtration membrane module for this purpose, because it has the advantage of achieving a large filtration flow rate for each module, it is mainly used to supply raw water to the outside of the hollow fiber membrane and perform filtration. As a required property of the filter membrane module for this application, it is required to make the quality of ultrapure water, that is, the number of particles in the filtered water, the conductivity of the filtered water, and TOC (Total Organic Carbon) within a short time after the start of use , Total organic carbon), etc. to reach the required level. Therefore, in the filtration membrane module of this application, a washing step for reducing the emission of particulates from the filter, the dissolution of ionic components and organic matter is provided at the final stage of the manufacturing process of the product, and the washing is carried out to a clean Shipped in the state up to the state. On the other hand, in order to maintain its filtration performance and inhibit the proliferation of microorganisms in the product, the filter membrane module must be stored in a humid state after use with a preservation solution with bactericidal and bacteriostatic effects. In the present invention, a glycerin aqueous solution, an alcohol aqueous solution, or a sodium hypochlorite aqueous solution is used as a storage solution (for example, refer to Patent Document 1). However, as mentioned above, the filter membrane module used in the ultra-pure water production line is required to meet the water quality as ultra-pure water within a short period of time from the beginning of use. Therefore, if organic substances such as glycerin, alcohol, and sodium are used, Preservation liquids such as metal ion components have the problem that the cleaning takes time. Therefore, as the storage solution for this application, an aqueous formaldehyde solution that inhibits the growth of microorganisms even at a low concentration, or an aqueous hydrogen peroxide solution that does not leave organic matter and ionic components and has a bactericidal effect has been used. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 6-296838

[Problems to be Solved by the Invention] However, when a formaldehyde aqueous solution is used, although the reproduction of microorganisms can be suppressed at a low concentration of less than 1%, it will affect the reduction of TOC. On the other hand, although hydrogen peroxide water inhibits the reproduction of microorganisms and does not affect TOC, but because of the strong oxidizing power of hydrogen peroxide, it will make polymer membranes that are commonly used as raw materials for filtration membranes for this purpose. Gradually deteriorate, and the separation performance of the membrane may be reduced or damaged. The present invention aims to solve the above problems, and an object thereof is to provide a filtration membrane module that maintains the filtration performance of the filtration membrane, inhibits the reproduction of microorganisms, and does not affect the water quality after the start of use, a method for manufacturing the same, and a filtration membrane module. The setting method. [Technical means to solve the problem] The present inventors and others have made intensive research and verification in order to satisfy the various requirements mentioned above. As a result, it was confirmed that all requirements were satisfied by sealing the sterilized water as a preservation solution at a high temperature, and a method for producing the same was found, and the present invention was conceived. That is, the filter membrane module of the present invention is provided with a filter membrane used for liquid filtration, and a housing containing the filter membrane, and is characterized in that the housing is filled with sterilized pure water as a means for holding the filter membrane. Preservative for filtration performance. In the above-mentioned filter membrane module of the present invention, it is preferable that the content of organic matter in the preservation solution is 5 ppm or more and less than 50 ppm in terms of TOC (Total Organic Carbon). In the above-mentioned filter membrane module of the present invention, it is preferable that the concentration of the metal ions contained in the preservation solution is 10 ppb or more and less than 100 ppb. In the above-mentioned filter membrane module of the present invention, it is preferable that the concentration of chloride ions contained in the preservation solution is 25 ppb or more and less than 250 ppb. The manufacturing method of the filtering membrane module of the present invention is characterized in that it is a method of manufacturing the following filtering membrane module, the filtering membrane module is provided with a filtering membrane used for liquid filtration, and a housing containing the filtering membrane, And the shell is filled with sterilized pure water as a preservation liquid to maintain the filtering performance of the filter membrane, and the manufacturing method is to seal the filtered and sterilized pure water into the shell containing the filter membrane at 80 ° C. The shell sealed with pure water is heat-treated at a temperature above 100 ° C, thereby sterilizing the pure water in the filter membrane module to prepare a preservation solution. Further, in the method for manufacturing a filter membrane module of the present invention, in the step of heating the housing sealed with pure water, in order to reduce the pressure rise caused by the thermal expansion of the sealed pure water, it is preferable. A pressure buffer mechanism is provided on the raw water side of the filter membrane module. In addition, in the above-mentioned manufacturing method of the filter membrane module of the present invention, in the step of performing heat treatment on the shell sealed with pure water, in order to absorb the volume expansion of the sealed pure water caused by heat, it is preferably A volume expansion absorption mechanism is arranged on the raw water side of the filter membrane module. Moreover, in the above-mentioned method for manufacturing a filtration membrane module of the present invention, it is preferable that the pure water filtered and sterilized is water obtained by filtering through an ultrafiltration membrane or a reverse osmosis membrane, and the pure water contains 50 nm or more The fine particles are 10 particles / L or more and 200 particles / L or less. In the method for manufacturing a filter membrane module of the present invention, it is preferable that the content of organic matter in pure water is 5 ppm or more and less than 50 ppm by TOC (Total Organic Carbon). In the method for manufacturing a filter membrane module of the present invention, the concentration of metal ions contained in pure water is preferably 10 ppb or more and less than 100 ppb. In the method for manufacturing a filter membrane module of the present invention, the concentration of chloride ions contained in pure water is preferably 25 ppb or more and less than 250 ppb. In addition, in the step of heating the shell sealed with pure water, it is preferable to provide a pressure buffer mechanism on the raw water side of the filter membrane module in order to reduce the pressure rise caused by the thermal expansion of the sealed pure water. At the same time, in order to absorb the volume expansion of the pure water enclosed by heat, a volume expansion absorption mechanism is set on the raw water side of the filter membrane module, and the filter side of the filter membrane module is set to a closed state. Moreover, in the above-mentioned method for manufacturing a filter membrane module of the present invention, it is preferable that the filter membrane module is a hollow fiber membrane module that contains a hollow fiber membrane as a filter membrane in the housing, and may have a structure similar to that of the hollow fiber membrane. In the filtering side port communicating with the hollow part and the raw water side port communicating with the outer side of the hollow fiber membrane, a volume expansion absorption mechanism is provided in the raw water side port in the step of heating the shell sealed with pure water, and simultaneously pressure The buffer mechanism is set in a state in which the pressure buffer mechanism contains a tightening member, and the filtering side port is set to a closed state. After the heat treatment step, the volume expansion absorption mechanism is replaced with a tightening member in the pressure buffer mechanism. Then, remove the pressure buffer mechanism and the volume expansion absorption mechanism. Moreover, in the above-mentioned method for manufacturing a filter membrane module of the present invention, it is preferable that the filter membrane module is a hollow fiber membrane module that contains a hollow fiber membrane as a filter membrane in the housing, and may have a structure similar to that of the hollow fiber membrane. In the filtering side port communicating with the hollow part and the raw water side port communicating with the outer side of the hollow fiber membrane, a volume expansion absorption mechanism is provided in the raw water side port in the step of heating the shell sealed with pure water, and simultaneously The volume expansion absorption mechanism is provided with a pressure buffer mechanism that allows gas to pass through but does not allow bacteria to permeate, and further sets a gas inflow prevention member that prevents the inflow of external air into the raw water side port in a state that the gas inflow member contains a fastening member, The filtering side port is closed, and after the heat treatment step, the volume expansion absorption mechanism is replaced with a fastening member in the gas inflow prevention member, and then the volume expansion absorption mechanism and the gas provided with the pressure buffer mechanism are removed. Inflow prevention member. The setting method of the filtration membrane module of the present invention is a method of installing the above-mentioned filtration membrane module on the piping of a water treatment device, which is characterized in that: the fastening members of the filter side port and the raw water side port of the closed filter membrane module are removed Except that the pure water enclosed in the filter membrane module is discarded to the piping of the water treatment device, the piping of the water treatment device is installed. [Effects of the invention] According to the filter membrane module of the present invention, since pure water sterilized is sealed as a preservation liquid for the filter membrane module to maintain the filtering performance, the filtering performance of the membrane can be maintained and the filtration inside the module can be suppressed. Multiplication of microorganisms. That is, the filter module can be stored for a long time without using chemicals, and the cleaning time at the start of use can be greatly reduced. Moreover, in the above-mentioned filter membrane module of the present invention, when the content of organic matter in the preservation solution is set to 5 ppm or more and less than 50 ppm in terms of TOC, water with less organic matter content is prepared in this way. , And can significantly reduce the cleaning time of organic matter at the beginning of use. Furthermore, when the metal ion contained in the preservation solution is set to 10 ppb or more and less than 100 ppb, the washing time of the metal components at the start of use can be significantly reduced. In addition, when the chloride ion contained in the preservation solution is 25 ppb or more and less than 250 ppb, by containing such a small amount of chloride ions, a sufficient amount can be obtained even if it is not heated to an excessively high temperature. Bactericidal. According to the manufacturing method of the filtration membrane module of the present invention, pure water filtered and sterilized is sealed in a housing, and the housing sealed with pure water is heated at a temperature of 80 ° C or higher and less than 100 ° C. In this way, the pure water in the filtration membrane module is sterilized to make a preservation solution, so the filtration performance of the membrane can be maintained, and the proliferation of microorganisms in the module can be suppressed. Further, in the step of performing heat treatment on the case sealed with pure water, when a pressure buffer mechanism is provided on the raw water side of the filter membrane module in order to reduce the pressure rise caused by the thermal expansion of the sealed pure water , It can prevent the expansion of the water caused by heating, which will cause the pressure in the filter module to rise and damage the casing or the hollow fiber membrane. When the filter side is completely sealed, it is possible to prevent contamination from the outside. In addition, in the step of performing heat treatment on the shell sealed with pure water, when a volume expansion absorption mechanism is provided on the raw water side of the filter membrane module in order to absorb the volume expansion caused by heat of the sealed pure water, The volume expansion during heat treatment is absorbed, and then the expansion portion is contracted by cooling, so that it can flow into the module from the raw water side of the filter membrane module again, and the filter module can be filled with liquid. .

Hereinafter, a hollow fiber membrane module using one embodiment of the filter membrane module of the present invention will be described with reference to the drawings. The hollow fiber membrane module of this embodiment can be used in a filtering device for producing ultrapure water. The hollow fiber membrane module of this embodiment can be used for external pressure filtration immediately before supplying ultrapure water produced using a microfiltration membrane, ion exchange resin, or reverse osmosis filtration membrane to the point of use, and can be used as a terminal filtration Device to remove particles. In addition, as a hollow fiber membrane module, high filtration performance is required in order to realize the miniaturization of the equipment. However, the hollow fiber membrane module of this embodiment can be made into a hollow fiber membrane mold that can increase the filtration flow rate per unit volume. group. FIG. 1 is a cross-sectional view showing a schematic configuration of a hollow fiber membrane module 1 according to this embodiment. 2 is a perspective view of the hollow fiber membrane module 1 shown in FIG. 1 after being exploded. As shown in FIG. 1, the hollow fiber membrane module 1 of this embodiment includes a hollow fiber membrane bundle 3 that bundles a plurality of hollow fiber membranes 3 a, and a cylindrical casing 5 that houses the hollow fiber membrane bundle 3. Caps 10 and 11 for piping connection are formed at both ends of the casing 5 and are formed with connecting pipes 10a and 11a. The caps 10 and 11 for piping connection are fixed to the casing 5 by nuts 13. The nut 13 is screwed with the male threads formed on the sides of the two ends of the housing 5 to lock the nut 13, thereby using the O-ring 12 arranged in the groove of the cover 10, 11 to connect the two ends of the housing with the cover 10, 11. Sealed. Further, upper and lower nozzles 5a and 5b are formed at both end portions of the casing 5, respectively, to allow fluid to flow. The upper nozzle 5 a and the lower nozzle 5 b are provided so as to protrude in a direction orthogonal to the longitudinal direction of the casing 5. At both end surfaces of the hollow fiber membrane bundle 3, each of the hollow fiber membranes 3a is opened, and the hollow fiber membranes 3a are bonded to each other through a potting material to form a bonding portion 14. In the external pressure filtration, for example, liquid flows from the lower nozzle 5b, and the liquid penetrates from the outer surface of each hollow fiber membrane 3a between the two end portions 14a, and passes through the liquid in the hollow portion of each hollow fiber membrane 3a. The pipes 10a, 11a of the covers 10, 11 flow out. As the hollow fiber membrane 3a, a microfiltration membrane, an ultrafiltration membrane, or the like can be used. The raw material of the hollow fiber membrane is not particularly limited, and examples thereof include polyfluorene, polyetherfluorene, polyacrylonitrile, polyimide, polyetherimine, polyfluorene, polyetherketone, polyetheretherketone, and polyethylene. , Polypropylene, poly (4-methylpentene), ethylene-vinyl alcohol copolymer, cellulose, cellulose acetate, polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene, etc. These composite raw materials can also be used. The inner diameter of the hollow fiber membrane 3a is 50 μm to 3000 μm, and preferably 500 μm to 2000 μm. When the inner diameter is small, the pressure loss becomes large and adversely affects filtration. Therefore, the inner diameter of the hollow fiber membrane 3a is preferably set to 50 μm or more. When the inner diameter is set to be large, it is difficult to maintain the shape of the film during spinning. Therefore, it is preferably set to 3000 μm or less. As the potting material, polymer materials such as epoxy resin, vinyl ester resin, polyurethane resin, unsaturated polyester resin, olefin polymer, silicone resin, and fluorine-containing resin are preferable, and these polymer materials can be used. Either of these may be used in combination of a plurality of polymer materials. Furthermore, in the manufacturing process of ultrapure water, heat resistance to hot water and low dissolution of the constituent members are required. Therefore, as the raw material of the hollow fiber membrane 3a or the casing 5, it is preferable to use a polyfluorene-based material having less elution. For the same reason, epoxy resin is preferably used as the potting material. Further, in the hollow fiber membrane module 1 of this embodiment, sterilized pure water is used as a preservation liquid. The so-called preservation liquid is a liquid used to maintain the filtering performance of the hollow fiber membrane 3a, and is filled between the storage portion 5c, the lids 10, 11 and the adhesive portion 14 formed between the adhesive portions 14 formed at both ends of the casing 5. Liquid in the hollow space and the porous portion of the hollow fiber membrane 3a. Here, the so-called pure water in the present invention means water obtained by reducing ionic components and having a water conductivity of 1 μS / cm or less, and filtering through a reverse osmosis membrane or an ultrafiltration membrane. Moreover, in the hollow fiber membrane module 1 of this embodiment, it is preferable that the organic substance content in the storage solution is 1 ppm or more and less than 50 ppm in terms of TOC (Total Organic Carbon). If TOC is 1 ppm or more, organic matter in pure water is preferentially oxidized during heating and sterilization of pure water described below, and therefore, oxidative degradation of the hollow fiber membrane 3a due to heating can be suppressed. The TOC is more preferably 5 ppm or more. In addition, if it is less than 50 ppm, the concentration of organic matter in the storage solution of the hollow fiber membrane module 1 at the beginning of use can be quickly reduced, and even when the bacteria are not completely killed by heat sterilization, it can be used. Because it has less carbon source, it can inhibit the proliferation of bacteria. Furthermore, in the hollow fiber membrane module 1 of this embodiment, the concentration of metal ions contained in the storage solution is preferably 10 ppb or more and less than 100 ppb. In the ultra-pure water manufacturing process, metal ions that will adversely affect semiconductor manufacturing should be avoided. The smaller the content, the better. On the other hand, in consideration of sterilization, it is known that metal ions exhibit a sterilizing effect. By containing metal ions within a range that does not adversely affect semiconductor manufacturing, the sterilizing effect by heating can be improved. Similarly, in the hollow fiber membrane module 1 of this embodiment, the concentration of chloride ions contained in the preservation solution is preferably 25 ppb or more and less than 250 ppb. In semiconductor manufacturing, chloride ions can also erode circuits, so they are required to be managed to extremely low concentrations in ultrapure water. On the other hand, since chloride ion exhibits a bactericidal effect, it is preferably contained in pure water used as a storage solution in a range that does not adversely affect semiconductor manufacturing. According to the hollow fiber membrane module 1 of the present embodiment described above, ultrapure water that can suppress the proliferation of fungi during storage and that meets the water quality requirements for semiconductor manufacturing can be easily manufactured. Next, a manufacturing method of the hollow fiber membrane module 1 according to this embodiment will be described. In the manufacturing method of the hollow fiber membrane module 1 of this embodiment, first, the filtered and sterilized pure water is sealed in the housing 5 of the hollow fiber membrane module 1 shown in FIG. 1 in a state before the preservation liquid is filled. . As the pure water, water obtained by filtering through a reverse osmosis membrane or an ultrafiltration membrane as described above is used. The fine particles of 50 nm or more contained in pure water are preferably 10 particles / L or more and 200 particles / L or less. Moreover, it is preferable to use water whose content of organic matter in TOC is 1 ppm or more and less than 50 ppm. The TOC is more preferably 5 ppm or more. Further, the concentration of metal ions contained in pure water is preferably 10 ppb or more and less than 100 ppb, and the concentration of chloride ions contained in pure water is preferably 25 ppb or more and less than 250 ppb. Next, in the manufacturing method of the hollow fiber membrane module 1 of this embodiment, the hollow fiber membrane module 1 (housing that is sealed with pure water filtered and sterilized) is sealed at a temperature of 80 ° C or higher and less than 100 ° C. 5) Perform heat treatment. In this way, by further sterilizing the filtered pure water by sterilization, the storage solution of the hollow fiber membrane module 1 can be made into a bacteria-free state. In addition, as a method of sterilizing water, there are also additions of chemicals. However, in the case of a hollow fiber membrane module used in an ultrapure water manufacturing process, heating and sterilization without adding unnecessary components must be performed. In addition, in the case of sterilizing pure water by heating as in the present embodiment, even if it does not reach 80 ° C, most of the germs can be killed over time, and a case of storage for a period of more than 3 months is considered. In this case, it is preferable that the bacteria are sufficiently killed by heating in advance at 80 ° C or higher. When the heating temperature is set to 100 ° C or higher, pure water boils, and the hollow fiber membrane 3a in the hollow fiber membrane module 1 is shaken, which may cause damage or damage due to the difference in the thermal expansion rate of the components. possibility. From these viewpoints, the temperature of the heat treatment is preferably 80 ° C. or higher and less than 100 ° C. as in the present embodiment, and more preferably 85 ° C. or higher and 95 ° C. or lower. Here, when the hollow fiber membrane module 1 is heat-treated in the manner described above, if it is closed by a rigid member that is hardly deformed by pressure, thermal expansion of pure water causes the pressure inside the module to rise. And the hollow fiber membrane 3a or the casing 5 may be damaged. As a method to prevent the pressure from rising, there is a method in which the inside of the module is communicated with the outside, but in this case, the water that expands in volume due to heat treatment will overflow to the outside, and the volume will shrink due to cooling. As a result of inhalation of external air, there is a possibility that fungi will be drawn into the module from the atmosphere at this time. In order to avoid this situation, it is considered to implement a heat treatment step in a sterile room, but a large hollow fiber membrane module used in an ultrapure water manufacturing process is difficult to manufacture in a sterile room. Therefore, in the manufacturing method of the hollow fiber membrane module 1 of this embodiment, in order to reduce the pressure rise caused by the thermal expansion of the enclosed pure water in the heat treatment step, the hollow fiber membrane module 1 The lower nozzle 5b is provided with a pressure buffer mechanism. Furthermore, since the hollow fiber membrane module 1 of this embodiment is used for external pressure filtration, the lower nozzle 5b corresponds to the raw water side port of the present invention. As a pressure buffering mechanism that buffers the pressure caused by the expansion and prevents the inflow of external air, for example, as shown in FIG. 3, the pressure is connected to a rubber balloon or a plastic bag including a dry state at the nozzle 5b on the lower side of the hollow fiber membrane module 1. The method of the buffer mechanism 21 is simple and preferable. However, usually rubber-like soft substances are not heat-resistant, and substances added in order to make them flexible can be dissolved in the contacted pure water, which may reduce the purity of the preservation solution. Therefore, it is better to use materials such as polyethylene. And plastic bags such as polypropylene are heat-resistant and have fewer additives. Also, as described above, the expansion of the plastic bag in the dry state can be used to absorb the volume expansion. However, if a large amount of water overflows into the bag, the amount of the preservation solution that should be sealed in the module is reduced as the seal. One of the purposes of the film is that the drying prevention function becomes insufficient. In order to avoid this, in the manufacturing method of the hollow fiber membrane module 1 of this embodiment, in the heat treatment step, in order to absorb the volume expansion caused by heating of the enclosed pure water, it is preferable to use the hollow fiber membrane module. 1 The lower nozzle 5b is provided with a volume expansion absorption mechanism. As the volume expansion absorption mechanism, for example, as shown in FIG. 3, polyvinylidene fluoride or polypropylene used for connecting a pipe including an ultrapure water device with less heat resistance and less concern about dissolution as shown in FIG. 3 is preferable. The volume expansion and absorption mechanism 20 of the liquid receiver. Further, it is more preferable to connect the pressure buffer mechanism 21 including a member capable of buffering pressure, such as a bag made of polyethylene or polypropylene, in a form covering the liquid receiver. In this way, by having both the pressure buffer mechanism 21 and the volume expansion absorption mechanism 20, the influence of thermal expansion caused by heating can be suppressed, and there is no case where external air is sucked due to cooling, and sterilization by heat treatment can be performed. Moreover, during the above-mentioned heat treatment, as shown in FIG. 3, the upper pipe 10a, the lower pipe 11a, and the upper nozzle 5a are blocked by the fastening members 10b, 11b, and 23, respectively, and are sealed. The upper pipe 10a and the lower pipe 11a correspond to the filtering side port in the present invention. Furthermore, in the manufacturing method of the hollow fiber membrane module 1 of this embodiment, as shown in FIG. 3, it is preferable that the pressure buffer mechanism 21 includes a fastening member 22 therein. Further, it is preferable to replace the volume expansion absorption mechanism 20 with the bolting member 22 in the pressure buffer mechanism 21 after the heat treatment step, and then remove the pressure buffer mechanism 21 and the volume expansion absorption mechanism 20. By adopting this method, the lower nozzle 5b can be hermetically closed in the state of the lock system. In the manufacturing method of the hollow fiber membrane module 1 of this embodiment, the installation of the volume expansion absorption mechanism 20 and the pressure buffer mechanism 21 and the replacement of the fastening member 22 are all performed at the nozzle 5b on the lower side of the raw water side. Therefore, even if fungal contamination occurs, it only occurs on the raw water side where the bolting member 22 is replaced, and it is possible to prevent fungal contamination from occurring in the completely closed system that is separated by the hollow fiber membrane 3a, that is, the filtering side. In addition, in the step of performing the heat treatment, as shown in FIG. 4, a structure for reducing the pressure rise caused by the thermal expansion of the enclosed pure water and absorbing the volume expansion of the enclosed pure water can be adopted. The structure is not limited to the structure shown in FIG. 3. In the hollow fiber membrane module 1 shown in FIG. 4, as a volume expansion absorption mechanism, a polypropylene (PP) bottle 24 and a tube 25 are provided. The polypropylene bottle 24 is attached to the lower nozzle 5b on the raw water side via a tube 25, and a filter made of polytetrafluoroethylene (PTFE) with a hole diameter of 0.2 μm is provided on the upper portion of the polypropylene bottle 24. The device 26 serves as a pressure buffer mechanism. The vent filter 26 allows gas to pass through, but does not allow bacteria to pass through. Furthermore, in the hollow fiber membrane module 1 shown in FIG. 4, a polyethylene bag 27 is provided as a gas inflow prevention member that prevents external air from flowing into the lower nozzle 5 b. The polyethylene bag 27 is provided so as to cover the lower nozzle 5b in a state in which the fastening member 22 is contained therein. In addition, the portion of the tube 25 (the portion indicated by the dashed oval in FIG. 4) passing through the polyethylene bag 27 is hermetically sealed. Further, it is preferable to replace the tube 25 with a fastening member 22 in a polyethylene bag 27 after the heat treatment step, and then replace the polyethylene bag 27, the tube 25, and a polypropylene (PP) bottle. 24 and the vent filter 26 are removed from the lower nozzle 5b. Next, an example in which the hollow fiber membrane module 1 of the present embodiment is installed in the water treatment device 100 for ultra-pure manufacturing will be described with reference to FIG. 5, and the hollow fiber membrane module using the present embodiment will be described. The filtering method of group 1 will be described. In addition, in this water treatment device 100 for ultra-pure manufacturing, a sweep flow filtration method in external pressure filtration is assumed. As shown in FIG. 5, the water treatment device 100 is used as a final filter of ultrapure water, for example, and supplies the water to be treated from the lower nozzle 5b to the storage portion 5c outside the hollow fiber membrane 3a, and filters the water to the On the inside (hollow portion) side, filtered water (ultra-pure water) is discharged from the pipes 10a, 11a at both ends of the hollow fiber membrane bundle 3. The circulating water (concentrated water) is discharged through the upper nozzle 5a. The water treatment device 100 includes a supply pipe 101 connected to the lower nozzle 5b of the hollow fiber membrane module 1 to supply water to be treated, and a circulation pipe 102 connected to the upper nozzle 5a to send circulating water. Further, a pressure gauge, various valves 101a, 102a, and the like are arranged in the middle of the supply pipe 101 or the circulation pipe 102. The water treatment apparatus 100 includes a first filtered water collection pipe 103 and a second filtered water collection pipe 104 that serve as a flow path of the filtered water. The first filtered water collecting pipe 103 or the second filtered water collecting pipe 104 is connected to a combined pipe 105 of filtered water, and the combined pipe 105 is connected to an external pipe (not shown). In addition, a pressure gauge, various valves 105a, and the like are arranged in the merging pipe 105. In addition, when the hollow fiber membrane module 1 is installed in the water treatment device 100, firstly, the fastening members 10b, 11b, 22, and 23 of the closed hollow fiber membrane module 1 are removed, and the hollow fiber membrane module 1 is sealed. The pure water (preservation liquid) is discarded outside the pipes of the water treatment apparatus 100. Then, the hollow membrane module 1 is attached to a pipe of the water treatment apparatus 100 thereafter. Generally, when a sterilized hollow fiber membrane module is installed in a water treatment device, in order to prevent contamination of fungi, it is installed in a piping in a closed form, or in a state where the preservation solution in the hollow fiber membrane module is not discarded. Under installation, the storage solution in the hollow fiber membrane module is discarded while being replaced with the supply water. However, in the case of a water treatment device for ultrapure water used in semiconductor devices and the like, if the preservation liquid in the hollow fiber membrane module is caused to flow into the system, the cleanliness of the water of the ultrapure water is reduced. It takes time to become clean in the system. Therefore, in this embodiment, the storage liquid in the hollow fiber membrane module 1 is actively discarded to the outside of the system, and then installed in the water treatment device 100. The air-fiber membrane module 1 is arranged vertically with the upper nozzle 5a side facing upward. The upper nozzle 5a is connected to the circulation pipe 102, and the pipe 10a of the cover 10 is connected to the first filtered water collection pipe 103. The lower nozzle 5b is connected to the supply pipe 101, and the pipe 11a of the cover 11 is connected to the second filtered water collecting pipe 104. The water to be treated is introduced from the supply pipe 101 through the lower nozzle 5b to the storage section 5c of the hollow fiber membrane module 1 under a specific pressure. In the casing 5, most of the treated water introduced is filtered by the hollow fiber membrane 3a to reach the hollow portion, and moves upward or downward as filtered water. The filtered water moved to the upper or lower side flows into the cover 10 or 11 from the opening at the end of the hollow fiber membrane 3a, and passes through each of the pipes 10a, 11a, the first filtered water collecting pipe 103 or the second filtered water collecting pipe 104 Then, it is discharged to the merging pipe 105 and collected through an external pipe. On the other hand, the water to be treated that has not penetrated the hollow fiber membrane 3 a and rose in the storage portion 5 c in the housing 5 is discharged from the upper nozzle 5 a as circulating water and sent to the circulation pipe 102. [Examples] Hereinafter, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to these examples. In the following examples and comparative examples, a hollow fiber membrane module was used. The characteristics and various water quality analysis methods are shown below. [About Hollow Fiber Membrane] Material: Polyfluorene Division Molecular Weight: 6000 Da (Ultrafiltration Membrane) Inner Diameter / Outer Diameter: 0.6 mm / 1.0 mm [Housing for making hollow fiber membrane module] Material: Polyurethane shape: Cylindrical size: Inner diameter / outer diameter of the cylindrical portion of the filter area: 154 mm / 170 mm Inner diameter / outer diameter of the cylindrical portion of the nozzle portion: 162 mm / 183 mm Inner diameter of the nozzle: 58 mm Length of the cylindrical case / The distance between the centers of the nozzles: 1050 mm / 872 mm [Confirmation of sterilization effect] Sampling the water enclosed in the hollow fiber membrane module, using the HPC Total Count Sampler (Millipore) Type: MHPC10025) to determine the presence or absence of bacteria. When used as a hollow fiber membrane module, UltraDI-50 manufactured by Particle Measuring Systems was used to confirm the state of bacteria counted in the form of fine particles in filtered water. [Analysis of Contained Content of Preservation Solution] The analysis of the concentration of various components in the preservation solution (pure water) was performed using the following equipment. Microparticles: UltraDI-50 TOC manufactured by Particle Measuring Systems: TOC5000A manufactured by Shimadzu Corporation Metal ion concentration: 7500cs chloride ion manufactured by Agilent Technologies: 881Compact IC manufactured by Metrohm [Example 1] Ultrafiltration will be used Pure water obtained by membrane filtration was sealed in a hollow fiber membrane module, and the hollow fiber membrane module was placed in an oven, and was subjected to a heat treatment at 90 ° C for 16 hours, so that it was sealed inside the module and sterilized. The state of pure water. In addition, during the heat treatment, a nozzle made of polyethylene (PE) was installed on the raw water side as a pressure buffer mechanism, and a nozzle made of polypropylene (PP) was installed on the raw water side as a volume expansion absorption. mechanism. After the heat treatment was completed, the nozzle was sealed with a specific fastening member, and stored in a storage room whose temperature was adjusted to 20 ° C to 25 ° C for 3 months. After 3 months of storage, the pure water sealed as a preservation solution was sampled, and the number of germs in the preservation solution was counted. The concentrations of TOC, metal ions, and chloride ions in the storage solution were measured together. The results are shown in Table 1. Using this hollow fiber membrane module to manufacture ultrapure water, as a result, filtered water that can be used as ultrapure water can be obtained immediately from the start of operation. [Examples 2 and 3] Except that the heating temperature and heating time were changed to the conditions described in Table 1, in the same manner as in Example 1, the number of bacterial counts after heat treatment and storage, and the TOC in the storage solution were measured. , Metal ion, and chloride ion concentration. The results are shown in Table 1. In Example 3, although the bacterial count was 3 after 3 months of storage, the hollow fiber membrane modules of this example were used to manufacture ultrapure water. As a result, it was immediately available from the start of operation and could be used as ultrapure water. The quality of the filtered water. [Examples 4, 5, and 6] In the same manner as in Example 1, the counts of the number of germs after heat treatment and storage, and the respective concentrations of TOC, metal ions, and chloride ions in the storage solution were measured. The results are shown in Table 1. The manufacture of ultrapure water is performed using each hollow fiber membrane module of this embodiment, and as a result, filtered water that can be used as ultrapure water can be obtained immediately from the start of operation. [Example 7] Except that the pressure buffer mechanism was not provided, the nozzle on the raw water side was opened, and the heat treatment was performed without the volume absorption mechanism. Except for this, the health after heat treatment and storage was measured in the same manner as in Example 1. Count of bacteria, concentration of TOC, metal ion, and chloride ion in pure water. The results are shown in Table 1. Since a large amount of water overflows from the nozzle during the heating process, an air accumulation portion is generated in the module when it is cooled to normal temperature. In addition, the bacterial count after storage for 3 months was 29. Therefore, the manufacturing test of ultrapure water using the hollow fiber membrane module of this example was not implemented. [Example 8] Except not using a polypropylene cup as a volume expansion absorption mechanism, in the same manner as in Example 1, the number of bacterial counts after heat treatment and storage, TOC in pure water, metal ions, And chloride ion concentration. The results are shown in Table 1. During the heat treatment, it was confirmed that water leaked into the polyethylene bag as a pressure buffer mechanism. The hollow fiber membrane module of this embodiment is used to manufacture ultrapure water. As a result, filtered water that can be used as ultrapure water can be obtained immediately from the start of operation. [Example 9] Pure water obtained by filtering with an ultrafiltration membrane was sealed in a hollow fiber membrane module, and the hollow fiber membrane module was placed in an oven and subjected to a heat treatment at 90 ° C for 16 hours to make It is in a state in which sterilized pure water is enclosed in the module. Furthermore, in Example 9, when the structure shown in FIG. 4 was used for the heat treatment, a nozzle made of a polypropylene (PP) bottle mounted on the raw water side via a tube was used as a volume expansion absorption mechanism, A filter (PTFE filter) made of polytetrafluoroethylene (PTFE) with a pore diameter of 0.2 μm was mounted on the upper part of the acrylic bottle as a pressure buffer mechanism. After the heat treatment was completed, the nozzle was sealed with a specific fastening member previously placed in a polyethylene bag mounted on the nozzle, and stored in a storage room whose temperature was adjusted to 20 ° C to 25 ° C for 3 months. After 3 months of storage, the pure water sealed as a preservation solution was sampled, and the number of germs in the preservation solution was counted. The concentrations of TOC, metal ions, and chloride ions in the storage solution were measured together. The manufacture of ultrapure water was carried out using the hollow fiber membrane module of Example 9. As a result, filtered water that can be used as ultrapure water was immediately obtained from the start of operation. [Comparative Example 1] Pure water obtained by filtration using an ultrafiltration membrane was sealed in a hollow fiber membrane module at the same time as in Example 1 as a preservation liquid and sealed. The module was stored in a storage room whose temperature was adjusted to 20 ° C to 25 ° C for 3 months. After 3 months of storage, the pure water sealed as a preservation solution was sampled, and the number of germs in the preservation solution was counted. The concentrations of TOC, metal ions, and chloride ions in the storage solution were measured together. The results are shown in Table 1. In this comparative example, a large amount of bacteria (100 or more and difficult to count) were confirmed from pure water as a preservation solution. The hollow fiber membrane module was used to manufacture ultrapure water. As a result, a large number of fine particles derived from germs were observed in the filtered water. Compared with Example 1, it would take 14 times longer to reduce the fine particles. [Table 1]

1‧‧‧ hollow fiber membrane module

3‧‧‧ hollow fiber membrane bundle

3a‧‧‧ hollow fiber membrane

5‧‧‧shell

5a‧‧‧upper nozzle

5b‧‧‧Lower side nozzle

5c‧‧‧Storage Department

10‧‧‧ cover

10a‧‧‧pipe

10b‧‧‧ Tightening member

11‧‧‧ cover

11a‧‧‧pipe

11b‧‧‧ Tightening member

12‧‧‧O-ring

13‧‧‧ Nut

14‧‧‧ Follow-up

20‧‧‧Volume expansion absorption mechanism

21‧‧‧pressure buffer mechanism

22‧‧‧ Tightening member

23‧‧‧ Tightening member

24‧‧‧ Polypropylene (PP) bottles

25‧‧‧tube

26‧‧‧ Vent Filter

27‧‧‧ Bags made of polyethylene

100‧‧‧ over device

101‧‧‧ supply piping

101a‧‧‧Various valves

102‧‧‧Circular piping

102a‧‧‧Various valves

103‧‧‧The first filtered water collection pipe

104‧‧‧Second filtered water collection pipe

105‧‧‧ Confluence

105a‧‧‧Various valves

FIG. 1 is a cross-sectional view showing a configuration of a hollow fiber membrane module using one embodiment of the filter membrane module of the present invention. Figure 2 is an exploded perspective view of a hollow fiber membrane module. FIG. 3 is a diagram showing a specific example of a pressure buffer mechanism and a volume expansion absorption mechanism. FIG. 4 is a diagram showing another example of the pressure buffer mechanism and the volume expansion absorption mechanism. FIG. 5 is a diagram showing a detailed configuration of each part of a filtering device using the hollow fiber membrane module shown in FIG. 1.

Claims (15)

A filter membrane module is provided with a filter membrane used for liquid filtration and a housing for containing the filter membrane, and is characterized in that the housing is filled with sterilized pure water as a means for holding the filter membrane. Preservative for filtration performance. For example, the filtration membrane module of claim 1, wherein the content of organic matter in the storage solution is 5 ppm or more and less than 50 ppm by TOC (Total Organic Carbon). For example, the filtration membrane module of claim 1, wherein the concentration of the metal ions contained in the storage solution is 10 ppb or more and less than 100 ppb. The filter membrane module according to any one of claims 1 to 3, wherein the concentration of the chloride ion contained in the storage solution is 25 ppb or more and less than 250 ppb. A manufacturing method of a filtering membrane module, characterized in that it is a method for manufacturing a filtering membrane module, which is provided with a filtering membrane used for liquid filtration and a housing for containing the filtering membrane, and The above-mentioned case is filled with sterilized pure water as a preservation liquid to maintain the filtering performance of the above-mentioned filter membrane, and the manufacturing method is to seal the filtered and sterilized pure water into the case containing the above-mentioned filter membrane, and The housing sealed with pure water is heated at a temperature of 80 ° C or higher and less than 100 ° C, thereby sterilizing the pure water in the filter membrane module to prepare the preservation solution. For example, in the method for manufacturing a filtration membrane module according to claim 5, wherein in the step of heating the shell sealed with pure water, in order to reduce the pressure rise caused by the thermal expansion of the sealed pure water, A pressure buffer mechanism is provided on the raw water side of the filter membrane module. For example, the manufacturing method of the filtration membrane module of claim 5 or 6, wherein in the step of heating the above-mentioned case sealed with pure water, in order to absorb the heat-induced volume expansion of the sealed pure water, A volume expansion absorption mechanism is provided on the raw water side of the filter membrane module. For example, the manufacturing method of the filtration membrane module of claim 5 or 6, wherein the pure water filtered and sterilized is water obtained by filtering through an ultrafiltration membrane or reverse osmosis membrane, and the pure water contained in The number of fine particles is 10 particles / L or more and 200 particles / L or less. For example, the method for manufacturing a filtration membrane module according to claim 5 or 6, wherein the content of organic matter in the pure water is 5 ppm or more and less than 50 ppm by TOC (Total Organic Carbon). For example, the manufacturing method of the filtration membrane module of claim 5 or 6, wherein the concentration of the metal ions contained in the pure water is 10 ppb or more and less than 100 ppb. For example, the manufacturing method of the filtration membrane module of claim 5 or 6, wherein the concentration of the chloride ion contained in the pure water is 25 ppb or more and less than 250 ppb. For example, in the method for manufacturing a filtration membrane module according to claim 5, wherein in the step of heating the shell sealed with pure water, in order to reduce the pressure rise caused by the thermal expansion of the sealed pure water, A pressure buffer mechanism is provided on the raw water side of the filter membrane module, and a volume expansion absorption mechanism is provided on the raw water side of the filter membrane module to absorb the volume expansion caused by heat of the enclosed pure water, and the filter membrane is provided. The filter side of the module is closed. The manufacturing method of the filter membrane module according to claim 12, wherein the filter membrane module is a hollow fiber membrane module that contains a hollow fiber membrane as the filter membrane in the housing, and has a hollow portion similar to the hollow fiber membrane. In the connected filtering side port and the raw water side port communicating with the outer side of the hollow fiber membrane, in the step of heating the shell filled with pure water, the volume expansion absorption mechanism is provided in the raw water side port, and at the same time, The pressure buffer mechanism is provided in a state in which the pressure buffer mechanism includes a fastening member, and the filtering side port is set to a closed state. After the heat treatment step, the volume expansion absorption mechanism is replaced in the pressure buffer mechanism. It is the above-mentioned fastening member, and then the pressure buffer mechanism and the volume expansion absorption mechanism are removed. The manufacturing method of the filter membrane module according to claim 12, wherein the filter membrane module is a hollow fiber membrane module that contains a hollow fiber membrane as the filter membrane in the housing, and has a hollow portion similar to the hollow fiber membrane. In the connected filtering side port and the raw water side port communicating with the outer side of the hollow fiber membrane, in the step of heating the shell sealed with pure water, the volume expansion absorption mechanism is provided in the raw water side port, and The volume expansion absorption mechanism is provided with the pressure buffering mechanism that allows gas to pass through but does not allow bacteria to pass through, and further, a gas inflow prevention member that prevents inflow of external air is provided on the raw water side in a state that the gas inflow member includes a fastening member Port, and the filtering side port is set to a closed state. After the heat treatment step, the volume expansion absorption mechanism is replaced with the bolting member in the gas inflow prevention member, and the pressure buffer is removed after the removal. The volume expansion absorption mechanism and the gas inflow prevention member of the mechanism. A method for setting a filtration membrane module, which is a method for installing a filtration membrane module manufactured using the manufacturing method of claim 13 or 14 on a piping of a water treatment device, which is characterized in that: the above-mentioned filtration membrane module is sealed. The fastening members of the filtering side port and the raw water side port are removed, and the pure water sealed in the filtering membrane module is discarded out of the pipes of the water treatment device, and then the pipes of the water treatment device are installed.