CN116528967A - Hollow fiber membrane module - Google Patents
Hollow fiber membrane module Download PDFInfo
- Publication number
- CN116528967A CN116528967A CN202180080556.4A CN202180080556A CN116528967A CN 116528967 A CN116528967 A CN 116528967A CN 202180080556 A CN202180080556 A CN 202180080556A CN 116528967 A CN116528967 A CN 116528967A
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- CN
- China
- Prior art keywords
- hollow fiber
- fiber membrane
- fiber membranes
- fixing portion
- adhesive fixing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000012528 membrane Substances 0.000 title claims abstract description 546
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 530
- 239000000853 adhesive Substances 0.000 claims abstract description 218
- 230000001070 adhesive effect Effects 0.000 claims abstract description 218
- 230000002093 peripheral effect Effects 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 30
- 229920001187 thermosetting polymer Polymers 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 11
- 239000004840 adhesive resin Substances 0.000 claims description 3
- 229920006223 adhesive resin Polymers 0.000 claims description 3
- 239000000463 material Substances 0.000 description 55
- 238000004382 potting Methods 0.000 description 49
- 238000005259 measurement Methods 0.000 description 23
- 239000002033 PVDF binder Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000009826 distribution Methods 0.000 description 17
- 229910052602 gypsum Inorganic materials 0.000 description 10
- 239000010440 gypsum Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 241001354471 Pseudobahia Species 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- 238000005266 casting Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000011085 pressure filtration Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 206010042496 Sunburn Diseases 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/031—Two or more types of hollow fibres within one bundle or within one potting or tube-sheet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
- D01F6/12—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polymers of fluorinated hydrocarbons
Abstract
Provided is a hollow fiber membrane module capable of suppressing breakage of a hollow fiber membrane. In a hollow fiber membrane module in which both ends of a bundle of hollow fiber membranes are housed in a housing via an adhesive fixing portion, when a horizontal line is drawn perpendicular to a vertical line extending from the upper vertex toward the center of the end face and passing through the center, and a point corresponding to a portion of the minimum thickness on the outer peripheral surface of the adhesive fixing portion is set as an upper vertex on the end face of the adhesive fixing portion of the hollow fiber membrane opening, (the number of hollow fiber membranes located on the upper side of the horizontal line)/(the number of hollow fiber membranes located on the lower side) is 0.9 to 1.1.
Description
Technical Field
The present invention relates to a hollow fiber membrane module.
Background
Generally, hollow fiber membrane modules are broadly classified into internal pressure type and external pressure type. The external pressure type hollow fiber membrane module is generally configured such that both ends of a cylindrical housing are sealed with a potting material (adhesive), and a bundle of hollow fiber membranes having both ends bonded and fixed by the potting material is housed in the housing. The external pressure type hollow fiber membrane component comprises a single-end water collection component with one end of the hollow fiber membrane sealed and the other end open and a two-end water collection component with two open ends of the hollow fiber membrane.
In the production of hollow fiber membrane modules, for example, a centrifugal bonding method is used. In the centrifugal bonding method, a cylindrical case is horizontally placed and rotated, and a potting agent is solidified at both ends of the case by centrifugal force. Therefore, when the filling rate of the hollow fiber membrane is low, the hollow fiber membrane is bonded and fixed in a biased state by gravity.
When the external pressure type hollow fiber membrane module is used for sterilization or turbidity removal, physical cleaning such as back flushing or air washing is required to be periodically performed to restore the filtration performance in order to perform stable filtration operation. When such air washing is performed, if the density distribution of the hollow fiber membranes inside the case is deviated, the hollow fiber membranes are easily broken by a large swing.
For this reason, in order to prevent the density distribution variation of the hollow fiber membranes, for example, patent documents 1 and 2 describe a hollow fiber membrane module in which a cross-shaped or rod-shaped restricting member for preventing the density distribution variation of the hollow fiber membranes is provided at an end portion in a bundle of the hollow fiber membranes and is bonded and fixed.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2015-131267
Patent document 2: japanese patent laid-open No. 2000-185220
Disclosure of Invention
Problems to be solved by the invention
However, since the hollow fiber membranes cannot be disposed at the location where the restriction member is disposed, there is a problem in that a relatively high-density portion and a low-density portion of the hollow fiber membranes exist inside the housing.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a hollow fiber membrane module capable of preventing variation in density distribution of hollow fiber membranes in a housing and suppressing breakage of the hollow fiber membranes.
Means for solving the problems
The gist of the present invention is as follows.
[1] A hollow fiber membrane module, the hollow fiber membrane module comprising: a tubular casing, a hollow fiber membrane bundle formed by bundling a plurality of hollow fiber membranes, a first adhesive fixing part and a second adhesive fixing part,
the two end parts of the hollow fiber membrane bundle are respectively accommodated in the cylindrical shell through the first bonding fixing part and the second bonding fixing part;
the first and second adhesive fixing portions have substantially circular end faces perpendicular to a longitudinal direction of the housing, and hollow portions of the plurality of hollow fiber membranes are open at least one of the end faces;
In the first adhesive fixing portion and/or the second adhesive fixing portion having the end face of the hollow portion opening of the hollow fiber membranes, the hollow fiber membrane bundles are adhered and fixed to the housing by filling the adhesive resin with a prescribed thickness in the longitudinal direction in a state in which a restricting member restricting the deflection of the plurality of hollow fiber membranes is not included in a region between the outer surfaces of the plurality of hollow fiber membranes and the inner surface of the housing;
when a horizontal line is drawn perpendicular to a vertical line extending from the upper vertex toward the center of the end face and passing through the center, a ratio of the number of hollow fiber membranes located above the horizontal line to the number of hollow fiber membranes located below (the number of hollow fiber membranes located above)/(the number of hollow fiber membranes located below) is 0.9 or more and 1.1 or less.
[2]The hollow fiber membrane module according to item 1, wherein, when the package is defined on the end surface of the hollow opening of the hollow fiber membrane of the first adhesive fixing portion and/or the second adhesive fixing portion A first perfect circle including a perfect circle having a smallest diameter of all hollow fiber membranes present on an end face, a second perfect circle concentric with the first perfect circle and having a diameter smaller than 2cm than the first perfect circle, a first square having a largest one side of Ncm (where N is a natural number) as a square located at a center in the second perfect circle, and N obtained by dividing the first square into 1cm squares 2 In the case of the second squares, the ratio of (minimum value)/(maximum value) of the number of hollow fiber membranes included in each of the second squares is 0.4 or more.
[3] The hollow fiber membrane module according to item 1 or 2, wherein a diameter of an end surface of the hollow portion opening of the hollow fiber membrane is 150mm or more.
[4]The hollow fiber membrane module according to any one of items 1 to 3, wherein (thickness L of the adhesive fixing portion at one intersection of the outer peripheral surface and the horizontal line) 1 And a thickness L of the adhesive fixing portion at the other intersection point of the outer peripheral surface and the horizontal line 2 The average value of (1) - (the thickness L of the adhesive fixing portion at the center of the end face) О ) 1mm or more and 12mm or less, and,
(thickness L of the adhesive fixing portion at the other intersection point of the outer peripheral surface and a perpendicular line from the upper side apex toward the center of the end surface 4 ) - (thickness L of the adhesive securing portion at the upper side apex) 3 ) 3mm or more and 12mm or less.
[5] The hollow fiber membrane module according to any one of items 1 to 4, wherein the overall length of the housing is 1m and more.
[6] The hollow fiber membrane module according to any one of items 1 to 5, wherein a total cross-sectional area of all hollow fiber membranes/a cross-sectional area of a housing interior, that is, a filling rate of hollow fiber membranes on an end face of a hollow portion opening of the hollow fiber membranes is 10% or more and 45% or less.
[7] The hollow fiber membrane module according to item 6, wherein a total cross-sectional area of all the hollow fiber membranes/a cross-sectional area of the inside of the housing, that is, a packing ratio of the hollow fiber membranes on an end surface of the hollow openings of the hollow fiber membranes is 25% or more.
[8] The hollow fiber membrane module according to any one of items 1 to 7, wherein the resin constituting the first adhesive fixing portion and/or the second adhesive fixing portion having the end face of the hollow portion opening of the hollow fiber membrane is a single thermosetting resin having a D hardness of 60 or less at 25 ℃ in accordance with JIS K7215.
[9] The hollow fiber membrane module according to item 8, wherein the single thermosetting resin is a two-liquid curable thermosetting resin having a viscosity of 1pa·s or more and 10pa·s or less after 10 minutes from the start of two-liquid mixing and a viscosity exceeding 100pa·s after 30 minutes.
[10] The hollow fiber membrane module according to any one of items 1 to 9, wherein the plurality of hollow fiber membranes are composed of a fluororesin.
[11] The hollow fiber membrane module according to any one of items 1 to 10, wherein, on a virtual bonding interface in which an end surface of a hollow portion opening of the hollow fiber membrane is virtually moved in parallel toward a longitudinal center by an amount of a thickness of a portion having a minimum thickness in an outer peripheral surface of the first bonding fixing portion and/or the second bonding fixing portion, a total cross-sectional area of all hollow fiber membranes/a case inner cross-sectional area is 20% or more and 50% or less, and, on the virtual bonding interface, a point corresponding to a portion having a minimum thickness in the longitudinal direction on the outer peripheral surface is set to be an upper vertex, and when a horizontal line orthogonal to a vertical line extending from the upper vertex toward a center of the virtual bonding interface and passing through the center is drawn, a ratio of the number of hollow fiber membranes located on an upper side of the horizontal line to the number of hollow fiber membranes located on a lower side (the number of hollow fiber membranes located on the upper side)/(the number of hollow fiber membranes located on the lower side) is set to be 0.85 or more and 1.15 or less.
Effects of the invention
According to the present invention, it is possible to obtain a hollow fiber membrane module capable of preventing variation in density distribution of hollow fiber membranes in a housing and suppressing breakage of the hollow fiber membranes.
Drawings
FIG. 1 is a diagram showing a schematic structure of an embodiment of a hollow fiber membrane module 1 of the present invention
FIG. 2 is an enlarged sectional view of the upper part of the hollow fiber membrane module 1 shown in FIG. 1
FIG. 3 is a C-D line sectional view of the hollow fiber membrane module 1 shown in FIG. 1
Fig. 4 is a schematic view showing the appearance of the protection member 8 provided inside the housing 5
FIG. 5 is a schematic view for explaining the protrusion 50 of the hollow fiber membrane 2
FIG. 6 is a schematic view of the hollow fiber membrane module 1 shown in FIGS. 1 and 2 when the end face 21a of the second adhesive fixing portion 21 is viewed from the direction of arrow A
FIG. 7 is a schematic view showing a cross section of a part of the interior of the case 5 for explaining the position of the virtual bonding interface S'
FIG. 8 is a schematic view of the hollow fiber membrane module 1 shown in FIGS. 1 and 2 when the end face 21a of the second adhesive fixing portion 21 is viewed from the arrow A direction
FIG. 9 is a schematic view showing a cross section of a part of the interior of the case 5 for explaining the shape of the interface of the second adhesive fixing portion 21
FIG. 10 is a schematic view showing an end face of a second adhesive fixing portion of the hollow fiber membrane module of comparative example 1
Detailed Description
Hereinafter, an exemplary embodiment (hereinafter, also referred to as the present embodiment) for carrying out the present invention will be described in detail. The present invention is not limited to the embodiments described below, and various modifications and uses can be made within the scope of the gist shown in the present invention. In the drawings, the dimensions of the elements are shown with emphasis on illustration.
Structure of hollow fiber Membrane Module 1
Next, the hollow fiber membrane module 1 of the present embodiment will be described with reference to the drawings. The hollow fiber membrane module 1 of the present embodiment is used in various fields such as sewage, food industry, general industry, medical treatment, and physical chemistry. Fig. 1 is a diagram showing a schematic structure of a hollow fiber membrane module 1 of the present embodiment; fig. 2 is an enlarged sectional view of a part of the hollow fiber membrane module 1 shown in fig. 1. In fig. 1, the vertical direction is indicated by arrows as an upward direction T and a downward direction B. In the following, the vertical direction shown in fig. 1 will be described as the vertical direction of the hollow fiber membrane module 1.
Fig. 1 shows an embodiment of an external pressure type hollow fiber membrane module, but the present embodiment may also be applied as an internal pressure type hollow fiber membrane module.
As shown in fig. 1, the hollow fiber membrane module 1 of the present embodiment schematically includes a cylindrical housing 5, a hollow fiber membrane bundle 3 in which a plurality of hollow fiber membranes 2 are bundled, a first adhesive fixing portion 20, and a second adhesive fixing portion 21. The hollow fiber membrane bundle 3 is housed in the tubular housing 5 at both end portions thereof via the first adhesive fixing portion 20 and the second adhesive fixing portion 21. The hollow fiber membrane module 1 of the present embodiment may be erected so that the longitudinal direction thereof becomes the vertical direction.
The total length of the case 5 is preferably 1m or more, more preferably 1.5m or more and 2.5m or less. This can reduce the space required for installing the water treatment facility and increase the flow rate of the filtration treatment of the hollow fiber membrane module 1.
< Shell 5 >
The substantially cylindrical housing 5 is configured by joining a first cylindrical member 51 located at a lower portion of the housing 5, a second cylindrical member 52 located at an upper portion of the housing 5 and integrally formed with the nozzle 52a, and a straight tubular third cylindrical member 53 disposed between the first cylindrical member 51 and the second cylindrical member 52 to each other. The nozzle 52a is provided on a side portion of the second tubular member 52 and is provided so as to protrude in a direction orthogonal to the longitudinal direction of the housing 5.
Covers 10 and 11 for piping connection having a hollow tapered shape, which are formed with pipes 10a and 11a for piping connection, are provided at both end openings of the housing 5, respectively, and the covers 10 and 11 for piping connection are fixedly attached to the housing 5 by a jig 13.
In the process of the external pressure filtration treatment of the present embodiment, the water to be treated (liquid to be treated) is supplied from the pipe 10a of the cap 10 into the hollow fiber membrane module 1, and the filtered water is discharged to the outside of the hollow fiber membrane module 1 through the pipe 11a of the cap 11 and the concentrated water through the nozzle 52 a. As another aspect, the housing 5 may further include a nozzle (not shown) on a side portion of the first tubular member 51, and the water to be treated (liquid to be treated) may be supplied to the hollow fiber membrane module 1 through the nozzle.
Annular grooves are formed in the end surfaces of the covers 10 and 11 on the side of the case 5 and the end surfaces of the covers 10 and 11 on the side of the case 5, and an annular sanitary pad (sanitary pad) 12 is sandwiched between the grooves. By means of this sanitary gasket 12, the space between the two ends of the housing 5 and the covers 10 and 11 is sealed, preventing water leakage from the hollow fiber membrane module 1.
< hollow fiber Membrane Beam >)
The hollow fiber membrane bundle 3 is housed in the housing 5 so as to extend over the entire length of the housing 5. The hollow fiber membrane bundle 3 is formed by bundling a plurality of hollow fiber membranes 2 each having a long, thin, hollow cylindrical shape. The hollow fiber membranes 2 constituting the hollow fiber membrane bundle 3 do not have to be all the same in length, but are preferably of a certain length. The inner space of the housing 5 is divided into an inner region and an outer region 5b as hollow portions of the hollow fiber membranes 2 by the hollow fiber membrane bundle 3.
The hollow fiber membrane 2 preferably has an inner diameter of 50 μm or more and 3000 μm or less, more preferably 500 μm or more and 2000 μm or less. In addition, a hollow fiber membrane having an inner diameter/outer diameter ratio of 0.3 or more and 0.8 or less is preferably used.
As the hollow fiber membrane 2, a reverse osmosis membrane, a nanofiltration membrane, an ultrafiltration membrane, and a microfiltration membrane can be used. The material of the hollow fiber membrane 2 is not particularly limited, and examples thereof include polysulfone, polyethersulfone, polyacrylonitrile, polyimide, polyetherimide, polyamide, polyetherketone, polyetheretherketone, polyethylene, polypropylene, poly (4-methylpentene), ethylene-vinyl alcohol copolymer, cellulose acetate, polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene, and the like, and composite materials thereof may be used.
In one embodiment, the plurality of hollow fiber membranes 2 are composed of a fluororesin, more preferably polyvinylidene fluoride. This can improve the ease of cleaning and durability of the hollow fiber membrane 2.
< first adhesive fixing portion 20 and second adhesive fixing portion 21>
A first adhesive fixing portion 20 and a second adhesive fixing portion 21 are formed at both end portions of the hollow fiber membrane bundle 3, each of which is substantially cylindrical, and each of which is formed by adhering and fixing the hollow fiber membranes 2 to each other and adhering and fixing the hollow fiber membrane bundle 3 to the inner wall of the housing 5. The first adhesive fixing portion 20 and the second adhesive fixing portion 21 have substantially circular end faces perpendicular to the longitudinal direction of the housing 5, and the hollow portions of the plurality of hollow fiber membranes 2 are opened at least one end face.
In the hollow fiber membrane module 1 of the present embodiment, in the adhesive fixing portion 20 and/or the adhesive fixing portion 21 having the end face of the hollow portion opening of the hollow fiber membranes 2, the hollow fiber membrane bundles 3 are adhered and fixed to the housing 5 in a liquid-tight state by filling the adhesive resin with a predetermined thickness in the longitudinal direction in a state where the restricting member restricting the deflection of the plurality of hollow fiber membranes 2 is not included in the region between the outer surfaces of the plurality of hollow fiber membranes 2 and the inner surface of the housing 5. Hereinafter, the term "adhesive fixing portion thickness" refers to the thickness of the first adhesive fixing portion 20 and the second adhesive fixing portion 21 in the longitudinal direction of the hollow fiber membrane module 1 in the same manner.
By not providing a restricting member (for example, such as restricting member 41 in fig. 10 described later) in the adhesive fixing portion 20 and/or the adhesive fixing portion 21 having the end surface of the hollow portion opening of the hollow fiber membrane 2, the hollow fiber membrane 2 can be uniformly arranged on the entire end surface. As a result, the density distribution of the hollow fiber membranes 2 can be made uniform on the end surface of at least one of the first adhesive fixing portion 20 and the second adhesive fixing portion 21, and as a result, the density distribution of the hollow fiber membranes 2 in the housing 5 can be made more uniform.
In one embodiment, as shown in fig. 1 and 2, in the second adhesive fixing portion 21, the upper ends of the hollow fiber membrane bundles 3 are opened, and the inner regions of the hollow fiber membranes 2 are opened to the piping 11a of the cap 11. On the other hand, the lower ends of the hollow fiber membrane bundles 3 are sealed by the first adhesive fixing portions 20. In other embodiments, the lower end opening upper end of the hollow fiber membrane bundle 3 may be sealed, or both ends of the hollow fiber membrane bundle 3 may be opened.
In the present embodiment, as shown in fig. 1, a plurality of through holes 20a are formed in the first adhesive fixing portion 20. The through hole 20a is formed parallel to the longitudinal direction of the housing 5, and is a hole for communicating the outer region 5b with the outer region 5c on the opposite side of the first adhesive fixing portion 20. In the filtering process, the water to be treated (liquid to be treated) flows in from the pipe 10a of the cover 10 provided outside the first adhesive fixing portion 20, and is supplied to the outside region 5b through the through hole 20a.
Fig. 3 is a C-D line sectional view of the hollow fiber membrane module 1 shown in fig. 1. In the present embodiment, as shown in fig. 3, the plurality of through holes 20a are formed to be uniformly distributed in the first adhesive fixing portion 20. Note that the through holes 20a are desirably formed so as to be uniformly distributed in the first adhesive fixing portion 20 as in the present embodiment, but are not limited thereto, and may be arranged in other ways. In addition, in another embodiment, in the case where the lower end of the hollow fiber membrane bundle 3 is opened, the first adhesive fixing portion 20 may not be formed with the through hole 20a.
The potting material constituting the first adhesive fixing portion 20 and the second adhesive fixing portion 21 is preferably a polymer material such as an epoxy resin, a vinyl ester resin, a urethane resin, an unsaturated polyester resin, an olefin polymer, a silicone resin, or a fluorine-containing resin, and any one of these polymer materials may be used, or a plurality of polymer materials may be used in combination.
< annular concave-convex portion 5a >)
As shown in fig. 1 and 2, the hollow fiber membrane module 1 of the present embodiment has annular concave-convex portions 5a located on the inner walls of both end portions of the housing 5. The annular concave-convex structure is formed on the side surfaces of the first adhesive fixing portion 20 and the second adhesive fixing portion 21 by the concave-convex structure of the annular concave-convex portion 5a. This can enlarge the bonding area between the case 5 and the first and second bonding/fixing parts 20 and 21, and can obtain a higher bonding force.
< rectifying tube 7 >)
As shown in fig. 1 and 2, the hollow fiber membrane module 1 of the present embodiment has a cylindrical rectifying tube 7 located at the outer periphery of the end portion of the upper side (the nozzle 52a side) of the hollow fiber membrane bundle 3. The rectifying tube 7 is provided between the opening of the inner wall side of the housing 5 of the nozzle 52a and the hollow fiber membrane bundle 3, and is provided so as to surround the outer periphery of the hollow fiber membrane bundle 3. The rectifying cylinder 7 secures a space between the hollow fiber membrane bundle 3 and the inner wall of the housing 5 in the vicinity of the nozzle 52 a. Accordingly, when the concentrated water is discharged from the nozzle 52a, the hollow fiber membrane 2 can be prevented from swinging toward the nozzle 52a, and breakage of the hollow fiber membrane 2 can be prevented. As another embodiment, the rectifying tube 7 may be provided on the outer periphery of the lower end of the hollow fiber membrane bundle 3.
As shown in fig. 1, the rectifying cylinder 7 has a floor drain-like cylindrical wall surface provided with a plurality of through holes 30. It is desirable that the through hole 30 of the rectifying cylinder 7 is formed in an area other than the area opposed to the opening of the inner side surface side of the housing 5 of the nozzle 52a, but not in the area opposed to the opening. This can control the flow of water, and can enhance the effect of preventing the hollow fiber membrane 2 from swinging toward the nozzle 52 a.
The rectifying tube 7 includes a flange 7a at the center-side end of the hollow fiber membrane module 1, and the rectifying tube 7 is fixed between the hollow fiber membrane bundle 3 and the inner wall of the housing 5 by sandwiching the flange 7a by the joint portion of the second tubular member 52 and the third tubular member 53. The other end portion of the rectifying tube 7 is bonded and fixed in the second bonding and fixing portion 21.
< protective Member 8 >)
Fig. 4 shows the appearance of the protection member 8 provided in the housing 5. In one embodiment, the hollow fiber membrane module 1 may include a cylindrical protection member 8 covering the outer peripheral surface of the hollow fiber membrane bundle 3. In fig. 4, the hollow fiber membrane bundle 3 and the rectifying tube 7 shown in fig. 1 are not shown. In fig. 1, the protection member 8 is not illustrated.
The protection member 8 is a member formed in a tubular shape as a net-like member, and has flexibility. As a material of the mesh-shaped protective member 8, a material having heat resistance such as PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene-hexafluoropropylene copolymer (4-6 fluorinated)), ETFE (tetrafluoroethylene-ethylene copolymer), PTFE (polytetrafluoroethylene (4 fluorinated), polysulfone, or the like is preferably used.
Both ends of the protection member 8 are located in the first adhesive fixing portion 20 and the second adhesive fixing portion 21, respectively, and are adhered to the inner wall of the case 5 by the first adhesive fixing portion 20 and the second adhesive fixing portion 21.
During the external pressure filtration treatment, the water to be treated supplied to the outer region 5b permeates the protection member 8, then permeates the outer surfaces of the hollow fiber membranes 2, and the filtered water passing through the hollow portions of the hollow fiber membranes 2 is discharged from the pipe 11a of the cap 11, and the concentrated water is discharged from the nozzle 52 a.
Cleaning treatment
In the hollow fiber membrane module 1 of the present embodiment, after being used for the external pressure filtration treatment as described above, a cleaning treatment by air washing is periodically performed. Specifically, the washing water is supplied from the upper second adhesive fixing portion 21 side, and the air is supplied to the through hole 20a of the lower first adhesive fixing portion 20, whereby the supplied two fluids are discharged from the nozzle 52a of the second tubular member 52, and the hollow fiber membrane 2 is shaken to remove the dirt adhering to the membrane surface.
End face of hollow fiber membrane 2 with hollow portion open
As described above, the first adhesive fixing portion 20 and/or the second adhesive fixing portion 21 has a substantially circular end surface of the hollow portion opening of the hollow fiber membrane 2. Here, the substantially circular shape means a shape including not only a perfect circle but also an ellipse. When the end face is elliptical, the end face diameter means the minor axis of the ellipse. The diameter of the end surface matches the inner diameter of the end portion on the surface perpendicular to the longitudinal direction of the housing 5.
In one embodiment, as shown in fig. 2, the hollow portion of the hollow fiber membrane 2 is opened on the end face 21a of the second adhesive fixing portion 21. In another embodiment, the hollow portion of the hollow fiber membrane 2 may be opened at the end face of the first adhesive fixing portion 20, and the hollow portion of the hollow fiber membrane 2 may be opened at the first adhesive fixing portion 20 and the second adhesive fixing portion 21.
Diameter >, diameter
The diameter of the end face of the hollow opening of the hollow fiber membrane 2 is preferably 50mm or more, or 100mm or more, or 150mm or more, or 165mm or more; and preferably 300mm or less or 250mm or less. This makes it possible to achieve space saving of the installation area of the water treatment device and to uniformly inject the potting material into the required portion inside the case 5.
< filling Rate >
In one embodiment, the total cross-sectional area of all the hollow fiber membranes 2/the internal cross-sectional area of the housing 5), that is, the filling ratio of the hollow fiber membranes 2 on the end face of the hollow portion opening of the hollow fiber membranes 2 is preferably 45% or less or 40% or less. This makes it possible to form a proper gap between the hollow fiber membranes 2 and to uniformly inject the potting material into the desired portion inside the case 5.
The total cross-sectional area of all the hollow fiber membranes 2/the internal cross-sectional area of the housing 5), that is, the filling ratio of the hollow fiber membranes 2 on the end surface of the hollow opening of the hollow fiber membranes 2 is preferably 10% or more, or 25% or more, or 30% or more. As a result, the ratio of the potting material in the adhesive fixing portion 20 and/or the adhesive fixing portion 21 is suppressed to be small, and thus occurrence of cracks and peeling at the adhesive fixing portion 20 and/or the adhesive fixing portion 21 due to curing shrinkage can be suppressed.
The cross-sectional area of all the hollow fiber membranes 2 described above is set to be the cross-sectional area of the hollow portion including the hollow fiber membranes 2. The total cross-sectional area of all the hollow fiber membranes 2 is the product of the cross-sectional area of the hollow fiber membranes 2 and the number of the hollow fiber membranes 2. The filling rate may be calculated by dividing the total cross-sectional area by the internal cross-sectional area of the housing 5.
Resin material constituting end face of hollow opening
The resin (potting material) constituting the first adhesive fixing portion 20 and/or the second adhesive fixing portion 21 having the end face of the hollow opening of the hollow fiber membrane 2 is preferably a single thermosetting resin having a D hardness of 60 or less at 25 ℃ in accordance with JIS K7215. By using a single resin, there is no fear that the resins are peeled off from each other, and occurrence of cracks at the adhesive fixing portion 20 and/or the adhesive fixing portion 21 can be prevented. By setting the resin hardness to 60 or less, the hollow fiber membranes 2 can be flexibly moved in the vicinity of the interface of the adhesive fixing portion 20 and/or the adhesive fixing portion 21, and breakage of the hollow fiber membranes 2 can be suppressed. Here, the "interface of the adhesive fixing portion" is a surface located on the opposite side of the end surfaces of the first adhesive fixing portion 20 and the second adhesive fixing portion 21, and is a surface facing the center side of the housing 5, and the same applies hereinafter.
The D hardness of the resin material is more preferably 58 or less, and still more preferably 56 or less. This can further suppress breakage of the hollow fiber membranes 2 in the vicinity of the interface between the adhesive fixing portions 20 and/or 21. From the viewpoint of obtaining good fixing strength, the D hardness of the resin material is preferably 45 or more or 50 or more. The value of the hardness of the resin material constituting the end face of the adhesive fixing portion 20 and/or the adhesive fixing portion 21 can be obtained by measuring, for example, a portion of the end face composed of only the resin material.
The single thermosetting resin is preferably a two-part curable thermosetting resin. In the measurement with a B-type viscometer, the viscosity of the two-part curable thermosetting resin is preferably 1pa·s or more and 10pa·s or less after 10 minutes from the start of the two-part mixing, and the viscosity exceeds 100pa·s after 30 minutes.
By setting the viscosity of the thermosetting resin to 1pa·s or more 10 minutes after the start of the two-liquid mixing, unnecessary impregnation of the hollow fiber membrane 2 with the thermosetting resin can be suppressed. On the other hand, if the viscosity after 10 minutes from the start of the two-liquid mixing is 10pa·s or less, the injected state of the thermosetting resin tends to become more uniform. In addition, by making the viscosity after 30 minutes exceed 100pa·s, the thermosetting resin can be inhibited from exuding to the hollow portion of the hollow fiber membrane 2. The viscosity after 10 minutes from the start of the two-liquid mixing is more preferably 1.5 Pa.s or more; and more preferably 8pa·s or less or 5pa·s or less. The viscosity after 30 minutes from the start of the two-liquid mixing is more preferably 150pa·s or more.
Protrusion 50
Fig. 5 is a schematic view showing the potting material P and the hollow fiber membranes 2 constituting the second adhesive fixing portion 21. As shown in fig. 5, in each hollow fiber membrane 2 near the interface S of the potting material P, there is a portion where the potting material P is cured in a state of penetrating the hollow fiber membrane 2. This portion is referred to as the tab 50.
The protruding portion 50 is formed when the first adhesive fixing portion 20 and the second adhesive fixing portion 21 are cured in the manufacturing process of the hollow fiber membrane module 1. When the adhesive fixing portions 20 and 21 are formed by the centrifugal bonding method, the case 5 is placed so that the longitudinal direction thereof is horizontal, and the potting material P is injected into both end portions and rotated in the horizontal direction around the center portion of the case 5. As a result, the potting material P gathers on both sides of the case 5 by centrifugal force, thereby forming the first adhesive fixing portion 20 and the second adhesive fixing portion 21. At this time, a part of the potting material P permeates toward the central portion side of each hollow fiber membrane 2 due to the capillary phenomenon, and is cured in this state to form the protruding portion 50.
The minimum length of the protrusion 50 from the interface S of the potting material P is preferably 3mm or more and 20mm or less. Here, the interface S of the potting material P is the surface of the potting material P except for the protruding portion 50 formed in the hollow fiber membrane 2. The minimum length mentioned above is the length of the shortest protrusion 50 among the plurality of protrusions 50 formed in each hollow fiber membrane 2.
The length of the protrusion 50 is obtained by detaching the hollow fiber membrane module 1, cutting each hollow fiber membrane 2 from the interface S of the potting material P, and measuring the height of the portion from the interface S to the potting material P of the hollow fiber membrane 2.
In the present invention, the inventors found that, when the minimum length of the protruding portion 50 is short, the hollow fiber membranes 2 cannot be flexibly bent in the vicinity of the interface S of the potting material P, and therefore the hollow fiber membranes 2 are more likely to break by the swing. Further, the inventors found that when the packing density of the hollow fiber membranes 2 is high, the length of the protruding portions 50 becomes short.
The reason why the length of the protruding portion 50 becomes shorter when the density of the hollow fiber membrane 2 is high will be described below. In the step of forming the first adhesive fixing portion 20 and the second adhesive fixing portion 21, when the packing density of the hollow fiber membranes 2 is high, the distance between adjacent hollow fiber membranes 2 is short and close, so that the potting material P is difficult to be injected in the longitudinal direction of the case 5. As a result, since the interface S is formed in a state of high viscosity in which the capillary phenomenon does not occur, the protruding portion 50 is not formed or the length of the protruding portion 50 is shortened. Further, when the filling density of the hollow fiber membranes 2 is high, the potting material P cannot uniformly fill the end of the case 5, and potting failure tends to occur easily.
Density distribution of hollow fiber membrane 2
Fig. 6 is a schematic view of the hollow fiber membrane module 1 shown in fig. 1 and 2 when the end face 21a of the second adhesive fixing portion 21 is viewed from the arrow a direction. Fig. 7 is a schematic view showing a cross section of a part of the inside of the housing 5. Hereinafter, the density distribution of the hollow fiber membranes 2 in the hollow fiber membrane module 1 of the present embodiment will be described with reference to fig. 6 and 7.
< macroscopic Density distribution on the end faces of the openings of hollow fiber Membrane 2 >
The hollow fiber membrane module 1 of the present embodiment is characterized in that, on the end surface of the hollow fiber membrane 2 of the first adhesive fixing portion 20 and/or the second adhesive fixing portion 21 (in the embodiment shown in fig. 6, the end surface 21a of the second adhesive fixing portion 21), a point corresponding to a portion having the smallest thickness in the longitudinal direction on the outer peripheral surface of the first adhesive fixing portion 20 and/or the second adhesive fixing portion 21 having the end surface is set as an upper vertex R, and when a horizontal line orthogonal to a vertical line from the upper vertex R toward the center of the end surface and passing through the center is drawn, a ratio of the number of hollow fiber membranes 2 located on the upper side to the number of hollow fiber membranes 2 located on the lower side (the number of hollow fiber membranes 2 on the upper side)/(the number of hollow fiber membranes 2 on the lower side) is set to be 0.9 or more and 1.1 or less. The above ratio is preferably 0.92 or more or 0.95 or more; and is preferably 1.08 or less or 1.05 or less.
The above will be specifically described. The second adhesive fixing portion 21 shown in fig. 7 is uneven in thickness, and a large-thickness portion and a small-thickness portion are present in the first adhesive fixing portion 20 and the second adhesive fixing portion 21. In the second adhesive fixing portion 21 shown in fig. 7, the distance between the points R-R' is the minimum thickness on the outer peripheral surface of the second adhesive fixing portion 21. In fig. 7, when the end face 21a of the second adhesive fixing portion 21 is viewed from the upper side, a portion on the outer peripheral surface of the second adhesive fixing portion 21 where the thickness is smallest corresponds to the point R.
In fig. 6, the horizontal line E-F is a horizontal line that is orthogonal to a vertical line from the upper apex R toward the center of the end face 21a and passes through the center. The hollow fiber membrane module 1 of the present embodiment is characterized in that the end surface 21a is divided into an upper region and a lower region by a horizontal line E-F, and the ratio of the number of hollow fiber membranes 2 located on the upper side to the number of hollow fiber membranes 2 located on the lower side (the number of hollow fiber membranes 2 on the upper side)/(the number of hollow fiber membranes 2 on the lower side) is 0.9 or more and 1.1 or less. When the hollow fiber membranes 2 are present on the horizontal line E to F, the number of hollow fiber membranes 2 is counted in a region where the cross-sectional area of the hollow fiber membranes 2 is large.
As a result, the density distribution of the hollow fiber membranes 2 can be made uniform on the end face 21a of the second adhesive fixing portion 21, which is one end of the hollow fiber membrane bundle 3, and breakage of the hollow fiber membranes 2 due to swing can be suppressed. Further, as a result of the uniform density distribution of the hollow fiber membranes 2 on the end surface 21a as a whole, the value of the minimum length of the protruding portion 50 in the vicinity of the second adhesive fixing portion 21 can be increased as compared with the case where there is a portion where the density of the hollow fiber membranes 2 is locally high. By increasing the minimum length of the protruding portion 50, the hollow fiber membrane 2 can be flexibly bent in the vicinity of the second adhesive fixing portion 21, and breakage of the hollow fiber membrane 2 due to swing can be prevented.
In fig. 6 and 7, the end face of the hollow fiber membrane 2 that is open is described as the second adhesive fixing portion 21, but the same applies to the case where the end face of the hollow fiber membrane 2 that is open is the first adhesive fixing portion 20.
< Density distribution on virtual bonding interface S)
In one embodiment, on the virtual bonding interface S 'in which the end face 21a of the hollow opening of the hollow fiber membrane 2 of the second bonding/fixing part 21 shown in fig. 7 is virtually moved in parallel toward the longitudinal center by the amount of the thickness R-R' of the portion of the outer peripheral surface of the second bonding/fixing part 21 having the smallest thickness in the longitudinal direction, the total cross-sectional area of all the hollow fiber membranes 2/the internal cross-sectional area of the housing 5 is preferably 20% or more, or 22% or more, or 25% or more; and is preferably 50% or less, or 48% or less, or 45% or less.
By setting the filling ratio at the virtual bonding interface S', that is, the total cross-sectional area of all the hollow fiber membranes 2/the internal cross-sectional area of the housing 5) to 50% or less, the gaps between the hollow fiber membranes 2 can be sufficiently ensured, and the potting material can be easily and uniformly injected between the hollow fiber membranes 2. On the other hand, setting the filling ratio to 20% or more can suppress the ratio of the potting material in the first adhesive fixing portion 20 and/or the second adhesive fixing portion 21 to be small, and thus can suppress occurrence of cracks or peeling at the first adhesive fixing portion 20 and/or the second adhesive fixing portion 21 due to curing shrinkage.
In one embodiment, when a horizontal line is drawn on the virtual bonding interface S ' orthogonal to a vertical line extending from the upper vertex R ' toward the center of the virtual bonding interface S ' and passing through the center, a ratio of the number of hollow fiber membranes 2 located on the upper side to the number of hollow fiber membranes 2 located on the lower side (the number of hollow fiber membranes 2 on the upper side)/(the number of hollow fiber membranes 2 on the lower side) is preferably 0.85 or more, or 0.88 or more, or 0.90 or more; and is preferably 1.15 or less, or 1.12 or less, or 1.10 or less. When the hollow fiber membranes 2 are present on the horizontal line, the number of hollow fiber membranes 2 is counted in a region where the cross-sectional area of the hollow fiber membranes 2 is large. The same applies to the case where the end face of the hollow fiber membrane 2 that is open is the first adhesive fixing portion 20.
Thus, the density distribution of the hollow fiber membranes 2 can be made uniform throughout the virtual bonding interface S' of the first bonding and fixing portion 20 and/or the second bonding and fixing portion 21. By making the density distribution of the hollow fiber membranes 2 uniform throughout the virtual bonding interface S' closer to the central portion of the hollow fiber membrane bundle 3 than the end surfaces of the first bonding fixing portion 20 and/or the second bonding fixing portion 21, breakage of the hollow fiber membranes 2 due to oscillation can be further suppressed.
Further, as a result of making the density distribution of the hollow fiber membranes 2 uniform throughout the virtual bonding interface S' of the first bonding fixing section 20 and/or the second bonding fixing section 21, the minimum value of the length of the protruding sections 50 in the hollow fiber membrane bundle 3 can be increased as compared with the case where there is a portion where the density of the hollow fiber membranes 2 is locally high. By increasing the minimum value of the length of the protruding portion 50, the hollow fiber membrane 2 can be flexibly bent in the vicinity of the interface of the first adhesive fixing portion 20 and/or the second adhesive fixing portion 21, and breakage of the hollow fiber membrane 2 due to swing can be prevented.
< microcosmic Density distribution on open end faces of hollow fiber Membrane 2 >
Fig. 8 is a schematic view of the hollow fiber membrane module 1 shown in fig. 1 and 2 when the end face 21a of the second adhesive fixing portion 21 is viewed from the arrow a direction. In the hollow fiber membrane module 1 according to one embodiment, a first perfect circle F1, which is a perfect circle including the smallest diameter of all hollow fiber membranes existing on the end face, a second perfect circle F2 concentric with the first perfect circle F1 and having a diameter smaller than the first perfect circle F1 by 2cm, a first square F3, which is the largest of squares having one side of Ncm (where N is a natural number), which is the center located in the second perfect circle F2 (i.e., concentric with the perfect circle F2), and N, which is a square having 1cm square, are defined on the end face of the hollow fiber membrane 2 of the first adhesive fixing portion 20 and/or the second adhesive fixing portion 21 (in the embodiment shown in fig. 8, the end face 21a of the second adhesive fixing portion 21) 2 In the case of the second squares F4, the ratio of (minimum value)/(maximum value) of the number of hollow fiber membranes 2 included in each second square F4 is preferably 0.4 or more, or 0.42 or more, or 0.45 or more. In the case where the hollow fiber membranes 2 are present on the sides of the second square F4, the number is counted as the second square containing the largest proportion of the cross-sectional area of the hollow fiber membranes 2. In fig. 8, the end face of the hollow fiber membrane 2 that is open is described as the second adhesive fixing portion 21, but the end face of the hollow fiber membrane 2 that is open is the first oneThe same applies to the case of bonding the fixing portion 20.
In the module, if there is an excessively dense region of the hollow fiber membranes, the adhesive is less likely to penetrate between the hollow fiber membranes in this region, and the thickness of the adhesive-bonded portion tends to be small. On the other hand, if there is an excessively open region of the hollow fiber membrane, the hollow fiber membrane tends to swing easily and breakage easily occurs in this region. The above-mentioned (minimum value)/(maximum value) is smaller than the above-mentioned range, which means that the degree of partial over-dense or over-sparse filling of the hollow fiber membrane is small, and the above-mentioned problem can be well avoided. The (minimum)/(maximum) ratio is preferably 1.
< shape of first adhesive fixing portion 20 and second adhesive fixing portion 21 >
Fig. 9 is a schematic view showing a cross section of a part of the interior of the case 5 in order to explain the shape of the interface of the second adhesive fixing portion 21. Fig. 9A is a sectional view of the housing 5 according to the horizontal line E-F in fig. 6. In the cross section shown in fig. 9 (a), the interface of the second adhesive fixing portion 21 is in the shape of an arc with both ends high and the center low. This is because the potting material is affected by centrifugal force (arrow G in fig. 9 (a)) in the centrifugal bonding process, and the shape of the circular arc depends on the radius of rotation in the centrifugal bonding process and the inner diameter of the case 5.
In the present embodiment, (the thickness L of the second adhesive fixing portion 21 at one intersection of the outer peripheral surface of the second adhesive fixing portion 21 and the horizontal line EF) 1 And a thickness L of the second adhesive fixing portion 21 at the other intersection point of the outer peripheral surface and the horizontal line EF 2 ) - (the average value of the second adhesive fixing portion 21 at the center of the end face 21a of the second adhesive fixing portion 21) О ) The difference is preferably 1mm or more, or 1.5mm or more, or 2mm or more; and preferably 12mm or less, or 10mm or less, or 8mm or less. The same applies to the first adhesive fixing portion 20.
Fig. 9 (B) is a schematic diagram showing a cross section of a part of the interior of the case 5 based on a perpendicular line from the upper side apex R toward the center of the end surface 21a of the second adhesive fixing portion 21 in fig. 6. The vertical direction of the case 5 in the centrifugal bonding step corresponds to the vertical direction of fig. 9 (B). In the cross section shown in fig. 9 (B), the interface of the second adhesive fixing portion 21 is inclined with the upper side low and the lower side high. In the centrifugal bonding step, the potting material receives gravity in the vertical direction in the drawing and centrifugal force in the outward direction from the rotation center (arrow G in fig. 9B), and therefore the degree of inclination of the interface depends on the magnitude of the centrifugal force.
In the present embodiment, the thickness L of the second adhesive fixing portion 21 at the other intersection point of the perpendicular line (from the upper side apex R toward the center of the end surface 21a of the second adhesive fixing portion 21) and the outer peripheral surface of the second adhesive fixing portion 21 4 ) Thickness L of second adhesive fixing portion 21 at upper vertex R 3 ) Preferably 3mm or more, or 3.5mm or more, or 4mm or more; and is preferably 12mm or less, or 11mm or less, or 10mm or less. The same applies to the first adhesive fixing portion 20.
< thickness of first adhesive fixing portion 20 and second adhesive fixing portion 21 >)
The thickness of the first adhesive fixing portion 20 and/or the second adhesive fixing portion 21 having the end face of the hollow opening of the hollow fiber membrane 2 is preferably small in local variation. Fig. 10 is a view showing an end face of a hollow opening of a hollow fiber membrane of a conventional hollow fiber membrane module shown in comparative example 1 described later. In the conventional hollow fiber membrane module, as shown in fig. 10, since the membrane bundle is formed by providing the restricting member 41, the density of the hollow fiber membranes is partially generated in the hollow fiber membrane bundle, and when the potting material is injected, the potting material is injected according to the density of the hollow fiber membranes, and the variation in the thickness of the adhesive fixing portion is large. In this way, when the variation in thickness of the first adhesive fixing portion 20 and/or the second adhesive fixing portion 21 is large, there is a problem that the partial pressure resistance is weak, etc., but as described above, the problem can be solved by reducing the variation in thickness of the first adhesive fixing portion 20 and/or the second adhesive fixing portion 21.
Examples
Next, examples and comparative examples of the hollow fiber membrane module of the present invention will be described, but the present invention is not limited to these examples.
Example 1
16500 PVDF (polyvinylidene fluoride) hollow fiber membranes (Asahi chemical Co., ltd.) were bundled to a length of 2.3m, lifted vertically, and cut off from the lower end face to align. Next, a repair tape was attached to the circumference of the bundle over the entire circumference so that the circumference was 170 mm. Further, 300g of polyurethane resin SA-8100A/SA-8100B (manufactured by SANYU REC) was measured with a mixing jet, and immersed in the lower surface of the film bundle for 30 seconds, and then immediately separated. Thereafter, the resin was left at room temperature for 4 hours, and the polyurethane resin impregnated in the lower surface of the bundle was cured to seal the hollow portion while defining the diameter of the bundle. The thus-produced film bundle was inserted into a housing having a second cylindrical member (end surface diameter 218 mm) with a rectifying cylinder having an inner diameter of 216mm mounted inside. The hollow fiber membrane used had an average pore diameter of 0.1 μm, an inner diameter of 0.6mm and an outer diameter of 1.0mm.
Next, a columnar member is inserted into the end of the hollow fiber membrane bundle on the first tubular member side at a position where the through hole is to be formed.
Next, the adhesive fixing portion forming containers to which the potting material introduction tube is attached are fixed to both ends of the case, and the potting material is injected into the first tubular member and the second tubular member of the case while being rotated in the horizontal direction. As the potting material, a two-component thermosetting urethane resin (product name: SA-6330A2/SA-6330B5, manufactured by SANYU REC Co., ltd.) was used, and its viscosity after 10 minutes after mixing was 3.5 Pa.s, and its viscosity after 30 minutes was 210 Pa.s, measured at 25 ℃. At the time of stopping the flow of the potting material by the curing reaction, the rotation of the centrifuge was stopped, the potting material was taken out, and heated to 50 ℃ in an oven to cure the potting material. Further, the viscosity after 10 minutes and the viscosity after 30 minutes after mixing were measured by a type B viscometer.
Then, the end of the case on the second tubular member side was cut off to set the total length of the case to 2.1m, and the hollow opening on one side of the hollow was closed at the stage before bonding. On the other hand, the columnar member is removed from the first adhesive fixing portion on the first cylindrical member side, thereby forming a plurality of through holes. In addition, the effective membrane length of the hollow fiber membrane module is 2m.
In this case, when a horizontal line is drawn to be perpendicular to a vertical line extending from the apex toward the center of the end face and passing through the center, the number of hollow fiber membranes on the upper side of the horizontal line is 8099 and the number of hollow fiber membranes on the lower side of the horizontal line is 8401, with the point corresponding to the portion of the outer peripheral surface of the second adhesive fixing portion where the thickness is smallest being the upper apex. That is, the ratio of the number of hollow fiber membranes to the number of hollow fiber membranes located at the lower side (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.96. The filling rate of the produced hollow fiber membrane module was 34.7%.
The end face of the hollow fiber membrane opening of the second adhesive fixing portion was defined with a first perfect circle which is a perfect circle having the smallest diameter and containing all the hollow fiber membranes present on the end face, a second perfect circle concentric with the first perfect circle and smaller than the second perfect circle by 2cm in diameter, a first square having a size of 10cm square with the largest dimension among squares having one side of Ncm (where N is a natural number) located at the center in the second perfect circle, and 100 (=10×10) second squares obtained by dividing the first square into 1cm squares. Regarding the number of hollow fiber membranes included in each second square, the minimum value of the 100 is 50 and the maximum value is 91, and thus (minimum value)/(maximum value) =0.55. In the case where the hollow fiber membranes are present on the sides of the second square, the number of the second square including the largest proportion of the cross-sectional area of the hollow fiber membranes is counted.
In the second adhesive fixing portion, (L) 1 And L 2 Average of (d) o ＝6mm，L 4 -L 3 Values of = 9mm.
The (JIS K7215) D hardness of the resin fixing portion on the end face of the produced hollow fiber membrane module was 55D. In the measurement of the hardness of the resin fixing portion, the load holding time was set to 10 seconds, and the value of the hardness was an average value of 5 points randomly selected on the end face of the adhesive fixing portion.
The filling rate of the hollow fiber membranes at the virtual bonding interface S' of the second bonding fixing part of the manufactured hollow fiber membrane module was 32.6%. In the virtual bonding interface S ', when a horizontal line is drawn perpendicular to a vertical line extending from the upper vertex toward the center of the virtual bonding interface S' and passing through the center, the ratio of the number of hollow fiber membranes located above the horizontal line to the number of hollow fiber membranes located below (the number of hollow fiber membranes located above)/(the number of hollow fiber membranes located below) is 0.92.
Next, the hollow fiber membrane module was attached to the filtration apparatus with the side of the hollow portion open as the upper side, and the following physical cleaning durability test was performed.
From the second adhesive fixing part side at the upper side, 7m 3 The washing water was supplied at a flow rate of/hr while 8.5Nm 3 The flow rate of/hr supplies air to the through hole of the first adhesive fixing portion on the lower side. The two fluids supplied are discharged from the nozzle of the upper second tubular member. The above operation was continuously performed except for the leak test performed every month. In addition, the water temperature was kept at 10 ℃ during operation.
After 6 months of operation, 5 leaks were generated due to breakage of the hollow fiber membranes. After the test, the membrane module was disassembled, and the state of the second adhesive fixing portion was confirmed, wherein the thickest portion of the second adhesive fixing portion was 70mm, the thinnest portion was 66mm, and the (maximum thickness) - (minimum thickness) was 4mm. The minimum length of the protruding portion in the longitudinal direction of the hollow fiber membrane was 5mm.
Example 2
A hollow fiber membrane module was produced and evaluated in the same manner as in example 1, except that 11000 hollow fiber membranes (manufactured by sunburst chemical reaction) made of PVDF (polyvinylidene fluoride) were used, a repair tape was adhered to the entire circumference of the membrane bundle so that the circumference was 135mm, the end surface diameter of the second tubular member used was 168mm, and the inner diameter of the rectifying tube was 165 mm.
In this case, when a horizontal line is drawn to be perpendicular to a vertical line extending from the vertex toward the center of the end face and passing through the center, the number of hollow fiber membranes on the upper side of the horizontal line is 5365 and the number of hollow fiber membranes on the lower side is 5635, the point corresponding to the portion of the outer peripheral surface of the second adhesive fixing portion where the thickness is smallest is defined as the upper vertex on the end face of the hollow fiber membrane opening of the second adhesive fixing portion. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.95. The filling rate of the produced hollow fiber membrane module was 39%. Other measurement results and the like are shown in Table 1.
Example 3
A hollow fiber membrane module was produced and evaluated in the same manner as in example 1, except that 11500 hollow fiber membranes (manufactured by sunglass chemical reaction) made of PVDF (polyvinylidene fluoride) were used, and the hollow fiber membranes used had an average pore diameter of 0.1 μm, an inner diameter of 0.7mm and an outer diameter of 1.22 mm.
In this case, when a horizontal line is drawn on the end surface of the hollow fiber membrane opening of the second adhesive fixing portion, which is perpendicular to a perpendicular line extending from the vertex toward the center of the end surface and passes through the center, with a point corresponding to a portion of the outer peripheral surface of the second adhesive fixing portion where the thickness is smallest as an upper vertex, the number of hollow fiber membranes on the upper side of the horizontal line is 5703 and the number of hollow fiber membranes on the lower side thereof is 5797. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.98. The filling rate of the produced hollow fiber membrane module was 36%. Other measurement results and the like are shown in Table 1.
Example 4
A hollow fiber membrane module was produced and evaluated in the same manner as in example 2, except that 6600 hollow fiber membranes (manufactured by asahi chemical industry) made of PVDF (polyvinylidene fluoride) were used, and the hollow fiber membranes used had an average pore diameter of 0.1 μm, an inner diameter of 0.7mm, and an outer diameter of 1.22 mm.
In this case, when a horizontal line is drawn on the end surface of the hollow fiber membrane opening of the second adhesive fixing portion, which is perpendicular to a perpendicular line extending from the vertex toward the center of the end surface and passing through the center, with a point corresponding to a portion of the outer peripheral surface of the second adhesive fixing portion where the thickness is smallest as an upper vertex, the number of hollow fiber membranes on the upper side of the horizontal line is 3215 and the number of hollow fiber membranes on the lower side thereof is 3385. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.95. The filling rate of the produced hollow fiber membrane module was 34.8%. Other measurement results and the like are shown in Table 1.
Example 5
A hollow fiber membrane module was produced and evaluated in the same manner as in example 2, except that 6000 hollow fiber membranes (manufactured by sunglass chemical industry) made of PVDF (polyvinylidene fluoride) were used, and the hollow fiber membranes used had an average pore diameter of 0.02 μm, an inner diameter of 0.7mm and an outer diameter of 1.3 mm.
In this case, when a horizontal line is drawn on the end surface of the hollow fiber membrane opening of the second adhesive fixing portion, which is orthogonal to a perpendicular line extending from the vertex toward the center of the end surface and passes through the center, with a point corresponding to a portion of the outer peripheral surface of the second adhesive fixing portion where the thickness is smallest as an upper vertex, the number of hollow fiber membranes on the upper side of the horizontal line is 2970 and the number of hollow fiber membranes on the lower side thereof is 3030. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.98. The filling rate of the produced hollow fiber membrane module was 35.9%. Other measurement results and the like are shown in Table 1.
Example 6
A hollow fiber membrane module was produced in the same manner as in example 3, except that 8300 hollow fiber membranes (manufactured by Asahi chemical Co., ltd.) made of PVDF (polyvinylidene fluoride) were used, and a two-component thermosetting polyurethane resin (manufactured by Sanyo chemical Co., ltd.: JA-553/JB-553 (trade name), a viscosity after 10 minutes after mixing measured at 25℃of 2.5 Pa.s, and a viscosity after 30 minutes measured at 25℃of 170 Pa.s) was used as a potting material, and the evaluation was performed.
In this case, when a horizontal line is drawn on the end surface of the hollow fiber membrane opening of the second adhesive fixing portion, which is orthogonal to a perpendicular line extending from the vertex toward the center of the end surface and passes through the center, with a point corresponding to a portion of the outer peripheral surface of the second adhesive fixing portion where the thickness is smallest as an upper vertex, the number of hollow fiber membranes on the upper side of the horizontal line is 4071 and the number of hollow fiber membranes on the lower side thereof is 4229. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.96. The filling rate of the produced hollow fiber membrane module was 26.0%. In this hollow fiber membrane module, a gap is visible in the longitudinal direction in a part of the circumferential direction of the surface where the adhesive fixing portion and the housing are adhered. Other measurement results and the like are shown in Table 1.
Example 7
A hollow fiber membrane module was produced and evaluated in the same manner as in example 1, except that 8800 hollow fiber membranes (manufactured by Asahi chemical Co., ltd.) made of PVDF (polyvinylidene fluoride), 1.6m of the total length of the bundling membrane, a repair tape was adhered to the entire circumference of the membrane bundle so that the circumference was 110mm, the end face diameter of the second tubular member used was 140mm, the inner diameter of the rectifying tube was 135mm, and 1.4m of the total length of the casing after cutting the end of the hollow fiber membrane bundle was used.
In this case, when a horizontal line is drawn to be perpendicular to a vertical line extending from the apex toward the center of the end face and passing through the center, the number of hollow fiber membranes on the upper side of the horizontal line is 4316 and the number of hollow fiber membranes on the lower side is 4484, with the point corresponding to the portion of the outer peripheral surface of the second adhesive fixing portion where the thickness is smallest being the upper apex. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.96. The filling rate of the produced hollow fiber membrane module was 44.9%. Other measurement results and the like are shown in Table 1.
Example 8
A hollow fiber membrane module was produced and evaluated in the same manner as in example 1, except that 3100 hollow fiber membranes (manufactured by sunburn chemical reaction) made of PVDF (polyvinylidene fluoride) were used, a repair tape was adhered to the entire circumference of the membrane bundle so that the circumference was 75mm, the end face diameter of the second tubular member used was 84mm, and the inner diameter of the rectifying tube was 79 mm.
In this case, when a horizontal line is drawn on the end surface of the hollow fiber membrane opening of the second adhesive fixing portion, which is perpendicular to a perpendicular line extending from the vertex toward the center of the end surface and passing through the center, with a point corresponding to a portion of the outer peripheral surface of the second adhesive fixing portion where the thickness is smallest as an upper vertex, the number of hollow fiber membranes on the upper side of the horizontal line is 1485 and the number of hollow fiber membranes on the lower side thereof is 1615. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.92. The filling rate of the produced hollow fiber membrane module was 43.9%. Other measurement results and the like are shown in Table 1.
Example 9
A hollow fiber membrane module was produced and evaluated in the same manner as in example 4, except that the total length of the bundle of hollow fiber membranes (manufactured by asahi chemical industry) was 1.2m, and the total length of the case after cutting the end of the bundle of hollow fiber membranes was 1.0 m.
At this time, when a horizontal line is drawn to be orthogonal to a vertical line extending from the vertex toward the center of the end face and passing through the center, the number of hollow fiber membranes on the upper side of the horizontal line is 3294 and the number of hollow fiber membranes on the lower side is 3306, with the point corresponding to the portion of the outer peripheral surface of the second adhesive fixing portion where the thickness is smallest being the upper vertex. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 1.00. The filling rate of the produced hollow fiber membrane module was 34.8%. Other measurement results and the like are shown in Table 1.
Example 10
A hollow fiber membrane module was produced and evaluated in the same manner as in example 4, except that 11000 hollow fiber membranes (manufactured by asahi chemical industry) made of PVDF (polyvinylidene fluoride) were used.
In this case, when a horizontal line is drawn on the end surface of the hollow fiber membrane opening of the second adhesive fixing portion, which is orthogonal to a perpendicular line extending from the vertex toward the center of the end surface and passes through the center, with a point corresponding to a portion of the outer peripheral surface of the second adhesive fixing portion where the thickness is smallest as an upper vertex, the number of hollow fiber membranes on the upper side of the horizontal line is 5527 and the number of hollow fiber membranes on the lower side thereof is 5473. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 1.01. The filling rate of the produced hollow fiber membrane module was 58.0%. Other measurement results and the like are shown in Table 1.
Example 11
A hollow fiber membrane module was produced and evaluated in the same manner as in example 1, except that 21000 hollow fiber membranes (manufactured by Asahi chemical Co., ltd.) made of PVDF (polyvinylidene fluoride) were used.
In this case, when a horizontal line is drawn on the end surface of the hollow fiber membrane opening of the second adhesive fixing portion, which is perpendicular to a perpendicular line extending from the vertex toward the center of the end surface and passes through the center, with a point corresponding to a portion of the outer peripheral surface of the second adhesive fixing portion where the thickness is smallest as an upper vertex, the number of hollow fiber membranes on the upper side of the horizontal line is 10286 and the number of hollow fiber membranes on the lower side thereof is 10714. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.96. The filling rate of the produced hollow fiber membrane module was 44.2%. Other measurement results and the like are shown in Table 1.
Example 12
A hollow fiber membrane module was produced and evaluated in the same manner as in example 2, except that 6000 hollow fiber membranes (manufactured by sunburst chemical Co., ltd.) made of PVDF (polyvinylidene fluoride) were used.
In this case, when a horizontal line is drawn on the end surface of the hollow fiber membrane opening of the second adhesive fixing portion, which is orthogonal to a perpendicular line extending from the vertex toward the center of the end surface and passes through the center, with a point corresponding to a portion of the outer peripheral surface of the second adhesive fixing portion where the thickness is smallest as an upper vertex, the number of hollow fiber membranes on the upper side of the horizontal line is 2846 and the number of hollow fiber membranes on the lower side thereof is 3154. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.90. The filling rate of the produced hollow fiber membrane module was 21.3%. In this hollow fiber membrane module, a gap is visible in the longitudinal direction in a part of the circumferential direction of the surface where the adhesive fixing portion and the housing are adhered. Other measurement results and the like are shown in Table 1.
Comparative example 1
16500 PVDF (polyvinylidene fluoride) hollow fiber membranes (Asahi chemical Co., ltd.) were bundled and inserted into a housing having a second tubular member (end surface diameter 218 mm) with a rectifying tube having an inner diameter of 216mm attached thereto. The hollow fiber membrane used had an average pore diameter of 0.1 μm, an inner diameter of 0.6mm and an outer diameter of 1.0mm.
Next, 12 restriction members (members formed by casting an adhesive similar to the potting material described below into a mold in advance and curing the same) having a cylindrical shape with an outer diameter of 11mm were inserted and arranged as shown in fig. 10 at the end of the hollow fiber membrane bundle on the side of the hollow portion, which was closed with gypsum. On the other hand, a columnar member is inserted into the end of the hollow fiber membrane bundle on the first cylindrical member side at a position where the through hole is to be formed. Thereafter, a hollow fiber membrane module was produced in the same manner as in example 1, and evaluation thereof was performed.
As shown in fig. 10, when a horizontal line is drawn to the end surface of the hollow opening of the hollow fiber membrane, which is orthogonal to a perpendicular line extending from the point R toward the center of the end surface and passes through the center, and the point R corresponding to the portion of the outer peripheral surface of the second adhesive fixing portion having the end surface of the hollow opening of the hollow fiber membrane, which has the smallest thickness, is set as the upper vertex, the number of hollow fiber membranes on the upper side of the horizontal line is 7641 and the number of hollow fiber membranes on the lower side thereof is 8859. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.86.
Next, the hollow fiber membrane module was attached to the filtration apparatus with the side of the hollow portion open as the upper side, and the following physical cleaning durability test was performed.
From the second adhesive fixing part side at the upper side, 7m 3 The washing water was supplied at a flow rate of/hr while 8.5Nm 3 The flow rate of/hr supplies air to the through hole of the first adhesive fixing portion on the lower side. The two fluids supplied are discharged from the nozzle of the upper second tubular member. The above operation was continuously performed except for the leak test performed every month. In addition, the water temperature was kept at 10 ℃ during operation.
After 6 months of operation, leakage due to membrane breakage occurred 105. After the test, the membrane module was disassembled, and the state of the second adhesive fixing portion was confirmed, wherein the thickness of the second adhesive fixing portion was in the range of 54mm to 69mm, and the minimum value of the length of the protruding portion was 2mm at the maximum. Other measurement results and the like are shown in Table 2.
Comparative example 2
A hollow fiber membrane module was produced and evaluated in the same manner as in comparative example 1, except that a restricting member was not used at the end of the hollow fiber membrane bundle on the side where the hollow portion was closed with gypsum.
In this case, when a horizontal line is drawn to be perpendicular to a vertical line extending from the vertex toward the center of the end face and passing through the center, the number of hollow fiber membranes on the upper side of the horizontal line is 6513 and the number of hollow fiber membranes on the lower side of the horizontal line is 9987, with the point corresponding to the portion having the smallest thickness on the outer peripheral surface of the adhesive fixing portion of the end face having the hollow opening of the hollow fiber membrane being the upper vertex. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.65. Other measurement results and the like are shown in Table 2.
Comparative example 3
A hollow fiber membrane module was produced and evaluated in the same manner as in comparative example 1, except that a plate-like restriction member (a member formed by casting an adhesive similar to a potting material described below into a mold in advance and curing the adhesive), 11500 hollow fiber membranes made of PVDF (polyvinylidene fluoride) (manufactured by rising chemical reaction), and hollow fiber membranes used having an average pore diameter of 0.1 μm, an inner diameter of 0.7mm, and an outer diameter of 1.22mm were disposed at the end of a hollow fiber membrane bundle on one side of the hollow portion with gypsum, and the thickness was 3mm, the width was 210mm, and the length was 50 mm.
In this case, when a horizontal line is drawn to be perpendicular to a vertical line extending from the vertex toward the center of the end face and passing through the center, the number of hollow fiber membranes on the upper side of the horizontal line is 5350 and the number of hollow fiber membranes on the lower side of the horizontal line is 6150, with the point corresponding to the portion having the smallest thickness on the outer peripheral surface of the adhesive fixing portion of the end face having the hollow opening of the hollow fiber membrane being the upper vertex. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.87. Other measurement results and the like are shown in Table 2.
Comparative example 4
A hollow fiber membrane module was produced and evaluated in the same manner as in comparative example 1, except that a restricting member was not used at the end of the hollow fiber membrane bundle on the side where the hollow portion was closed with gypsum, 11000 PVDF (polyvinylidene fluoride) hollow fiber membranes (manufactured by sunburst chemical) were used, the end surface diameter of the second tubular member used was 168mm, and the inner diameter of the rectifying tube was 165 mm.
In this case, when a horizontal line is drawn to be perpendicular to a vertical line extending from the vertex toward the center of the end face and passing through the center, the number of hollow fiber membranes on the upper side of the horizontal line is 4453 and the number of hollow fiber membranes on the lower side of the horizontal line is 6547, with the point corresponding to the portion having the smallest thickness on the outer peripheral surface of the adhesive fixing portion of the end face having the hollow opening of the hollow fiber membrane being the upper vertex. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.68. Other measurement results and the like are shown in Table 2.
Comparative example 5
11000 PVDF (polyvinylidene fluoride) hollow fiber membranes (Asahi chemical Co., ltd.) were bundled and inserted into a housing having a second tubular member (168 mm in end diameter) with a rectifying tube having an inner diameter of 165mm attached thereto. The hollow fiber membrane used had an average pore diameter of 0.1 μm, an inner diameter of 0.6mm and an outer diameter of 1.0mm. As shown in fig. 10, 12 restriction members (members formed by casting an adhesive similar to the potting material described below into a mold in advance and curing the same) having a cylindrical shape with an outer diameter of 11mm were inserted and placed in the end portion of the hollow fiber membrane bundle on the side of the hollow portion, which was closed with gypsum. On the other hand, a columnar member is inserted into the end of the hollow fiber membrane bundle on the first cylindrical member side at a position where the through hole is to be formed. Thereafter, a hollow fiber membrane module was produced in the same manner as in example 1, and evaluation thereof was performed.
In this case, when a horizontal line is drawn to be perpendicular to a vertical line extending from the vertex toward the center of the end face and passing through the center, the number of hollow fiber membranes on the upper side of the horizontal line is 5180 and the number of hollow fiber membranes on the lower side of the horizontal line is 5820, with the point corresponding to the portion having the smallest thickness on the outer peripheral surface of the adhesive fixing portion of the end face having the hollow opening of the hollow fiber membrane being the upper vertex. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.89. Other measurement results and the like are shown in Table 2.
Comparative example 6
A hollow fiber membrane module was produced and evaluated in the same manner as in comparative example 1, except that a restricting member was not used at the end of the hollow fiber membrane bundle on the side where the hollow portion was closed with gypsum, 3100 PVDF (polyvinylidene fluoride) hollow fiber membranes (manufactured by asahi chemical), the end face diameter of the second cylindrical member used was 84mm, and the inner diameter of the rectifying tube was 79 mm.
In this case, when a horizontal line is drawn to be perpendicular to a vertical line extending from the vertex toward the center of the end face and passing through the center, the number of hollow fiber membranes on the upper side of the horizontal line is 1329 and the number of hollow fiber membranes on the lower side of the horizontal line is 1771, with the point corresponding to the portion having the smallest thickness on the outer peripheral surface of the adhesive fixing portion of the end face having the hollow opening of the hollow fiber membrane being the upper vertex. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.82. Other measurement results and the like are shown in Table 2.
Comparative example 7
A hollow fiber membrane module was produced and evaluated in the same manner as in comparative example 1, except that the total length of the bundle of hollow fiber membranes (manufactured by asahi chemical industry) was 1.2m, and the total length of the case after cutting the end of the bundle of hollow fiber membranes was 1.0 m.
In this case, when a horizontal line is drawn to be perpendicular to a vertical line extending from the vertex toward the center of the end face and passing through the center, the number of hollow fiber membranes on the upper side of the horizontal line is 7384 and the number of hollow fiber membranes on the lower side of the horizontal line is 9116, the point corresponding to the portion having the smallest thickness on the outer peripheral surface of the adhesive fixing portion of the end face having the hollow opening of the hollow fiber membrane is set as the upper vertex. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.81. Other measurement results and the like are shown in Table 2.
Comparative example 8
A hollow fiber membrane module was produced and evaluated in the same manner as in comparative example 1, except that a restriction member was not used at the end of the hollow fiber membrane bundle on the side where the hollow portion was closed with gypsum, 10000 PVDF (polyvinylidene fluoride) hollow fiber membranes (manufactured by asahi chemical), the end face diameter of the second cylindrical member used was 168mm, the inner diameter of the rectifying tube was 165mm, and the average pore diameter of the hollow fiber membranes used was 0.1 μm, the inner diameter was 0.7mm, and the outer diameter was 1.22 mm.
In this case, when a horizontal line is drawn to be perpendicular to a vertical line extending from the vertex toward the center of the end face and passing through the center, the number of hollow fiber membranes on the upper side of the horizontal line is 4448 and the number of hollow fiber membranes on the lower side of the horizontal line is 5552, with the point corresponding to the portion having the smallest thickness on the outer peripheral surface of the adhesive fixing portion of the end face having the hollow opening of the hollow fiber membrane being the upper vertex. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.80. Other measurement results and the like are shown in Table 2.
Comparative example 9
A hollow fiber membrane module was produced and evaluated in the same manner as in comparative example 1, except that a restricting member was not used at the end of the hollow fiber membrane bundle on the side where the hollow portion was closed with gypsum, 5600 PVDF (polyvinylidene fluoride) hollow fiber membranes (manufactured by sunburst chemical) were used, the end surface diameter of the second tubular member used was 168mm, and the inner diameter of the rectifying tube was 165 mm.
In this case, when a horizontal line is drawn to be perpendicular to a vertical line extending from the vertex toward the center of the end face and passing through the center, the number of hollow fiber membranes on the upper side of the horizontal line is 2202 and the number of hollow fiber membranes on the lower side of the horizontal line is 3398, with the point corresponding to the portion having the smallest thickness on the outer peripheral surface of the adhesive fixing portion of the end face having the hollow opening of the hollow fiber membrane being the upper vertex. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.65. In this hollow fiber membrane module, a gap is visible in the longitudinal direction in a part of the circumferential direction of the surface where the adhesive fixing portion and the housing are adhered. Other measurement results and the like are shown in Table 2.
Comparative example 10
A hollow fiber membrane module was produced in the same manner as in comparative example 1, except that a restriction member was not used at the end of a hollow fiber membrane bundle on the side where the hollow portion was closed with gypsum, 6600 PVDF (polyvinylidene fluoride) hollow fiber membranes (manufactured by Asahi chemical Co., ltd.), the end face diameter of the second cylindrical member used was 168mm, the inner diameter of the rectifying tube was 165mm, and a two-component thermosetting polyurethane resin (manufactured by TOSOH Co., ltd.: KC-462/N-4273 (trade name), the viscosity after 10 minutes after mixing measured at 25 ℃ C.: 5 Pa.s, and the viscosity after 30 minutes measured at 25 ℃ C.: 850 Pa.s) was used as a potting material, and evaluated.
In this case, when a horizontal line is drawn to be perpendicular to a vertical line extending from the vertex toward the center of the end face and passing through the center, the number of hollow fiber membranes on the upper side of the horizontal line is 2763 and the number of hollow fiber membranes on the lower side of the horizontal line is 3837, with the point corresponding to the portion having the smallest thickness on the outer peripheral surface of the adhesive fixing portion of the end face having the hollow opening of the hollow fiber membrane being the upper vertex. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.72. Other measurement results and the like are shown in Table 2.
Comparative example 11
11500 PVDF (polyvinylidene fluoride) hollow fiber membranes (manufactured by Asahi chemical Co., ltd.) were bundled to a length of 2.3m, lifted vertically, and cut off from the lower end face to align the surfaces. The hollow portion was sealed with gypsum on one side of the thus-produced membrane bundle, and inserted into a housing having a second tubular member (end surface diameter 218 mm) with a rectifying tube having an inner diameter of 216mm attached thereto. The hollow fiber membrane used had an average pore diameter of 0.1 μm, an inner diameter of 0.7mm and an outer diameter of 1.22mm.
Next, a columnar member is inserted into the end of the hollow fiber membrane bundle on the first tubular member side at a position where the through hole is to be formed.
Next, the vessel for forming the adhesive fixing portion, to which the tube for introducing the potting material is attached, is fixed to the second cylindrical member of the case 5, and the potting material is injected into the second cylindrical member of the case by its own weight in the vertical direction. After the potting material is cured and stopped from flowing, the case 5 is turned upside down, and the container for forming the adhesive fixing portion to which the tube for introducing the potting material is attached is fixed to the first cylindrical member of the case, and the potting material is injected into the first cylindrical member of the case by its own weight in the vertical direction. As the potting material, a two-component thermosetting epoxy resin (trade name: A-751A/A-751B, manufactured by SANYU REC Co., ltd.) was used, and its viscosity after 10 minutes was 1.2 Pa.s after mixing measured at 25℃and its viscosity after 30 minutes was 2.0 Pa.s measured at 25 ℃. After the potting material was cured to stop fluidization, it was heated to 50℃in an oven and cured. Further, the viscosity after 10 minutes and the viscosity after 30 minutes after mixing were measured by a type B viscometer.
Then, the end of the case on the second tubular member side was cut off to set the total length of the case to 2.1m, and the hollow opening on one side of the hollow was closed at the stage before bonding. On the other hand, the columnar member is removed from the first adhesive fixing portion on the first cylindrical member side, thereby forming a plurality of through holes. In addition, the effective membrane length of the hollow fiber membrane module is 2m.
In this case, when a horizontal line is drawn to be perpendicular to a vertical line extending from the vertex toward the center of the end face and passing through the center, the number of hollow fiber membranes on the upper side of the horizontal line is 5602 and the number of hollow fiber membranes on the lower side of the horizontal line is 5898, with the point corresponding to the portion having the smallest thickness on the outer peripheral surface of the adhesive fixing portion of the end face having the hollow opening of the hollow fiber membrane being the upper vertex. That is, the ratio of (the number of hollow fiber membranes on the upper side)/(the number of hollow fiber membranes on the lower side) was 0.95.
Although the embodiments of the present invention have been described in detail above, the present invention may be variously modified in design within a scope not departing from the gist thereof.
TABLE 1
TABLE 2
Description of the reference numerals
1. Hollow fiber membrane module
2. Hollow fiber membrane
3. Hollow fiber membrane bundle
5. Shell body
5a annular concave-convex portion
5b outer region
5c outer region
7. Rectifying cylinder
7a flange
8. Protective member
10 11 cover
10a,11a pipeline
12. Sanitary pad
13. Clamp
20. First adhesive fixing part
20a through hole
21. Second adhesive fixing part
21a end face of the second adhesive fixing portion
30. Through hole
41. Limiting member
50. Protruding part
51. First tubular member
52. Second tubular member
53. Third tubular member
52a nozzle
P potting material
S potting material interface
S' virtual bonding interface
Claims (11)
1. A hollow fiber membrane module, the hollow fiber membrane module comprising: a tubular casing, a hollow fiber membrane bundle formed by bundling a plurality of hollow fiber membranes, a first adhesive fixing part and a second adhesive fixing part,
the two end parts of the hollow fiber membrane bundle are respectively accommodated in the cylindrical shell through the first bonding fixing part and the second bonding fixing part;
the first and second adhesive fixing portions have substantially circular end faces perpendicular to a longitudinal direction of the housing, and hollow portions of the plurality of hollow fiber membranes are open at least one of the end faces;
in the first adhesive fixing portion and/or the second adhesive fixing portion having the end face of the hollow portion opening of the hollow fiber membranes, the hollow fiber membrane bundles are adhered and fixed to the housing by filling the adhesive resin with a prescribed thickness in the longitudinal direction in a state in which a restricting member restricting the deflection of the plurality of hollow fiber membranes is not included in a region between the outer surfaces of the plurality of hollow fiber membranes and the inner surface of the housing;
When a horizontal line is drawn perpendicular to a vertical line extending from the upper vertex toward the center of the end face and passing through the center, a ratio of the number of hollow fiber membranes located above the horizontal line to the number of hollow fiber membranes located below (the number of hollow fiber membranes located above)/(the number of hollow fiber membranes located below) is 0.9 or more and 1.1 or less.
2. The hollow fiber membrane module according to claim 1, wherein, on the end face of the hollow opening of the hollow fiber membrane of the first adhesive fixing portion and/or the second adhesive fixing portion, when a first perfect circle is defined as a perfect circle including the smallest diameter of all hollow fiber membranes existing on the end face, a second perfect circle concentric with the first perfect circle and having a diameter smaller than 2cm than the first perfect circle, a first square being the largest of squares having one side of Ncm (where N is a natural number) located at the center within the second perfect circle, and N obtained by dividing the first square into 1cm squares 2 In the case of the second squares, the ratio of (minimum value)/(maximum value) of the number of hollow fiber membranes included in each of the second squares is 0.4 or more.
3. The hollow fiber membrane module according to claim 1 or 2, wherein a diameter of an end face of the hollow portion opening of the hollow fiber membrane is 150mm or more.
4. The hollow fiber membrane module according to any one of claims 1 to 3, wherein (a thickness L of the adhesive fixing portion at one intersection of the outer peripheral surface and the horizontal line) 1 And a thickness L of the adhesive fixing portion at the other intersection point of the outer peripheral surface and the horizontal line 2 The average value of (1) - (the thickness L of the adhesive fixing portion at the center of the end face) О ) 1mm or more and 12mm or less, and,
(thickness L of the adhesive fixing portion at the other intersection point of the outer peripheral surface and a perpendicular line from the upper side apex toward the center of the end surface 4 ) - (thickness L of the adhesive securing portion at the upper side apex) 3 ) 3mm or more and 12mm or less.
5. The hollow fiber membrane module according to any one of claims 1 to 4, wherein the overall length of the housing is 1m and more.
6. The hollow fiber membrane module according to any one of claims 1 to 5, wherein a total cross-sectional area of all hollow fiber membranes/a housing interior cross-sectional area, i.e., a filling rate of hollow fiber membranes on end faces of hollow portion openings of the hollow fiber membranes is 10% or more and 45% or less.
7. The hollow fiber membrane module according to claim 6, wherein a total cross-sectional area of all hollow fiber membranes/a cross-sectional area of a housing interior, i.e., a filling ratio of the hollow fiber membranes on an end face of the hollow portion opening of the hollow fiber membranes is 25% or more.
8. The hollow fiber membrane module according to any one of claims 1 to 7, wherein the resin constituting the first adhesive fixing portion and/or the second adhesive fixing portion having the end face of the hollow portion opening of the hollow fiber membrane is a single thermosetting resin having a D hardness of 60 or less at 25 ℃ according to JIS K7215.
9. The hollow fiber membrane module according to claim 8, wherein the single thermosetting resin is a two-liquid curable thermosetting resin having a viscosity of 1 Pa-s and more and 10 Pa-s and less after 10 minutes from the start of two-liquid mixing and a viscosity exceeding 100 Pa-s after 30 minutes.
10. The hollow fiber membrane module according to any one of claims 1 to 9, wherein the plurality of hollow fiber membranes are composed of a fluororesin.
11. The hollow fiber membrane module according to any one of claims 1 to 10, wherein, on a virtual bonding interface in which an end surface of a hollow portion opening of the hollow fiber membrane is virtually moved in parallel toward a longitudinal center by an amount of a thickness of a portion having a minimum thickness in an outer peripheral surface of the first bonding fixing portion and/or the second bonding fixing portion, a total cross-sectional area of all hollow fiber membranes/a case inner cross-sectional area is 20% or more and 50% or less, and, on the virtual bonding interface, a point corresponding to a portion having a minimum thickness in the longitudinal direction on the outer peripheral surface is set to be an upper vertex, and when a horizontal line orthogonal to a vertical line extending from the upper vertex toward a center of the virtual bonding interface and passing through the center is drawn, a ratio of the number of hollow fiber membranes located on the upper side to the number of hollow fiber membranes located on the lower side (the number of hollow fiber membranes located on the upper side)/(the number of hollow fiber membranes located on the lower side) is set to be 0.85 or more and 1.15 or less.
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| JP2020-198477 | 2020-11-30 | ||
| JP2020198477 | 2020-11-30 | ||
| PCT/JP2021/043905 WO2022114227A1 (en) | 2020-11-30 | 2021-11-30 | Hollow fiber membrane module |
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| CN116528967A true CN116528967A (en) | 2023-08-01 |
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| JPH06327905A (en) * | 1993-05-21 | 1994-11-29 | Toray Ind Inc | Degassing membrane module and its operation |
| JP4012640B2 (en) * | 1998-12-24 | 2007-11-21 | 旭化成ケミカルズ株式会社 | Hollow fiber membrane module |
| JP2006068689A (en) * | 2004-09-03 | 2006-03-16 | Toyobo Co Ltd | Drying method for bundle of hollow fiber membrane |
| TWI457169B (en) * | 2008-01-11 | 2014-10-21 | Sumitomo Electric Industries | Separation film element, separation film module and method for manufacturing separation film element |
| JP6276037B2 (en) * | 2014-01-10 | 2018-02-07 | 旭化成株式会社 | Hollow fiber membrane module and filtration method |
| WO2019092105A1 (en) * | 2017-11-09 | 2019-05-16 | Frank Wiese | Membrane bundle package having spacers |
-
2021
- 2021-11-30 WO PCT/JP2021/043905 patent/WO2022114227A1/en active Application Filing
- 2021-11-30 JP JP2022565512A patent/JPWO2022114227A1/ja active Pending
- 2021-11-30 CN CN202180080556.4A patent/CN116528967A/en active Pending
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| WO2022114227A1 (en) | 2022-06-02 |
| JPWO2022114227A1 (en) | 2022-06-02 |
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