WO2016035798A1 - 中空糸膜モジュールおよび中空糸膜モジュールの製造方法 - Google Patents
中空糸膜モジュールおよび中空糸膜モジュールの製造方法 Download PDFInfo
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- WO2016035798A1 WO2016035798A1 PCT/JP2015/074894 JP2015074894W WO2016035798A1 WO 2016035798 A1 WO2016035798 A1 WO 2016035798A1 JP 2015074894 W JP2015074894 W JP 2015074894W WO 2016035798 A1 WO2016035798 A1 WO 2016035798A1
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- hollow fiber
- fiber membrane
- flow path
- membrane module
- path member
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- 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
- B01D63/021—Manufacturing thereof
- B01D63/022—Encapsulating hollow fibres
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- 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
- B01D63/04—Hollow fibre modules comprising multiple hollow fibre assemblies
-
- 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
- B01D63/032—More than two tube sheets for one bundle
-
- 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
- B01D63/033—Specific distribution of fibres within one potting or tube-sheet
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
- B01D65/022—Membrane sterilisation
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/08—Flow guidance means within the module or the apparatus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/08—Flow guidance means within the module or the apparatus
- B01D2313/086—Meandering flow path over the membrane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/19—Specific flow restrictors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/44—Cartridge types
Definitions
- the present invention relates to a hollow fiber membrane module used in the water treatment field, the fermentation industry field, the pharmaceutical / medical field, the food industry field, and the like, and more specifically, deposits of suspended substances near the binding portion of the hollow fiber membrane module.
- the present invention relates to a hollow fiber membrane module to be suppressed and a manufacturing method thereof.
- a hollow fiber membrane module contains a hollow fiber membrane bundle in which approximately several hundred to several tens of thousands of hollow fiber membranes are bundled in a cylindrical case, and binds at least one end of the hollow fiber membrane bundle, It is the structure accommodated in the cylindrical case.
- Patent Document 1 discloses a module in which both ends of a hollow fiber membrane bundle are bonded and bonded, and a plurality of through holes are provided in one of the binding portions. It functions as a mouth, an air supply port for washing, and a suspended matter discharge port.
- the inside of the hollow fiber membrane module is sterilized or sterilized.
- general sterilization and sterilization methods include hot water sterilization, dry heat sterilization, boiling sterilization, steam sterilization, ultraviolet sterilization, gamma ray sterilization, and gas sterilization.
- hot water sterilization usually 80 ° C, 1 hour
- steam sterilization usually 121 ° C, 20 minutes
- the through hole serves as a steam drain outlet.
- steam drain accumulates in the staying part between the through holes above the bundling part, the temperature is not sufficiently increased. Lead to contamination with bacteria.
- This invention is made
- the present invention provides the following techniques (1) to (11).
- a cylindrical case having a first end and a second end in the height direction, and accommodated in the cylindrical case, the end on the first end side being closed, and an end on the second end side
- a hollow fiber membrane bundle having a plurality of hollow fiber membranes, the first bundling portion for bundling the end portion on the first end side of the hollow fiber membrane, and the first end side of the first bundling portion
- a hollow fiber membrane module comprising: a flow path member that directs at least a part of the fluid flowing out from the end on the end side in a direction intersecting a height direction of the cylindrical case.
- the at least one flow path member is provided so as to protrude from the end surface on the second end side of the first bundling portion, and is in contact with the surface on the second end side of the first bundling portion.
- the outer diameter R of the first bundling portion and the total area S of the openings of the flow path member satisfy 0.004 ⁇ S / R 2 ⁇ 1.2 (2) or (3) Hollow fiber membrane module.
- At least one terminal end of the first flow path is disposed in an area within a range of 3 mm in height from the lowest part of the second end side end face of the first bundling portion.
- the hollow fiber membrane module according to any one of (6).
- the total area of the first flow path in the cross section perpendicular to the height direction includes the first binding portion, and the area inside the cylindrical case in the cross section perpendicular to the height direction,
- the hollow fiber membrane module according to any one of (1) to (7), which is 2% or more and 35% or less.
- the hollow fiber membrane module includes a plurality of the first flow paths, and the flow path member changes an outflow direction from a part of the plurality of the first flow paths. In the cross section perpendicular to the height direction, of the first flow paths, the area of the flow path that supplies the flow whose direction is changed by the flow path member is the total of the first flow paths.
- the hollow fiber membrane module according to any one of (1) to (8), which is 30% or more and 90% or less with respect to the area.
- a method for producing a hollow fiber membrane module according to any one of (1) to (9), The following steps (a) to (d): (A) disposing a potting jig so as to surround at least one end of the hollow fiber membrane bundle having the plurality of hollow fiber membranes; (B) a step of forming a bundling portion in which the hollow fiber membranes are bonded and fixed by curing a potting agent in the potting jig; (C) removing the potting jig; (D) A method of manufacturing a hollow fiber membrane module, comprising: fixing the flow path member to the binding portion.
- the hollow fiber membrane module of the present invention includes a hollow fiber membrane, a first bundle side of the hollow fiber membrane that is closed and bundled, and a first bundle side from the first end side toward the second end side.
- the first flow path for guiding the fluid through the bundling portion and the flow of at least a part of the fluid that has flowed out from the end on the second end side of the first flow path is the height of the cylindrical case that accommodates the hollow fiber membrane bundle.
- a flow path member directed in a direction intersecting the vertical direction is provided. Since the flow direction determined in the first flow path can be changed by the flow path member, the staying portion between the first flow paths can be reduced on the first bundling portion.
- FIG. 1 is a schematic cross-sectional view of a hollow fiber membrane module 100A according to the prior art and a schematic view showing the flow from the bottom to the top of the fluid inside the module.
- FIG. 2 is a schematic cross-sectional view of a hollow fiber membrane module 100A according to the prior art and a diagram schematically showing the flow from above to below the fluid inside.
- FIG. 3 is a schematic cross-sectional view of the hollow fiber membrane module 100B according to the first embodiment of the present invention.
- FIG. 4 is an enlarged view of the first binding portion of the hollow fiber membrane module 100B according to the first embodiment of the present invention, and a diagram schematically showing how the fluid flows from the bottom to the top in the first flow path. .
- FIG. 1 is a schematic cross-sectional view of a hollow fiber membrane module 100A according to the prior art and a schematic view showing the flow from the bottom to the top of the fluid inside the module.
- FIG. 2 is a schematic cross-sectional view of a hollow fiber membrane module 100A
- FIG. 5 is a diagram showing an example of the shape of the flow path member of the present invention, where (a) is a baffle plate-shaped flow path member, (b) is a spherical flow path member, and (c) is a planar tip. (D) shows a channel member having a dome-shaped tip.
- FIG. 6 is an enlarged view of the first binding portion of the hollow fiber membrane module 100B according to the first embodiment of the present invention, and a diagram schematically showing how the fluid flows from the top to the bottom in the first flow path. .
- FIG. 7 is a diagram showing an example of the shape of the opening of the flow path member of the present invention.
- FIG. 8 is a view showing an example of the arrangement of the flow path member of the present invention
- (a) is a schematic cross-sectional view of the flow path member and the first binding part
- (b) is the flow path member and the first binding.
- It is a schematic top view of a part
- (c) is an enlarged view of a flow-path member
- FIG. 9 is a schematic top view of the flow path member and the first binding portion showing an example of the arrangement of the flow path member of the present invention.
- FIG. 10 is a flowchart showing an example of a method for manufacturing the hollow fiber membrane module 100B according to the first embodiment of the present invention.
- FIG. 11 is a diagram illustrating an example of a method for manufacturing the hollow fiber membrane module 100B according to the first embodiment of the present invention.
- the hollow fiber membrane module configuration of the present invention will be described in detail with reference to the drawings.
- “upper” and “lower” are based on the state shown in the figure and are for convenience.
- the side where the filtrate flows out is the “up” direction.
- the direction from “down” to “up” is expressed as “height direction” for convenience.
- the vertical direction coincides with the vertical direction in the figure.
- the direction of the flow path does not necessarily coincide with the height direction (direction perpendicular to the radial direction of the cylindrical case).
- the opening of the flow path only needs to be provided on the surface on the first end side and the surface on the second end side of the binding portion. That is, the flow path may be provided obliquely with respect to the height direction.
- FIG. 3 is a schematic longitudinal sectional view of the hollow fiber membrane module 100B according to the first embodiment of the present invention.
- the hollow fiber membrane module 100B includes a cylindrical case 1 having a first end 1a and a second end 1b in the height direction, and is accommodated in the cylindrical case 1, and is disposed on the first end 1a side.
- the hollow fiber membrane bundle 12 having a plurality of hollow fiber membranes 2 with the end portion (first end portion) closed and the end portion (second end portion) on the second end 1b side opened,
- a first bundling portion 3 for bundling the end portion on the first end 1a side
- a first flow path 4 for guiding fluid through the first bundling portion 3 from the first end 1a side toward the second end 1b side
- a flow path member 5 that directs at least a part of the fluid flowing out from the end of the first flow path 4 on the second end 1 b side in the radial direction of the cylindrical case 1.
- the rod-shaped cylindrical case 1 includes a hollow cylindrical case 1 and an upper cap 6 and a lower cap 7 provided at both ends of the cylindrical case 1.
- an upper cap 6 having a filtrate outlet 8 is provided at the upper part of the cylindrical case 1
- a lower cap 7 having a filtrate inlet 9 is provided at the lower part of the cylindrical case 1.
- the upper cap 6 and the lower cap 7 use, for example, a gasket 10 as shown in FIG. 3, and are fixed to the cylindrical case 1 with a clamp or the like.
- the saddle-shaped cylindrical case 1 has flanges 1D and 1E over the entire circumference of the cylindrical case 1 at its upper and lower ends. Further, a filtrate outlet 11 as a nozzle for discharging fluid (filtrate) is provided on the side of the cylindrical case 1 near the filtrate outlet 8, that is, near the second end 1b.
- the upper cap 6 has an inner diameter substantially equal to the inner diameter of the cylindrical case 1, and the upper end side is reduced in diameter to form the filtrate outlet 8.
- a step portion 6 ⁇ / b> A for forming a groove when connected to the cylindrical case 1 is formed over the entire circumference of the upper cap 6.
- the lower cap 7 has an inner diameter substantially equal to the inner diameter of the cylindrical case 1, and the lower end side of the lower cap 7 is reduced in diameter to form the filtrate inlet 9.
- the hollow fiber membrane module 100B includes a hollow fiber membrane bundle 12 including a plurality of hollow fiber membranes 2 and a bundling portion that binds the hollow fiber membranes 2 at the end of the hollow fiber membrane bundle 12.
- the bundling portion has a first bundling portion 3 disposed on the filtrate inlet 9 side of the cylindrical case 1 and a second bundling portion 13 disposed on the filtrate outlet 8 side of the cylindrical case 1.
- the hollow fiber membrane module 100B is disposed between the tubular case 1 and the hollow fiber membrane bundle 12 so as to be aligned in the radial direction of the filtrate outlet 11 and the cylindrical case 1, and has a plurality of side surfaces.
- a rectifying cylinder 15 having a rectifying hole 14, and the second bundling portion 13 is accommodated in the rectifying cylinder 15.
- the 1st binding part 3 arrange
- the fluid (arrow A) flowing out from the flow path member 5 is in the radial direction of the cylindrical case 1 with respect to the hollow fiber membrane 2. It acts as a force, and the hollow fiber membrane 2 is easily broken at this portion.
- a material having a certain degree of hardness is provided as a cushioning material around the hollow fiber membrane 2 on the end surface on the second end 1b side of the first binding unit 3, and the cushioning material (the second end 1b of the first binding unit 3).
- the hardness of the portion at the side end face is preferably less than D hardness 85, more preferably less than 60 D hardness. If the hardness is too low, there is a high possibility of breakage during handling of the hollow fiber membrane module 100B, preferably A hardness 10 or more, more preferably A hardness 30 or more.
- the hardness can be measured using a commercially available hardness meter based on JIS K 6253.
- the cushioning material may be used individually. In that case, the cushioning material may be used in the vicinity of the end surface on the second end 1b side of the first binding portion 3.
- the bundling method is not particularly limited as long as the mechanical strength, chemical durability, thermal durability, and the like of the bundling portion are satisfied, but the outer periphery of the hollow fiber membrane bundle 12 is covered with a heat shrinkable tube or the like, and heated and bundled And a method of arranging hollow fiber membranes on a sheet and bundling them together, and a method of bonding using a potting agent.
- the potting agent can contain a silicone resin, an epoxy resin, a polyurethane resin, or the like as a main component. Further, the potting agent may contain additives such as silica, glass and rubber other than the adhesive.
- the first binding part 3 is accommodated in a cylindrical first binding part case 16 having a bottom part below.
- the outer diameter of the first binding portion case 16 is configured to be smaller than the inner diameter of the cylindrical case 1.
- the first binding part case 16 is not necessarily required, it is used for protecting the first binding part 3, and the material is not particularly limited as long as it satisfies mechanical strength, chemical durability, thermal durability, etc.
- fluorine resin such as vinyl chloride resin, polypropylene resin, polysulfone resin, polytetrafluoroethylene, perfluoroalkoxy fluorine resin, polycarbonate, polypropylene, polymethylpentene, polyphenylene sulfide, polyether ketone, stainless steel, aluminum, etc. be able to.
- the first binding part 3 may be fixed to the cylindrical case 1, and the fixing method is not related to the present invention. Moreover, the shape of the 1st binding part case 16, and the presence or absence of the 1st binding part case 16 have nothing to do with this invention.
- the 1st binding part 3 has the 1st flow path 4 used as fluid flow paths, such as to-be-filtered liquid.
- the first flow path 4 includes a through hole 4 ⁇ / b> A provided in the first binding portion 3, a clearance 4 ⁇ / b> B between the cylindrical case 1 and the first binding portion 3, and the like.
- the total area of the first flow paths 4 in the cross section perpendicular to the height direction is the first binding portion. It is preferable that they are 2% or more and 35% or less with respect to the area inside the said cylindrical case in the cross section perpendicular
- the area of the first flow path 4 is small, the space between the through holes 4A that can be a staying location is widened, and even if the flow path member 5 is provided, it is difficult to obtain the effect of reducing the staying. Further, the pressure loss when the fluid passes through the first flow path 4 is large, and when the fluid flows from the bottom to the top, the pump power cost becomes large. Furthermore, when the fluid flows from the top to the bottom, the flow is unlikely to occur, and turbidity may block the first flow path.
- the area of the first flow path 4 is large, the cross-sectional area of the portion other than the hollow fiber membrane 2 in the first bundling portion 3 is small, so that the hollow fiber membranes 2 are closely packed and the first end of the hollow fiber membrane 2 is There is a possibility that problems such as poor sealing occur on the 1a side or turbidity deposited between the hollow fiber membranes 2 becomes difficult to be discharged.
- the pressure loss of the fluid is not sufficient and the flow flowing into the flow path member 5 is biased. Arise. If the flow flowing into the flow path member 5 is biased, the radial flow flowing out from the flow path member 5 is biased, the residence portion becomes large, and turbidity tends to accumulate.
- the first flow path 4 preferably includes a plurality of through-holes 4A, and the arrangement of each through-hole 4A is such that the positions of the vertices of many equilateral triangles, the positions of intersections of radiation and concentric circles, and the intersections on the lattice
- the position is arbitrary, but if there is a deviation in the interval between adjacent through-holes, the portion where the interval is larger than others tends to stay. Therefore, it is preferable to make the interval equal so that there is no great difference in the interval.
- At least one terminal end of the first flow path 4 is arranged in a region within a height of 3 mm from the lowest part of the end surface on the second end 1b side of the first binding portion 3.
- the end surface on the second end 1b side of the first binding unit 3 can be horizontal, but when potting is performed with the first binding unit case 16 tilted from the vertical direction, A slope is formed on the end surface on the second end 1b side.
- the cross-sectional shape perpendicular to the height direction of the through hole 4A is arbitrary such as a circle, an ellipse, a polygon, and a star.
- the flow path member 5 is disposed so as to change the direction of the flow that has flowed out from a part of the first flow paths 4, and the first flow path 4 in a cross section perpendicular to the height direction.
- the area of the flow path that supplies the flow whose direction is changed by the flow path member 5 is preferably 30% or more and 90% or less with respect to the total area of the first flow path 4.
- the pressure loss may be excessive when the fluid flows through the flow path member 5 from below, Further, when the fluid flows through the flow path member 5 from the top to the bottom, the flow is difficult to occur, and there is a possibility that the water is not sufficiently drained.
- the area of the flow path that supplies the flow whose direction is changed by the flow path member 5 is too small, the flow that passes through other than the flow path member 5 when the fluid flows through the first flow path 4 from the bottom to the top Becomes preferential, and the effect of reducing the staying portion by the flow path member 5 is not sufficiently obtained.
- the shape of the flow path member 5 is not particularly limited as long as the flow direction of the fluid flowing out from the first flow path 4 can be changed.
- the baffle plate-shaped flow path member 5A shown in FIG. (B) a spherical channel member 5B, (c) a channel member 5C having a planar tip, and (d) a channel member 5D having a dome-shaped tip.
- the fixing method of the flow path member 5 is not particularly limited as long as the mechanical strength is sufficient, a method of fixing to the first binding part 3, a method of fixing the scaffold of the flow path member 5 to the wall part of the through hole 4A, A method of fixing to the first binding part case 16, a method of fixing to the inner wall of the cylindrical case 1, and the like can be mentioned.
- the flow path member 5 and the first binding unit case 16 may be manufactured in advance as one member. Further, if the outer wall of the flow path member 5 has a sharp portion, a burr or the like, the hollow fiber membrane 2 may be damaged, and the filtrate to be filtered may leak to the filtrate side. Is preferably smooth. Taking these into consideration, in this embodiment, the flow path member 5 (5D) having a dome-shaped tip is shown in each drawing, but the shape of the flow path member 5 of the present invention is not limited to this.
- the driving force that causes the fluid to flow down may be only its own weight. Therefore, it is preferable to make the space that can be a staying portion as small as possible.
- the flow path member 5 serves as both a flow path for fluid flowing from the first end 1a side to the second end 1b side and a flow path for fluid flowing from the second end 1b side to the first end 1a side. It has an opening 5E.
- the opening 5E5 is preferably in contact with the surface of the first binding unit 3 on the second end 1b side.
- the opening 5E is in contact with the surface on the second end 1b side of the first bundling portion 3 so that a fluid flow is generated in the vicinity of the surface on the second end 1b side of the first bundling portion 3 where the suspended matter is easily deposited. be able to.
- the width of the portion in contact with the surface on the second end 1b side of the first bundling portion 3 is preferably 1 mm or more. If it is less than 1 mm, it takes time for drainage, or sufficient drainage cannot be performed, for example, the opening is blocked by turbidity contained in the liquid.
- the length of the opening 5E in the height direction of the soot channel member 5 is preferably 1 mm or more and 30 mm or less, and more preferably 5 mm or more and 20 mm or less.
- the length in the height direction of the opening 5E is 1 mm or more so that the pressure loss can be suppressed, so that a module operation that does not require a large pump power cost is possible. It becomes.
- blockage due to turbidity, etc., and blockage due to manufacturing errors are unlikely to occur.
- the proportion of the radial component in the flow flowing out from the flow path member 5 can be kept relatively large, so that suspended substances and the like are deposited.
- the effect of reducing the location (retention part) that is easy to do becomes higher.
- the width of the opening 5 ⁇ / b> E of the flow path member 5 is larger as it is positioned lower in the height direction, and can be gradually decreased upward.
- the vicinity of the surface on the second end 1b side of the first bundling portion 3 is a place where suspended substances are most easily deposited, but the opening has such a shape, so that the radial component of the flow at this place is Since it becomes large, the amount of suspended matter deposited can be reduced.
- the arrangement (that is, the number, position, and orientation) of the flow path member 5 is not particularly limited.
- the hollow fiber membranes 2 positioned in a space within a height of 30 mm from the end surface on the second end 1b side of the first binding unit 3 are in contact with the fluid flowing out from the opening 5E of at least one flow path member 5, respectively.
- the arrangement of the flow path member 5 is preferably set.
- FIGS. 8A and 8B are examples of such a configuration.
- the flow path member 5 is opened from the upper end surface of the bundling portion 3 to a height of 30 mm.
- each flow path member 5 is arrange
- the opening 5E of a certain flow path member 5 faces a non-opening (that is, a portion other than the opening 5E) of the flow path member 5 in the vicinity thereof. ing.
- the total area S of the openings 5E of the flow path member 5 and the outer diameter R on the second end 1b side of the first bundling portion 3 satisfy 0.004 ⁇ S / R 2 ⁇ 1.2.
- the S / R 2 value is 0.004 or more, the flow flowing out from the opening 5E of the flow path member 5 can be made uniform. Thereby, the flow that flows out from the opening 5E of the flow path member 5 reaches most of the hollow fiber membranes 2 in the vicinity of the end surface on the second end 1b side of the first bundling portion 3 and cleans the membrane surface. Furthermore, since the generation of a locally excessively strong flow from the opening 5E of the flow path member 5 is suppressed, a failure such as the hollow fiber membrane 2 being damaged by receiving a force higher than its own strength occurs. Hateful.
- the S / R 2 value is 1.2 or less, so that the flow velocity of the flow flowing out from the opening 5E of the flow path member 5 can be sufficiently increased, and the suspended matter or the like is likely to accumulate (retention portion). Can be reduced.
- each flow path member 5 may be provided uniformly on a surface perpendicular to the height direction of the flow path member 5, but may be unevenly distributed in an arbitrary direction.
- the flow in the hollow fiber membrane module 100 ⁇ / b> B is controlled by unevenly distributing the openings 5 ⁇ / b> E and changing the direction in which the area of the openings 5 ⁇ / b> E is large depending on each flow path member 5.
- a swirling flow can be generated.
- the flow path member 5 is a flow path member 5 (5D) having a dome-shaped tip as shown in FIG. 8C
- the flow path member 5 is located above the uppermost opening 5E.
- the depth L of the bag path surrounded by the inner wall of the flow path member 5 and the circle equivalent equivalent diameter D of the bag path satisfy L / D ⁇ 5.0.
- the equivalent circle diameter refers to the diameter of a circle when the shape of a cross section perpendicular to the height direction is replaced with a circle having the same area.
- the confined bag space in the flow path member 5 becomes a stagnant part, and turbidity is likely to accumulate, and sterilization and sterilization are likely to occur during hot water sterilization and steam sterilization.
- L / D ⁇ 5.0 the shape of the flow path member 5 can be made into a small shape with a recessed bag space, and the efficiency of sterilization and sterilization can be improved.
- the hollow fiber membrane module 100B of this embodiment includes a hollow fiber membrane 2 as a separation membrane. Hundreds to tens of thousands of hollow fiber membranes 2 are bundled to form a hollow fiber membrane bundle 12.
- the hollow fiber membrane 2 is advantageous because it generally has a specific surface area larger than that of a flat membrane, and the amount of liquid that can be filtered per unit time is large.
- the structure of the hollow fiber membrane 2 is a symmetrical membrane having a uniform pore diameter as a whole, an asymmetric membrane whose pore diameter changes in the thickness direction of the membrane, and a separation for separating the support layer and the target substance for maintaining strength. There are composite films having a functional layer.
- the average pore diameter of the hollow fiber membrane 2 may be appropriately selected depending on the separation target, but is preferably 10 nm or more and 220 nm or less for the purpose of separation of microorganisms such as bacteria and fungi and animal cells. If the average pore size is less than 10 nm, the water permeability becomes low, and if it exceeds 220 nm, microorganisms and the like may leak.
- the average pore size in the present invention is the pore size of the dense layer having the smallest pore size.
- the material of the separation membrane is not particularly limited.
- the separation membrane include polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, ethylene tetrafluoride / hexafluoropropylene copolymer, and ethylene / tetrafluoroethylene copolymer.
- Fluorine resins such as cellulose acetate, cellulose acetate propionate, cellulose esters such as cellulose acetate butyrate, polysulfone resins such as polysulfone and polyethersulfone, resins such as polyacrylonitrile, polyimide, and polypropylene can be contained. .
- separation membranes made of fluororesins and polysulfone resins have high heat resistance, physical strength, and chemical durability. Therefore, fermentation industry, pharmaceutical production, food industry, It can be suitably used for a hollow fiber membrane module in the treatment field and the like.
- the total area S of the openings 5E of the flow path member 5 and the outer diameter R on the second end 1b side of the first binding portion 3 satisfy 0.004 ⁇ S / R 2 ⁇ 1.2. It is preferable that 0.01 ⁇ S / R 2 ⁇ 0.86 is satisfied.
- the total area S and the outer diameter R satisfy this range, the flow that reduces the portion (retention part) where the suspended solids easily accumulate in the hollow fiber membrane module 100B is generated effectively and without large deviation. be able to.
- the hollow fiber membrane may be damaged by the flow from the opening 5E.
- the hollow fiber membrane 2 is preferably high in strength.
- the strength (breaking strength) per film is preferably 4.9 N or more, more preferably 5.9 N or more, and further preferably 7.8 N or more.
- Tensile strength (N) was measured using a tensile tester (TENSILON (registered trademark) / RTM-100 manufactured by Toyo Baldwin Co., Ltd.), and the separation membrane wetted with water was crossheaded with a test length of 50 mm and a full scale load of 5 kg. The measurement was performed at a speed of 50 mm / min, and the strength (N) was obtained by averaging the results of 10 measurements performed by changing the sample.
- the hollow fiber membrane 2 may further contain a hydrophilic resin in addition to the fluorine-based resin or the polysulfone-based resin.
- a hydrophilic resin in addition to the fluorine-based resin or the polysulfone-based resin.
- the hydrophilic resin may be any resin that can impart hydrophilicity to the separation membrane, and is not limited to a specific compound.
- cellulose ester, fatty acid vinyl ester, vinyl pyrrolidone, ethylene oxide, Propylene oxide, polymethacrylic acid ester resin, polyacrylic acid ester resin and the like are preferably used.
- a potting agent may be used for binding the hollow fiber membranes 2 in some cases.
- the hollow fiber membrane is filled in the potting part forming jig and fixed with a potting agent, but the hollow fiber membrane 2 is dried in advance for handling and adhesion problems.
- many of the hollow fiber membranes 2 are shrunk by drying and have a problem that the water permeability is lowered, those that are dried after being immersed in a glycerin aqueous solution are used.
- glycerin When dried after immersing in an aqueous glycerin solution, glycerin remains in the pores, so that shrinkage due to drying can be prevented, and water permeability can be restored by performing immersion treatment with a solvent such as ethanol after that. .
- the hollow fiber membrane module 100B can be used after steam sterilization or hot water sterilization. However, depending on the type of the hollow fiber membrane 2, there is a contraction caused by steam sterilization and hot water sterilization. Therefore, if steam sterilization or hot water sterilization is performed after the module is manufactured, the hollow fiber membrane 2 may be damaged by the shrinkage of the hollow fiber membrane 2, or the hollow fiber membrane 2 may fall off from the binding portion. Therefore, it is desirable to fabricate the module by treating the hollow fiber membrane 2 with steam treatment or warm water in advance and then shrinking it before end binding. Since steam sterilization is generally performed at 121 ° C. or higher, it is desirable to perform pretreatment with steam at 121 ° C. or higher. In general, hot water sterilization is performed at about 80 ° C., but the temperature is often changed depending on the process. Therefore, it is desirable to treat the hollow fiber membrane in advance with warm water that is higher than the assumed use temperature.
- the sum of the areas of the hollow fiber membrane 2 and the hollow part of the hollow fiber membrane 2 is the area of the end surface on the second end 1b side of the first binding part 3. On the other hand, it is preferably 35% or more and 65% or less.
- the filtration processing amount per unit volume of the hollow fiber membrane module becomes small, and the cost per filtration amount increases.
- the area occupied by the hollow fiber membrane 2 is large, the flow in the radial direction flowing out from the flow path member 5 is blocked, and the effect of reducing the retention cannot be sufficiently obtained, and it is difficult to install the flow path member.
- the hollow fiber membrane bundle 12 has a cylindrical shape through the binding portions 3 and 13 at both ends in a loose state in view of workability for producing the hollow fiber membrane module 100B and cleanability of the hollow fiber membrane 2 in module cleaning. It is preferable to accommodate in the case 1.
- the looseness means that the length of the hollow fiber membrane 2 in the portion is larger than the linear distance from the end surface on the second end 1b side of the first binding portion 3 to the end surface on the first end 1a side of the second binding portion 13. Indicates a long state.
- the second bundling part 13 On the second end 1b side of the cylindrical case 1, the second bundling part 13 that is the upper end side of the hollow fiber membrane module 100B is disposed.
- the second bundling portion 13 is configured by bundling a hollow fiber membrane bundle 12 composed of a large number of hollow fiber membranes 2.
- the hollow part of the hollow fiber membrane 2 is not sealed and is open, and the filtrate is taken out from the opening to the upper cap 6 side.
- the binding method and the material used are not particularly limited as long as the mechanical strength, chemical durability, thermal durability, and the like of the binding portion are satisfied. For example, the same method and material as those of the first binding portion 3 can be selected. .
- the outer diameter of the second bundling portion 13 is smaller than that of the cylindrical case 1. Further, a rectifying cylinder 15 exists between the cylindrical case 1 and the second bundling part, and the second bundling part 13 is fixed to the cylindrical case 1 or the rectifying cylinder 15, and the rectifying cylinder 15 is a cylindrical case. It is fixed to. Each fixing method has nothing to do with the present invention.
- the material of the cylindrical case 1 used in the hollow fiber membrane module 100B is not particularly limited as long as it satisfies mechanical strength, chemical durability, thermal durability, etc. Fluorine resins such as vinyl resin, polypropylene resin, polysulfone resin, polytetrafluoroethylene, perfluoroalkoxy fluorine resin, polycarbonate, polypropylene, polymethylpentene, polyphenylene sulfide, polyether ketone, stainless steel, aluminum, etc. it can.
- the material of the flow straightening cylinder 15 used in the hollow fiber membrane module 100B is not particularly limited, but can be selected from the same material as that of the cylindrical case 1, for example.
- the first bundling part 3 and the second bundling part 13 will be described by a method of manufacturing using a potting agent.
- a potting method centrifugal potting method in which liquid potting agent is infiltrated between hollow fiber membranes using centrifugal force and then hardened, and liquid potting agent is fed by a metering pump or head and allowed to flow naturally. Any of the stationary potting methods in which the hollow fiber membrane 2 is allowed to penetrate and then cured can be used.
- the centrifugal potting method allows the potting agent to easily permeate between the hollow fiber membranes by centrifugal force, and a high-viscosity potting agent can also be used.
- a polyurethane resin as a potting agent for adhering the hollow fiber membrane 2
- the polyurethane resin is used in the stationary potting method. Difficult to do. If the centrifugal potting method is used, pressure is generated in the direction of the end of the module due to centrifugal force, and air bubbles escape in the inner direction. Therefore, polyurethane resin can be used as a potting agent for adhering the hollow fiber membrane 2.
- stationary potting does not require large equipment such as a centrifugal molding machine.
- the end surface of the hollow fiber membrane 2 is opened by cutting the potting portion on the second end 1b side of the second binding portion.
- the sealing treatment it is possible to prevent the potting agent from further entering the hollow portion, and to prevent the occurrence of thread breakage in which the hollow portion is filled with the potting agent and the permeate does not come out.
- the inner surface of the first bundling part case 16 may be filed, plasma treatment, primer treatment, or the like may be performed.
- plasma treatment primer treatment, or the like may be performed. The same applies to the case where the second bundling portion is bonded to the inside of the rectifying cylinder 15.
- the hollow fiber membrane bundle 12 is installed in the centrifugal potting apparatus shown in FIG. 11 and centrifugal potting is performed to form the first binding portion and the second binding portion (step S1).
- the hollow fiber membrane bundle 12 is housed in the cylindrical case 1, the first end of the hollow fiber membrane 2 is in the first binding portion case 16, the second end of the hollow fiber membrane 2 is in the rectifying cylinder 15, Further, the flow straightening cylinders 15 are respectively inserted into the second binding part forming jig 17. Further, a pin 18 having the flow path member 5 fitted on the outer periphery is inserted into the through hole at the bottom of the first binding portion case 16, and the first binding portion case 16 is inserted into the first binding portion forming jig 19.
- the channel member 5 (5D) having a dome-shaped tip and the pin 18 are housed.
- the second end portion of the hollow fiber membrane 2 is previously sealed with a silicone adhesive.
- a potting agent feeder 20 is connected to the cylindrical case 1, and the entire bundling agent is rotated in a centrifugal molding machine so that the potting agent is fed by a centrifugal force to the first binding part case 16 and the second binding part forming jig. 17 can be supplied.
- the potting agent can be supplied to the first bundling part case 16 and the second bundling part forming jig 17 simultaneously or separately.
- the binding portion forming jigs 17 and 19 and the pin 18 are removed.
- the flow path member 5 is provided with an opening extending in advance in a portion buried with the potting agent, so that the second end 1 b of the first binding portion is removed after the pin 18 is removed.
- An opening in contact with the side end surface can be formed. Since the time and temperature required for curing vary depending on the type of potting agent, suitable conditions may be applied as appropriate.
- the flow path member 5 is fixed to the first bundling portion 3 at the same time as the first bundling portion 3 is molded. However, after the first bundling portion 3 is formed in advance, the flow path member 5 is You may fix to the 1 binding part 3.
- FIG. When the flow path member 5 is projected to the second end side of the first bundling portion, the length in the height direction of the flow path member 5 and the direction of the opening 5E are set to the shape of the first bundling portion. It can be adjusted in view of this.
- the flow path member 5 is detachably fixed to the first bundling portion 3, it is possible to adjust the shape and position of the flow path member 5 after operation evaluation of the hollow fiber membrane module.
- the CC line part of FIG. 11 is cut with the tip saw type rotary blade, and the second end of the hollow fiber membrane 2 is opened (step S2).
- the hollow cap membrane module 100B can be manufactured by fixing the lower cap 7 to the first end 1a side and the upper cap 6 to the second end 1b side of the cylindrical case 1 (step S3).
- the material of the binding part forming jig is not particularly limited as long as it satisfies heat resistance and chemical durability.
- vinyl chloride resin, nylon resin, fluorine resin, polypropylene resin, polyacetal resin, polyethylene resin Silicone resins are excellent in releasability and are preferably used.
- the potting part forming jig may be made of a single material or a combination of a plurality of materials so as to include at least one material as described above.
- the material of the pin is not particularly limited as long as it satisfies heat resistance, chemical durability, and the like.
- the same material as that for the binding portion forming jig can be used.
- a fluororesin coating or the like is preferably performed in order to improve releasability.
- the filtrate enters from the filtrate inlet 9 and enters the first flow path 4 from below from the first end 1a side of the first binding unit 3. Passing upward, the flow direction is changed by the flow path member 5 to the radial direction (flow of arrow A in FIG. 4).
- the liquid to be filtered advances to a certain extent, and then advances in a course in the height direction.
- the liquid to be filtered moves as a filtrate to a space surrounded by the second binding portion 13 and the upper cap 6. Thereafter, the filtrate is taken out of the module from the filtrate outlet 8.
- the membrane surface linear velocity in cross flow filtration is 0.1 m / s or more and 7 m / s or less. It is preferable that the film surface linear velocity is 0.3 m / s or more and 3 m / s or less because long-term stable operation can be performed by maintaining higher detergency.
- Cross-flow filtration is widely used especially in the fermentation industry field, pharmaceutical / medical field, and food industry field. Also, generally, after performing a filtration operation using a hollow fiber membrane module for a certain period of time, a step of cleaning the inside of the module is provided, and water, chemical liquid, gas, etc. are supplied from the filtrate inlet 9 Is done. In particular, hot water of about 80 ° C. or higher is supplied in a process that requires hot water sterilization.
- the present invention is not limited to the above-described embodiments, and modifications, improvements, etc. can be made as appropriate.
- the material, shape, dimension, numerical value, form, number, arrangement location, and the like of each component in the above-described embodiment are arbitrary and are not limited as long as the present invention can be achieved.
- a hollow fiber membrane module 100A shown in FIG. 1 is accommodated in a cylindrical case 1 having a first end and a second end in the height direction, and the end portion on the first end side.
- a hollow fiber membrane bundle 12 having a plurality of hollow fiber membranes 2 that are closed and open at an end portion on the second end side; a first binding portion 3 that binds an end portion on the first end side of the hollow fiber membrane 2; 4C of through-holes which lead a fluid toward the 1st binding part toward the 2nd end side from the 1st end side are provided.
- the fluid (arrow A) has directionality when passing through the through-hole 4C from the bottom to the top, and after flowing out from the through-hole 4C, it depends on the flow velocity and the flow resistance of the hollow fiber membrane bundle portion. , While maintaining the directionality at the time of passing through the through hole 4C. And after progressing to some extent, the directionality is lost along with the flow path change and flow resistance in the through hole 4C, and the flow becomes uniform. Therefore, the flow velocity between the through holes 4C immediately after exiting the through holes 4C is very small, and it tends to stay. As a result, a portion (retaining portion) P where suspended substances or the like are likely to accumulate is likely to be generated.
- the hollow fiber membrane module is subjected to a step of washing suspended substances adhering to the membrane surface after a filtration process for a certain period of time.
- washing wastewater such as backwash water is suspended. It will be discharged
- FIG. 2 shows how the suspended substance is discharged from the through hole 4C.
- the washing waste water (arrow B) containing suspended solids flows from the top to the vicinity of the binding portion with a uniform flow, flows toward the through holes 4C near the binding portion, and flows down through the through holes 4C to be discharged.
- a portion (stagnation portion) P where suspended substances or the like are likely to accumulate is easily generated between the through holes 4C.
- This membrane forming stock solution was uniformly applied to the surface of a hollow fiber membrane having a spherical structure, and immediately solidified in a water bath to produce a hollow fiber membrane 2 having a three-dimensional stitch structure formed on the spherical structure layer.
- the obtained hollow fiber membrane 2 had an outer diameter of 1010 ⁇ m, an inner diameter of 600 ⁇ m, and a membrane surface average pore diameter of 40 nm.
- the strength per film was 6.4N.
- 9000 hollow fiber membranes 2 were filled in a cylindrical case 1 (inner diameter 145 mm, outer diameter 155 mm, length 1000 mm). Furthermore, on the first end 1a side of the cylindrical case 1, the first binding part case 16 (inner diameter 138 mm, outer diameter 140 mm, length 30 mm), the pin 18, and the first binding part forming jig 19 are mounted. On the second end 1b side of the cylindrical case 1, a rectifying cylinder 15 and a second binding part forming jig 17 were mounted. Thus, the cylindrical case 1 fitted with the jig was installed in a centrifugal molding machine.
- a pin 18 having the flow path member 5 fitted to the outer periphery is inserted into the through hole 4A at the bottom of the first binding portion case 16, and the first binding portion case 19 is provided inside the first binding portion forming jig 19. 16, the pin 18, and the flow path member 5 were accommodated.
- the pin 18 serves as a flow path forming jig that forms a flow path in a portion that becomes a flow path of the flow path member 5.
- a mass ratio of bisphenol F type epoxy resin (manufactured by Huntsman, LST868-R14) and aliphatic amine-based curing agent is 100: 30.
- a total of 2000 g (1000 g per one end) was put in the potting agent feeder 20.
- the centrifugal molding machine is rotated, and the potting agent is filled in the second binding part forming jig 17 and the first binding part case 16 at both ends to form the first binding part 3 and the second binding part 13, and potting is performed.
- the agent was cured.
- the temperature in the centrifugal molding machine was 35 ° C.
- the rotation speed was 350 rpm
- the centrifugation time was 5 hours.
- the second bundling part forming jig 17 and the first bundling part case 16 serve as a potting jig that surrounds the end of the hollow fiber membrane bundle 12 and hardens the potting agent therein to form the bundling part. Fulfill.
- the binding portion forming jigs 17 and 19 and the pin 18 are removed and cured at room temperature for 24 hours, and then the end portion (the CC surface shown in FIG. 11) of the second binding portion 13 is cut with a tip saw type rotary blade. Then, the end face of the hollow fiber membrane 2 was opened.
- all the flow path members 5 are flow path members having a dome-shaped tip, and the width of the portion where the opening 5E is in contact with the surface on the second end 1b side of the first binding section 3 is 5 mm.
- the height of the opening 5E was 1 mm.
- an EPDM gasket 10 is attached to the flanges 1D and 1E (see FIG. 3) of the cylindrical case 1, and an upper cap 6 and a lower cap 7 are attached to obtain a hollow fiber membrane module 100B as shown in FIG. .
- ethanol was fed to the hollow fiber membrane module 100B and filtered, and the pores of the hollow fiber membrane 2 were filled with ethanol.
- RO water was fed and filtered, and ethanol was replaced with RO water.
- the liquid in the hollow fiber membrane module 100B is discharged from the filtrate inlet 9, the filtrate outlet 8 and the filtrate outlet 11 are opened for one week, and the filtrate inlet is opened.
- the hot air of 80 ° C. was supplied from 9 to the hollow fiber membrane module 100B and dried.
- the weight W0 of the dried hollow fiber membrane module 100B before supplying activated sludge and the weight W1 of the hollow fiber membrane module 100B dried after supplying activated sludge were measured.
- the difference in weight (W1 ⁇ W0) of the hollow fiber membrane module before and after supplying activated sludge was calculated.
- the minimum temperature at the five measurement points reached 121 ° C. within 15 minutes from the start of steam supply, and then maintained at 121 ° C. for 20 minutes. From this result, it can be said that the shape of the flow path member 5 of Example 1 can increase drainage from the filtrate inlet 9 and increase the efficiency of steam sterilization.
- the increase in the weight of the hollow fiber membrane module 100B by supplying activated sludge was as small as 3 g (Table 1).
- the minimum temperature at the five measurement points reached 121 ° C. within 15 minutes from the start of steam supply, and then maintained at 121 ° C. for 20 minutes. From this result, it can be said that the shape of the flow path member 5 of Example 2 can increase drainage from the filtrate inlet 9 and increase the efficiency of steam sterilization.
- Example 3 A hollow fiber membrane module 100B was produced in the same manner as in Example 1 except that the openings 5E of all the flow path members 5 were provided 10 mm above the end surface on the second end 1b side of the first binding unit 3. .
- the weight increase of the hollow fiber membrane module was 18 g (Table 1). When the hollow fiber membrane module was disassembled and the vicinity of the first binding portion 3 was observed, accumulation of turbidity was observed.
- the opening 5E of the flow path member 5 is provided 10 mm above the end surface on the second end 1b side of the first bundling portion 3, and therefore near the end surface on the second end 1b side of the first bundling portion 3. It is thought that stagnation occurred and turbidity accumulated. Further, no damage or the like was observed in the hollow fiber membrane 2 when observed.
- Example 3 when a steam sterilization test was performed in the same manner as in Example 1, the minimum temperature of the end surface on the second end 1b side of the first bundling portion 3 was 100 ° C. even 60 minutes after the start of steam supply. From this result, it can be said that the shape of the flow path member 5 of Example 3 impairs drainage from the filtrate inlet 9 and the efficiency of steam sterilization is low.
- the increase in the weight of the hollow fiber membrane module 100B due to the supply of activated sludge was 12 g (Table 1). Moreover, when the hollow fiber membrane module 100B was disassembled thereafter and the vicinity of the first binding portion 3 was observed, accumulation of turbidity was observed almost uniformly.
- the first bundling portion 3 and the opening 5E of the flow path member 5 do not have an effective shape for reducing the staying portion, and the flow rate of the fluid flowing out of the flow path member 5 is reduced. It is believed that there is. Further, no damage or the like was observed in the hollow fiber membrane 2 when observed.
- the minimum temperature at the five measurement points reached 121 ° C. within 15 minutes from the start of steam supply, and then maintained at 121 ° C. for 20 minutes. From this result, it can be said that the shape of the flow path member 5 of Example 4 can enhance drainage from the filtrate inlet 9 and increase the efficiency of steam sterilization.
- the hollow fiber membrane module 100B was disassembled thereafter and the vicinity of the first binding portion 3 was observed, it was unevenly distributed in part and accumulation of turbidity was observed.
- the increase in weight is due to the accumulation of turbidity, which indicates that the first binding portion 3 and the opening 5E of the flow path member 5 were not in an effective shape for the reduction of the retention portion, It became clear that the residence by the drift in the hollow fiber membrane module 100A was large. Further, when observed, about 12 hollow fiber membranes 2 were damaged.
- the minimum temperature at the five measurement points reached 121 ° C. within 25 minutes from the start of steam supply, and then maintained at 121 ° C. for 20 minutes. From this result, it can be said that the shape of the flow path member 5 of Example 5 can slightly enhance drainage from the filtrate inlet 9 but has relatively low steam sterilization efficiency.
- Example 6> The same hollow fiber membrane 2 was obtained except that the hollow fiber membrane 2 was manufactured with an outer diameter of 790 ⁇ m and an inner diameter of 470 ⁇ m. At this time, the strength per film was 3.9 N.
- the increase in the weight of the hollow fiber membrane module 100B by supplying activated sludge was as small as 3 g (Table 1). Further, when the hollow fiber membrane module 100B was subsequently disassembled and the vicinity of the first binding portion 3 was observed, no accumulation of turbidity was observed. However, when observed, damage was observed in 34 of the hollow fiber membranes 2.
- the shape of the opening part 5E of the 1st binding part 3 and the flow-path member 5 is an effective shape in order to suppress accumulation of turbidity, on the other hand, it is suitable with respect to the strength of the hollow fiber membrane 2 Indicates that it is not in range.
- the minimum temperature at the five measurement points reached 121 ° C. within 15 minutes from the start of steam supply, and then maintained at 121 ° C. for 20 minutes.
- the minimum temperature at the five measurement points reached 121 ° C. within 15 minutes from the start of steam supply, and then maintained at 121 ° C. for 20 minutes. From this result, it can be said that the shape of the flow path member 5 of Example 2 can increase drainage from the filtrate inlet 9 and increase the efficiency of steam sterilization.
- the hollow fiber membrane module of the present invention can be used in the fields of fermentation industry, pharmaceutical production, food industry, water treatment and the like.
- the hollow fiber membrane module of the present invention is used to filter a liquid with a large amount of turbidity, the amount of accumulated turbidity is suppressed, and the filtration can be performed stably over a long period of time.
- contamination by bacteria can be effectively suppressed, it is preferably applied to the fermentation industry field, pharmaceutical production field, food industry field, water treatment field and the like.
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Abstract
Description
(1)高さ方向における第1端と第2端とを有する筒状ケースと、前記筒状ケース内に収容され、前記第1端側の端部が閉塞され、前記第2端側の端部が開口する複数の中空糸膜を有する中空糸膜束と、前記中空糸膜の前記第1端側の端部を結束する第1結束部と、前記第1結束部の前記第1端側から前記第2端側に向けて前記第1結束部を通るように流体を導く第1流路と、前記第1流路の第2端側の終端で、前記第1流路の前記第2端側の終端から流出した前記流体の少なくとも一部の流れを、前記筒状ケースの高さ方向と交差する方向に向ける流路部材と、を備える中空糸膜モジュール。
(2)少なくとも一つの前記流路部材は、前記第1結束部の前記第2端側の端面から突出するように設けられ、前記第1結束部の前記第2端側の面と接する開口部を備える(1)に記載の中空糸膜モジュール。
(3)少なくとも一つの前記流路部材の前記高さ方向における前記開口部の長さは1mm以上30mm以下である(2)に記載の中空糸膜モジュール。
(4)前記第1結束部の外径Rと、前記流路部材の前記開口部の総面積Sが0.004≦S/R2≦1.2を満たす(2)または(3)に記載の中空糸膜モジュール。
(5)前記中空糸膜の破断強力FがF≧4.9Nを満たす(1)~(4)のいずれか一項に記載の中空糸膜モジュール。
(6)前記第1結束部の、前記第2端側端面におけるA硬度が10以上、かつD硬度が85未満である(1)~(5)のいずれか一項に記載の中空糸膜モジュール。
(7)前記第1結束部の第2端側端面のうち、最も低い部位から高さ3mm以内の範囲の領域に、少なくとも1つの前記第1流路の終端が配置されている(1)~(6)のいずれか一項に記載の中空糸膜モジュール。
(8)前記高さ方向に垂直な断面における前記第1流路の総面積が、前記第1結束部を含む、前記高さ方向に垂直な断面における前記筒状ケース内側の面積に対して、2%以上35%以下である(1)~(7)のいずれか一項に記載の中空糸膜モジュール。
(9)前記中空糸膜モジュールは、複数の前記第1流路を備え、前記流路部材は、複数の前記第1流路のうち、一部の流路からの流出方向を変更するように配置されており、 前記高さ方向に垂直な断面において、前記第1流路のうち、前記流路部材により方向が変更される流れを供給する流路の面積は、前記第1流路の総面積に対して30%以上90%以下である(1)~(8)のいずれか一項に記載の中空糸膜モジュール。
(10)(1)~(9)のいずれか一項に記載の中空糸膜モジュールの製造方法であって、
下記工程(a)~(e):
(a)複数の中空糸膜を有する中空糸膜束の少なくとも一方の端部に、前記流路部材を配置するステップと、
(b)前記流路部材の流路となる部分に流路形成治具を配置するステップと、
(c)前記複数の中空糸膜を有する中空糸膜束の少なくとも前記流路部材を配置した端部を囲むようにポッティング治具を配置するステップと、
(d)前記ポッティング治具内でポッティング剤を硬化することで、前記中空糸膜間と、前記流路部材を接着固定した結束部を成形するステップと、
(e)前記流路形成治具および前記ポッティング治具を取り外すステップと、を備える、中空糸膜モジュールの製造方法。
(11)(1)~(9)のいずれか一項に記載の中空糸膜モジュールの製造方法であって、
下記工程(a)~(d):
(a)前記複数の中空糸膜を有する中空糸膜束の少なくとも一方の端部を囲むようにポッティング治具を配置するステップと、
(b)前記ポッティング治具内でポッティング剤を硬化することで、前記中空糸膜間を接着固定した結束部を成形するステップと、
(c)前記ポッティング治具を取り外すステップと、
(d)前記結束部に、前記流路部材を固定するステップと、を備える、中空糸膜モジュールの製造方法。
I-1.中空糸膜モジュール
(1)モジュール構成概要
本発明の実施形態にかかる中空糸膜モジュールの構成について、図を参照しながら説明する。図3は、本発明の第1実施形態にかかる中空糸膜モジュール100Bの概略縦断面図である。
筒状ケース1の被ろ過液流入口9側、つまり中空糸膜モジュール100Bの下端側に配置される第1結束部3は、中空糸膜2を第1端部において、中空部を閉塞した状態で結束している。図4に示すように、第1結束部3の第2端1b側端面近傍において、流路部材5から流出した流体(矢印A)は、中空糸膜2に対し筒状ケース1の径方向の力として作用し、この部分で中空糸膜2の破断が発生しやすい。そのため、第1結束部3の第2端1b側端面において、ある程度硬度が低い材料が中空糸膜2の周囲に緩衝材としてあることが好ましく、緩衝材(第1結束部3の第2端1b側端面における部分)の硬度は好ましくはD硬度85未満、さらに好ましくはD硬度60未満である。また、硬度が低すぎる場合には、中空糸膜モジュール100Bの取り扱い中に破損等する可能性が高く、好ましくはA硬度10以上、さらに好ましくはA硬度30以上である。硬度の測定はJIS K 6253に基づいて、市販の硬度計を用いて行うことができる。緩衝材は個別に用いてもよく、その場合には、第1結束部3の第2端1b側端面近傍に用いればよい。
第1結束部3は被ろ過液等の流体流路となる第1流路4を有している。具体的には、第1流路4は、第1結束部3中に設けられた貫通孔4A、および筒状ケース1と第1結束部3のクリアランス4Bなどを含む。第1結束部3の第2端1b側端面近傍における流れの滞留部の発生を低減するためには、高さ方向に垂直な断面における第1流路4の総面積が、前記第1結束部を含む、前記高さ方向に垂直な断面における前記筒状ケース内側の面積に対して、2%以上35%以下であることが好ましい。第1流路4の面積が小さいと、滞留箇所になり得る各貫通孔4Aの間の空間が広くなり、流路部材5を設けても滞留を低減する効果が得られにくい。また、第1流路4を流体が通過するときの圧力損失が大きく、下から上に流体が流れる場合にはポンプ動力費が大きくなる。さらに、上から下に流体が流れる場合には流れが起こりにくく、濁質が第1流路を塞ぐ可能性がある。一方、第1流路4の面積が大きいと、第1結束部3における中空糸膜2以外の部分の断面積が小さくなるため、中空糸膜2が密集して中空糸膜2の第1端1a側に封止不良が生じる、或いは中空糸膜2間に堆積した濁質を排出しにくくなるなどの不具合が起こる可能性がある。さらに、第1流路4を流体が下から上に流れる場合に、第1流路4の面積が大きすぎると、流体の圧力損失が十分でなく、流路部材5に流入する流れに偏りが生じる。流路部材5に流入する流れに偏りがあると、流路部材5から流出する径方向の流れに偏りが生じ、滞留部が大きくなり、濁質が堆積しやすい。
流路部材5は、一部の第1流路4から流出した流れの方向を変更するように配置されており、高さ方向に垂直な断面において、第1流路4のうち、流路部材5により方向が変更される流れを供給する流路の面積は、第1流路4の総面積に対して30%以上90%以下であることが好ましい。流路部材5により方向が変更される流れを供給する第1流路4の面積が大きすぎると、流路部材5を下から上に流体が流れる場合に圧力損失が過大になる場合があり、さらに流路部材5を上から下に流体が流れる場合に流れが起こりにくく、十分に排水されない可能性がある。一方、流路部材5により方向が変更される流れを供給する流路の面積が小さすぎると、流体が第1流路4を下から上に流れる場合に、流路部材5以外を通過する流れが優先的になり、流路部材5による滞留部を小さくする効果が十分に得られない。
本実施形態の中空糸膜モジュール100Bは、分離膜として、中空糸膜2を備える。数百~数万本の中空糸膜2は、束ねられて、中空糸膜束12を形成する。中空糸膜2は一般的に平膜よりも比表面積が大きく、単位時間当たりにろ過できる液量が多いため有利である。中空糸膜2の構造としては全体的に孔径が一様な対称膜や、膜の厚み方向で孔径が変化する非対称膜、強度を保持するための支持層と対象物質の分離を行うための分離機能層を有する複合膜などが存在する。
筒状ケース1の第2端1b側には、中空糸膜モジュール100Bの上端側である第2結束部13が配置されている。第2結束部13は、多数本の中空糸膜2からなる中空糸膜束12を結束して構成される。ここで、中空糸膜2の中空部が封止されておらず、開口している状態となっており、開口部からろ過液を上部キャップ6側に取り出す。結束方法および用いる材質は、結束部の機械的強度、化学的耐久性、熱的耐久性などを満たせば特に限定されないが、例えば第1結束部3と同様の方法、材質を選択することができる。
中空糸膜モジュール100Bで使用する筒状ケース1の材質は機械的強度、化学的耐久性、熱的耐久性などを満たせば特に限定されないが、例えば塩化ビニル系樹脂、ポリプロピレン系樹脂、ポリスルホン系樹脂、ポリテトラフルオロエチレン、ペルフルオロアルコキシフッ素樹脂などのフッ素系樹脂、ポリカーボネート、ポリプロピレン、ポリメチルペンテン、ポリフェニレンサルファイド、ポリエーテルケトン、ステンレス、アルミニウムなどを挙げることができる。また中空糸膜モジュール100Bで使用する整流筒15の材質は特に限定されないが、例えば筒状ケース1と同様の材料から選択することができる。
以下に、本実施形態にかかる中空糸膜モジュールの製造方法について説明する。尚、ここに記載する製造方法は第1実施形態に限定されるものではなく、後述するいずれの実施形態でも同様の方法で中空糸膜モジュールを製造できる。
中空糸膜モジュール100Bを用いたろ過運転中には、被ろ過液は、被ろ過液流入口9から入り第1結束部3の第1端1a側から第1流路4を下から上に通過し、流路部材5により流れ方向が径方向に変更されて流れ出る(図4の矢印Aの流れ)。被ろ過液は、ある程度進んだ後に、高さ方向に進路を変えて進む。被ろ過液は、中空糸膜2内を通過した後、ろ過液として、第2結束部13と上部キャップ6で囲まれた空間に移動する。その後、ろ過液は、ろ過液出口8からモジュール外に取り出される。
図1に示す中空糸膜モジュール100Aは、高さ方向における第1端と第2端とを有する筒状ケース1と、筒状ケース1内に収容され、第1端側の端部が閉塞され、第2端側の端部が開口する複数の中空糸膜2を有する中空糸膜束12と、中空糸膜2の第1端側の端部を結束する第1結束部3と、第1結束部を第1端側から第2端側に向かって流体を導く貫通孔4Cと、を備えている。
以下、実施例により本発明を具体的に説明するが、本発明はこれによって限定されるものではない。
(a)中空糸膜の製造
重量平均分子量41.7万のフッ化ビニリデンホモポリマー38質量部とγ-ブチロラクトン62質量部を混合し、160℃で溶解した。この高分子溶液を85質量%γ-ブチロラクトン水溶液を中空部形成液体として随伴させながら二重管の口金から吐出し、口金の30mm下方に設置した温度20℃のγ-ブチロラクトン85質量%水溶液からなる冷却浴中で凝固させて球状構造からなる中空糸膜を作製した。次いで、重量平均分子量28.4万のフッ化ビニリデンホモポリマー14質量部、セルロースアセテートプロピオネート(イーストマンケミカル社製、CAP482-0.5)1質量部、N-メチル-2-ピロリドン77質量部、ポリオキシエチレンソルビタン脂肪酸エステル(三洋化成社製、イオネット(登録商標)T-20C)5質量部、水3質量部を混合し、95℃で溶解して高分子溶液を作製した。この製膜原液を、球状構造からなる中空糸膜の表面に均一に塗布し、すぐに水浴中で凝固させて球状構造層の上に三次元編目構造を形成させた中空糸膜2を作製した。得られた中空糸膜2は、外径1010μm、内径600μmで、膜表面平均孔径は40nmであった。膜1本当たりの強力は6.4Nであった。
上記(a)で得られた中空糸膜2を長さ1800mmにカットし、30質量%グリセリン水溶液に1時間浸漬後、風乾した。この中空糸膜2を125℃の水蒸気で1時間加熱処理して風乾させ、長さ1200mmにカットした。その後シリコーン接着剤(東レ・ダウコーニング社製、SH850A/B、2剤を質量比が50:50となるように混合したもの)で中空糸膜2の第2端側を目止めした。
工場排水を処理して得られた活性汚泥を活性汚泥量が3g/Lとなるように水道水で調整することで、実験用の被処理水を得た。
上記(b)で得られた中空糸膜モジュール100Bに、被ろ過液出口11から125℃の蒸気を供給し、5分間被ろ過液流入口9を大気圧開放して中空糸膜モジュール100B内のエアーを排出した後に、被ろ過液流入口9の先をスチームトラップに切り替えた。第1結束部3の第2端1b側端面の5箇所に温度センサをとりつけて、温度推移を測定した。
ろ過運転試験の結果、活性汚泥の供給による重量増加は2gと小さかった(表1)。また、その後中空糸膜モジュール100Bを解体し、第1結束部3付近を観察したところ、濁質の堆積は認められなかった。これは、本実施例の中空糸膜モジュール100Bでの滞留が少なかったことを示す。また、観察した際に中空糸膜2に損傷等は認められず、これは、第1結束部3および流路部材5の開口部5Eが滞留部の低減に対して効果的な形状となっていたのみでなく、中空糸膜2の強力に対して適切な範囲となっていることを示す。
全ての流路部材5の高さ方向における開口部5Eの長さが30mmであること以外は実施例1と同様にして中空糸膜モジュール100Bを作製し、ろ過運転試験を行った。このとき、流路部材5の開口部5Eの総面積Sと、第1結束部3の第2端1b側の外径Rとは、S/R2=0.66となった。活性汚泥の供給による中空糸膜モジュール100Bの重量増加は3gと小さかった(表1)。
流路部材5を備えない中空糸膜モジュール100Aを使用した以外は、実施例2と同様にしてろ過運転試験を行った。活性汚泥の供給による中空糸膜モジュール100Aの重量は約26g増加した(表2)。また、中空糸膜モジュール100Aを解体し、観察したところ、第1結束部3上端付近に濁質の堆積が認められた。重量増加は濁質の堆積によるものであり、これは流路部材5を備えない場合には、中空糸膜モジュール100A内での滞留が大きかったことを示す。また、観察した際に中空糸膜2に損傷等は認められなかった。また、蒸気滅菌試験の結果、蒸気供給開始から15分以内に、5個の測定箇所での最低温度は121℃に達し、その後20分間121℃を維持した。
全ての流路部材5の開口部5Eが、第1結束部3の第2端1b側端面から10mm上から設けられていること以外は実施例1と同様にして中空糸膜モジュール100Bを作製した。このとき、実施例1と同様で、流路部材5の開口部5Eの総面積Sと、第1結束部3の第2端1b側の外径Rとは、S/R2=0.022となった。
濾過運転試験の結果、中空糸膜モジュールの重量増加は18gであった(表1)。中空糸膜モジュールを解体し、第1結束部3付近を観察したところ、濁質の堆積が認められた。これは、流路部材5の開口部5Eが、第1結束部3の第2端1b側端面から10mm上から設けられているために、第1結束部3の第2端1b側端面付近において滞留が発生し、濁質が堆積したと考えられる。また、観察した際に中空糸膜2に損傷等は認められなかった。
全ての流路部材5の開口部5Eの高さ方向における長さが40mmであること以外は実施例1と同様にして中空糸膜モジュール100Bを作製し、ろ過運転試験を行った。このとき、流路部材5の開口部5Eの総面積Sと、第1結束部3の第2端1b側の外径Rとは、S/R2=0.88となった。活性汚泥の供給による中空糸膜モジュール100Bの重量増加は12gであった(表1)。また、その後中空糸膜モジュール100Bを解体し、第1結束部3付近を観察したところ、濁質の堆積がおおよそ均一に認められた。これは、第1結束部3および流路部材5の開口部5Eが滞留部の低減に対して効果的な形状となっておらず、流路部材5から流出する流体の流速が遅くなったためであると考えられる。また、観察した際に中空糸膜2に損傷等は認められなかった。
全ての流路部材5の開口部5Eの第1結束部3の第2端1b側の面と接する部分の幅が2mmであること以外は実施例1と同様にして中空糸膜モジュール100Bを作製し、ろ過運転試験を行った。このとき、流路部材5の開口部5Eの総面積Sと、第1結束部3の第2端1b側の外径Rとは、S/R2=0.0088となった。活性汚泥の供給による中空糸膜モジュール100Bの重量増加は11gであった(表1)。また、その後中空糸膜モジュール100Bを解体し、第1結束部3付近を観察したところ、一部に偏在して濁質の堆積が認められた。重量増加は濁質の堆積によるものであり、これは、第1結束部3および流路部材5の開口部5Eが滞留部の低減に対して効果的な形状となっていなかったことを示し、中空糸膜モジュール100A内での偏流による滞留が大きかったことが明らかとなった。また、観察した際に中空糸膜2はおよそ12本に損傷が認められた。第1結束部3および流路部材5の開口部5Eの形状は、偏流によって一部の場所において過剰な速度を有する流れが発生し、中空糸膜2の強力に対して適切な範囲となっていないことを示す。
中空糸膜2を外径790μm、内径470μmで製作した以外は、同じ中空糸膜2を得た。このとき、膜1本当たりの強力は3.9Nであった。また、この中空糸膜2を筒状ケース1に15200本収容した以外は、実施例1であること以外は実施例1と同様にして中空糸膜モジュール100Bを作製し、ろ過運転試験を行った。このとき、流路部材5の開口部5Eの総面積Sと、第1結束部3の第2端1b側の外径Rとは、実施例1と同様にS/R2=0.022となった。活性汚泥の供給による中空糸膜モジュール100Bの重量増加は3gと小さかった(表1)。また、その後中空糸膜モジュール100Bを解体し、第1結束部3付近を観察したところ、濁質の堆積は認められなかった。しかし、観察した際に中空糸膜2の内34本に損傷は認められた。第1結束部3および流路部材5の開口部5Eの形状は、濁質の堆積を抑制するために効果的な形状となっているが、一方で中空糸膜2の強力に対して適切な範囲となっていないことを示す。
全ての流路部材5の開口部5Eの第1結束部3の第2端1b側の面と接する部分の幅が6.5mmであること以外は実施例2と同様にして中空糸膜モジュール100Bを作製し、ろ過運転試験を行った。このとき、流路部材5の開口部5Eの総面積Sと、第1結束部3の第2端1b側の外径Rとは、S/R2=0.86となった。活性汚泥の供給による中空糸膜モジュール100Bの重量増加は3gと小さかった(表1)。
100B 中空糸膜モジュール
1 筒状ケース
1D 鍔部
1E 鍔部
2 中空糸膜
3 第1結束部
4 第1流路
4A 貫通孔
4B クリアランス
5 流路部材
5A 邪魔板状の流路部材
5B 球状の流路部材
5C 平面状先端を持つ流路部材
5D ドーム状先端を持つ流路部材
5E 開口部
6 上部キャップ
7 下部キャップ
8 ろ過液出口
9 被ろ過液流入口
10 ガスケット
11 被ろ過液出口(ノズル)
12 中空糸膜束
13 第2結束部
14 整流孔
15 整流筒
16 第1結束部ケース
17 第2結束部成形用治具
18 ピン
19 第1結束部成形用治具
P 懸濁物質等が堆積しやすい箇所(滞留部)
Claims (11)
- 高さ方向における第1端と第2端とを有する筒状ケースと、
前記筒状ケース内に収容され、前記第1端側の端部が閉塞され、前記第2端側の端部が開口する複数の中空糸膜を有する中空糸膜束と、
前記中空糸膜の前記第1端側の端部を結束する第1結束部と、
前記第1結束部の前記第1端側から前記第2端側に向けて前記第1結束部を通るように流体を導く第1流路と、
前記第1流路の前記第2端側の終端で、前記第1流路の前記第2端側の終端から流出した前記流体の少なくとも一部の流れを、前記筒状ケースの高さ方向と交差する方向に向ける流路部材と、
を備える中空糸膜モジュール。 - 請求項1に記載の中空糸膜モジュールであって、
少なくとも一つの前記流路部材は、前記第1結束部の前記第2端側の端面から突出するように設けられ、前記第1結束部の前記第2端側の面と接する開口部を備える中空糸膜モジュール。 - 請求項2に記載の中空糸膜モジュールであって、
少なくとも一つの前記流路部材の前記高さ方向における前記開口部の長さは1mm以上30mm以下である中空糸膜モジュール。 - 請求項2または3に記載の中空糸膜モジュールであって、
前記第1結束部の外径Rと、前記流路部材の前記開口部の総面積Sが0.004≦S/R2≦1.2を満たす中空糸膜モジュール。 - 請求項1から4のいずれか1項に記載の中空糸膜モジュールであって、
前記中空糸膜の破断強力FがF≧4.9Nを満たす中空糸膜モジュール。 - 請求項1から5のいずれか1項に記載の中空糸膜モジュールであって、
前記第1結束部の、前記第2端側端面におけるA硬度が10以上、かつD硬度が85未満である中空糸膜モジュール。 - 請求項1から6のいずれか1項に記載の中空糸膜モジュールであって、
前記第1結束部の第2端側端面のうち、最も低い部位から高さ3mm以内の範囲の領域に、少なくとも1つの前記第1流路の終端が配置されている中空糸膜モジュール。 - 請求項1から7のいずれか1項に記載の中空糸膜モジュールであって、
前記高さ方向に垂直な断面における前記第1流路の総面積が、前記第1結束部を含む、前記高さ方向に垂直な断面における前記筒状ケース内側の面積に対して、2%以上35%以下である中空糸膜モジュール。 - 請求項1から8のいずれか1項に記載の中空糸膜モジュールであって、
前記中空糸膜モジュールは、複数の前記第1流路を備え、前記流路部材は、複数の前記第1流路のうち、一部の流路からの流出方向を変更するように配置されており、前記高さ方向に垂直な断面において、前記第1流路のうち、前記流路部材により方向が変更される流れを供給する流路の面積は、前記第1流路の総面積に対して30%以上90%以下である中空糸膜モジュール。 - 請求項1から9のいずれか1項に記載の中空糸膜モジュールの製造方法であって、
下記工程(a)~(e):
(a)複数の中空糸膜を有する中空糸膜束の少なくとも一方の端部に、前記流路部材を配置するステップと、
(b)前記流路部材の流路となる部分に流路形成治具を配置するステップと、
(c)前記複数の中空糸膜を有する中空糸膜束の少なくとも前記流路部材を配置した端部を囲むようにポッティング治具を配置するステップと、
(d)前記ポッティング治具内でポッティング剤を硬化することで、前記中空糸膜間と、前記流路部材を接着固定した結束部を成形するステップと、
(e)前記流路形成治具および前記ポッティング治具を取り外すステップと、
を備える、中空糸膜モジュールの製造方法。 - 請求項1から9のいずれか1項に記載の中空糸膜モジュールの製造方法であって、
下記工程(a)~(d):
(a)前記複数の中空糸膜を有する中空糸膜束の少なくとも一方の端部を囲むようにポッティング治具を配置するステップと、
(b)前記ポッティング治具内でポッティング剤を硬化することで、前記中空糸膜間を接着固定した結束部を成形するステップと、
(c)前記ポッティング治具を取り外すステップと、
(d)前記結束部に、前記流路部材を固定するステップと、
を備える、中空糸膜モジュールの製造方法。
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| EP15837714.3A EP3189886A4 (en) | 2014-09-01 | 2015-09-01 | Hollow fiber membrane module and method for manufacturing hollow fiber membrane module |
| US15/507,522 US10350549B2 (en) | 2014-09-01 | 2015-09-01 | Hollow fiber membrane module and method for manufacturing hollow fiber membrane module |
| JP2015547580A JP6607038B2 (ja) | 2014-09-01 | 2015-09-01 | 中空糸膜モジュールおよび中空糸膜モジュールの製造方法 |
| CN202010406983.4A CN111514759B (zh) | 2014-09-01 | 2015-09-01 | 中空纤维膜模块和用于制造中空纤维膜模块的方法 |
| CN201580046910.6A CN106794427A (zh) | 2014-09-01 | 2015-09-01 | 中空纤维膜模块和用于制造中空纤维膜模块的方法 |
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| CN113039013A (zh) * | 2018-11-15 | 2021-06-25 | 旭化成株式会社 | 使用了多孔膜的过滤方法 |
| US12214316B2 (en) * | 2019-12-25 | 2025-02-04 | Sumitomo Electric Fine Polymer, Inc. | Method for manufacturing hollow fiber membrane module, and hollow fiber membrane module |
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| EP3189886A1 (en) | 2017-07-12 |
| CN106794427A (zh) | 2017-05-31 |
| JPWO2016035798A1 (ja) | 2017-06-15 |
| KR102332901B1 (ko) | 2021-11-30 |
| CN111514759B (zh) | 2022-05-10 |
| US10350549B2 (en) | 2019-07-16 |
| KR20170047249A (ko) | 2017-05-04 |
| JP6607038B2 (ja) | 2019-11-20 |
| CN111514759A (zh) | 2020-08-11 |
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