WO2018230631A1 - 外部潅流型中空糸膜モジュール - Google Patents
外部潅流型中空糸膜モジュール Download PDFInfo
- Publication number
- WO2018230631A1 WO2018230631A1 PCT/JP2018/022698 JP2018022698W WO2018230631A1 WO 2018230631 A1 WO2018230631 A1 WO 2018230631A1 JP 2018022698 W JP2018022698 W JP 2018022698W WO 2018230631 A1 WO2018230631 A1 WO 2018230631A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hollow fiber
- fiber membrane
- case
- liquid
- bundle
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 922
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 874
- 239000007788 liquid Substances 0.000 claims abstract description 216
- 230000002265 prevention Effects 0.000 claims abstract description 50
- 238000004382 potting Methods 0.000 claims description 115
- 230000010412 perfusion Effects 0.000 claims description 62
- 239000002131 composite material Substances 0.000 claims description 30
- 238000005452 bending Methods 0.000 claims description 21
- 238000005520 cutting process Methods 0.000 claims description 16
- 230000035699 permeability Effects 0.000 claims description 8
- 238000005192 partition Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 abstract description 11
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 51
- 239000000463 material Substances 0.000 description 39
- 238000000034 method Methods 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 238000004519 manufacturing process Methods 0.000 description 29
- 229920005989 resin Polymers 0.000 description 28
- 239000011347 resin Substances 0.000 description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 22
- 239000001301 oxygen Substances 0.000 description 22
- 229910052760 oxygen Inorganic materials 0.000 description 22
- 230000002093 peripheral effect Effects 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229920001903 high density polyethylene Polymers 0.000 description 7
- 239000004700 high-density polyethylene Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 229920005672 polyolefin resin Polymers 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000000452 restraining effect Effects 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- 238000009941 weaving Methods 0.000 description 3
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
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
- B01D63/021—Manufacturing thereof
- B01D63/0233—Manufacturing thereof forming the 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
- B01D63/024—Hollow fibre modules with a single potted end
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/0031—Degasification of liquids by filtration
-
- 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
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/021—Manufacturing thereof
-
- 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
- B01D63/024—Hollow fibre modules with a single potted end
- B01D63/0241—Hollow fibre modules with a single potted end being U-shaped
-
- 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
- B01D63/025—Bobbin units
-
- 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
- B01D63/02—Hollow fibre modules
- B01D63/033—Specific distribution of fibres 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
- B01D63/02—Hollow fibre modules
- B01D63/04—Hollow fibre modules comprising multiple hollow fibre assemblies
- B01D63/043—Hollow fibre modules comprising multiple hollow fibre assemblies with separate tube sheets
-
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
-
- 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
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/2653—Degassing
- B01D2311/2657—Deaeration
-
- 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
- B01D2313/19—Specific flow restrictors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2315/00—Details relating to the membrane module operation
- B01D2315/22—Membrane contactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/18—Use of gases
- B01D2321/185—Aeration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
Definitions
- the present invention relates to an external perfusion type hollow fiber membrane module.
- the present application includes Japanese Patent Application No. 2017-116620 filed in Japan on June 14, 2017, Japanese Patent Application No. 2017-117077 filed in Japan on June 14, 2017, and Japan Priority is claimed based on Japanese Patent Application No. 2017-173041 filed in Japan, the contents of which are incorporated herein by reference.
- the gas-liquid separation hollow fiber membrane module there are an internal perfusion type in which the liquid to be treated passes through the inside of the hollow fiber membrane and an external perfusion type in which the liquid to be treated passes outside the membrane of the hollow fiber membrane.
- the liquid to be treated is allowed to flow around the hollow fiber membrane in the case, and the hollow fiber membrane is evacuated to take the dissolved gas in the liquid to be treated into the membrane.
- An external perfusion-type hollow fiber membrane module that performs deaeration or supplies gas to the hollow fiber membrane and sucks into the liquid to be treated is known.
- the gas-liquid separation hollow fiber membrane module is installed in, for example, an inkjet discharge device or a pure water production device as a degassing module.
- an inkjet discharge device large-scale inkjet printers for business use, color filter manufacturing devices, etc. use a large amount of chemical solution, so the chemical solution tank is installed in the main body of the device. A chemical solution such as ink or a photoresist solution is sent out from the tank. At this time, if bubbles are included in the chemical solution, the discharge accuracy may be reduced, and the quality of the printed matter may be defective. In order to prevent this, a gas-liquid separation hollow fiber membrane module is provided. In recent years, the size and speed of the apparatus have been increased, and an external perfusion type hollow fiber module that can be processed with a lower pressure loss has been favorably used.
- an external perfusion type hollow fiber membrane module a module in which only the first end portion in the length direction of the hollow fiber membrane bundle in the case is fixed by a potting portion, or the first in the length direction of the hollow fiber membrane bundle in the case is used.
- a module in which both an end and a second end are fixed by a potting unit is known (Patent Documents 1 and 2). At least the open end of each hollow fiber membrane at the first end is fixed while maintaining the open state, so that the liquid to be treated is evacuated by evacuating the hollow fiber membrane, or gas in the hollow fiber membrane. Can be supplied to the liquid to be treated.
- one end of a hollow fiber membrane bundle 3110 in which a plurality of hollow fiber membranes 3111 are bundled in a columnar shape is a potting portion 3116 inside a case 3114.
- an external perfusion type hollow fiber membrane module 3101 in which the other end of the hollow fiber membrane bundle 3110 is a free end (for example, Patent Document 1).
- water flows through the first port 3124 provided in the case main body 3118 and flows out from the third port 3122 c provided in the second lid member 3122. Then, the liquid is perfused outside the hollow fiber membranes 3111 of the hollow fiber membrane bundle 3110.
- the 2nd port 3120c provided in the 1st cover member 3120 is connected with a vacuum pump, and the inside of each hollow fiber membrane 3111 is decompressed. Thereby, it can deaerate by taking in and sucking the dissolved gas in the liquid which is perfused outside in the membrane of each hollow fiber membrane 3111.
- modules such as Patent Documents 1 and 2 if the filling rate of the hollow fiber membrane in the case is too high, the filling operation of the hollow fiber membrane becomes difficult, the pressure loss increases, and the processing efficiency decreases. Therefore, it is generally adjusted so that the hollow fiber membrane is not overfilled in the case.
- the liquid to be treated introduced into the case is appropriately taken into the hollow fiber membrane bundle and processed, but in the case of processing at a high flow rate, the membrane is more than introduced into the membrane bundle.
- the amount of liquid to be processed that flows out of the case without being sufficiently processed by short-passing outside the bundle increases.
- the first problem of the present invention is to suppress the short path of the liquid to be processed in the case, and the liquid to be processed efficiently flows into the hollow fiber membrane regardless of the direction of the liquid to be processed, such as a vertical direction or a horizontal direction.
- the object is to provide an external perfusion-type hollow fiber membrane module having a high processing capacity that can be contacted.
- the hollow fiber membrane having a smaller outer diameter can be filled with more hollow fiber membranes in the case, and the contact with the liquid to be treated is more efficient. It becomes the target.
- the module is enlarged and the hollow fiber membrane is lengthened and the flow rate of the liquid to be treated is increased, if the hollow fiber membrane has a small outer diameter and low rigidity, the shape of the hollow fiber membrane bundle is reduced in the case. It becomes difficult to hold, the shape of the hollow fiber membrane bundle is disturbed, and the deaeration efficiency tends to be lowered.
- the second problem of the present invention is that, even when the module is enlarged and the hollow fiber membrane is elongated, and the flow rate of the liquid to be treated is increased, the shape retention of the hollow fiber membrane bundle can be secured, and the liquid to be treated is vertical. It is an object to provide an external perfusion-type hollow fiber membrane module that can suppress a decrease in deaeration efficiency in any direction such as a horizontal direction or a horizontal direction.
- the liquid to be perfused when the flow rate of the liquid to be perfused is increased by increasing the size of the module, the liquid is contained in the hollow fiber membrane bundle in the case. It tends to flow unevenly without spreading throughout, and the efficiency of deaeration or air supply tends to decrease.
- the third problem of the present invention is that even when the flow rate of the liquid to be perfused is increased by increasing the size of the module, the liquid can be prevented from flowing in the case and the deaeration or supply efficiency can be prevented from decreasing. It is to provide an external perfusion type hollow fiber membrane module that can be used.
- a hollow fiber membrane module for removing gas from a liquid to be treated or supplying gas to a liquid to be treated A hollow fiber membrane bundle formed by a plurality of aligned hollow fiber membranes, a case in which the hollow fiber membrane bundle is accommodated, and the liquid to be treated in a gap between the hollow fiber membrane bundle and the case
- a short path prevention body that blocks the flow At least the first end in the length direction of the hollow fiber membrane bundle is fixed in the case by the potting portion while maintaining the open state of the open end of each hollow fiber membrane,
- the external perfusion-type hollow, wherein the short path prevention body is provided on the downstream side of the liquid inflow port for allowing the liquid to be treated to flow around the hollow fiber membrane in the case so as to protrude from the inner surface of the case.
- the liquid to be processed flows in one direction in the length direction in the case, and a partition for changing the flow of the liquid to be processed is provided in the case in addition to the short path prevention body.
- a hollow fiber membrane module for removing gas from the liquid to be treated or supplying gas to the liquid to be treated A hollow fiber membrane bundle formed of a plurality of aligned hollow fiber membranes, and a case containing the hollow fiber membrane bundle, At least the first end in the length direction of the hollow fiber membrane bundle is fixed in the case by the potting portion while maintaining the open state of the open end of each hollow fiber membrane, An external perfusion-type hollow fiber membrane module, wherein the hollow fiber membrane has a Gurley bending resistance of 15 mN or more.
- External perfusion type hollow fiber membrane module [7] The external perfusion-type hollow fiber membrane module according to any one of [1] to [6], wherein the hollow fiber membrane has an outer diameter of 350 ⁇ m or less.
- the filling rate of the hollow fiber membrane bundle in the case in a cross section obtained by cutting the case in a direction perpendicular to the length direction of the hollow fiber membrane bundle is 20 to 50%.
- the plurality of hollow fiber membranes are bundled in a state of being folded in a U shape at the center in the length direction, and the open ends on both sides of each hollow fiber membrane at the first end portion are in an open state.
- the external perfusion-type hollow fiber membrane module according to any one of [1] to [9] which is fixed in the case by the potting portion while being kept.
- a hollow fiber membrane bundle in which a plurality of hollow fiber membranes are bundled in a cylindrical shape so that a hollow portion is formed inside, and a case in which the hollow fiber membrane bundle is accommodated,
- the first end portion in the length direction of the hollow fiber membrane bundle is fixed in the case by the potting portion with the end face of each hollow fiber membrane opened,
- the second end of the hollow fiber membrane bundle opposite to the first end is a free end,
- An external perfusion-type hollow fiber membrane module in which liquid is perfused outside the membrane of each hollow fiber membrane on the second end side of the potting portion in the case,
- An external perfusion-type hollow fiber membrane module in which only the hollow fiber membrane bundle is provided in a region between the potting portion and the second end portion in the case.
- a hollow fiber membrane module for removing gas from the liquid to be treated or supplying gas to the liquid to be treated A hollow fiber membrane bundle formed by a plurality of aligned hollow fiber membranes, a case in which the hollow fiber membrane bundle is accommodated, and the liquid to be treated in a gap between the hollow fiber membrane bundle and the case
- a short path prevention body that blocks the flow At least the first end in the length direction of the hollow fiber membrane bundle is fixed in the case by the potting portion while maintaining the open state of the open end of each hollow fiber membrane,
- the external perfusion-type hollow, wherein the short path prevention body is provided on the downstream side of the liquid inflow port for allowing the liquid to be treated to flow around the hollow fiber membrane in the case so as to protrude from the inner surface of the case.
- the plurality of hollow fiber membranes are bundled in a state of being folded in a U-shape at the center in the length direction, and the open ends on both sides of each hollow fiber membrane are in the open state at the first end portion.
- the external perfusion-type hollow fiber membrane module according to any one of [A1] to [A6], which is fixed in the case by the potting portion while being kept.
- External perfusion type hollow fiber membrane module is
- the other aspect of this invention has the following structures.
- the gas-liquid separation hollow fiber membrane module according to [B1] which is an external perfusion type in which a liquid to be treated is perfused outside the membrane of each hollow fiber membrane in the case.
- the gas-liquid separation hollow fiber membrane module according to any one of [B4].
- the hollow fiber membrane bundle is formed by bundling the plurality of hollow fiber membranes in a state where the hollow fiber membranes are folded in a U shape at the center in the length direction, The first end portion of the hollow fiber membrane bundle opposite to the U-turn portion of each hollow fiber membrane is fixed in the case by the potting portion with the end faces on both sides of each hollow fiber membrane open.
- [B7] The gas-liquid separation hollow fiber membrane module according to [B6], wherein the ends of the hollow fiber membranes are aligned at the second end opposite to the first end of the hollow fiber membrane bundle. .
- [B8] The gas-liquid separation hollow fiber membrane module according to any one of [B1] to [B7], wherein the plurality of hollow fiber membranes are bundled in a state of being connected to each other by warp.
- the other aspect of this invention has the following structures.
- the plurality of hollow fiber membranes are bundled in a state where each hollow fiber membrane is folded in a U shape at the center in the length direction, and the case is formed by the potting portion in a state where both end faces of each hollow fiber membrane are open.
- [C9] The external perfusion-type hollow fiber membrane module according to any one of [C1] to [C8], wherein the plurality of hollow fiber membranes are bundled in a state of being connected to each other by warp.
- the external perfusion-type hollow fiber membrane module according to the first aspect of the present invention having the above-described configuration [1] suppresses a short path of the liquid to be processed in the case and efficiently brings the liquid to be processed into contact with the hollow fiber membrane. High processing capacity.
- the external perfusion-type hollow fiber membrane module according to the second aspect of the present invention having the above-mentioned configuration [3] is used, even if the module is increased in size to make the hollow fiber membrane longer and the flow rate of the liquid to be treated becomes faster.
- the shape retention of the hollow fiber membrane bundle can be secured, and the deaeration efficiency can be suppressed from decreasing.
- the external perfusion-type hollow fiber membrane module according to the third aspect of the present invention having the configuration of [12] is used, even if the flow rate of the liquid to be perfused is increased by increasing the size of the module, the liquid flows unevenly in the case. This can be suppressed, and a reduction in the efficiency of deaeration or air supply can be suppressed.
- FIG. 1 It is sectional drawing which showed an example of the external perfusion type
- FIG. 1 It is sectional drawing which showed 1 process of the manufacturing method of the external perfusion type
- FIG. 5 is a graph showing a plot of dissolved oxygen removal rate versus treatment flow rate in Examples A1 to A4 of the present invention. It is sectional drawing which showed an example of the external perfusion type
- FIG. 6 is a graph showing a plot of dissolved oxygen removal rate versus treatment flow rate in Examples B1 to B7 of the present invention. It is sectional drawing which showed an example of the external perfusion type
- FIG. 7 is a graph showing a plot of dissolved oxygen removal rate versus treatment flow rate in Examples C1 and C2 of the present invention. It is sectional drawing which showed an example of the conventional external perfusion type
- FIG. 5 is a graph showing a plot of dissolved oxygen removal rates by water passage direction in Examples A5 to A6 of the present invention.
- FIG. 5 is a graph showing a plot of dissolved oxygen removal rate versus treatment flow rate in Examples C3 to C5 of the present invention.
- the external perfusion-type hollow fiber membrane module according to the first aspect of the present invention is a hollow fiber membrane module for removing gas from a liquid to be treated or supplying gas to the liquid to be treated.
- the external perfusion-type hollow fiber membrane module according to the first aspect of the present invention can be used for, for example, an inkjet discharge apparatus such as an inkjet printer or a color filter manufacturing apparatus.
- an example of the external perfusion-type hollow fiber membrane module according to the first aspect of the present invention will be described and described.
- the dimension of the figure illustrated in the following description is an example, Comprising:
- the 1st aspect of this invention is not necessarily limited to them, It implements by changing suitably in the range which does not change the summary. It is possible.
- the external perfusion-type hollow fiber membrane module 11 (hereinafter also referred to as “module 11”) of the present embodiment includes a hollow fiber membrane bundle 110, a case 112, and a short path prevention body 114. I have.
- the case 112 is provided on the cylindrical case body 116, the first lid member 118 provided on the first opening end 116 a side in the length direction of the case body 116, and the second opening end 116 b side of the case body 116. And a second lid member 120.
- the case 112 includes a case main body 116, a first lid member 118, and a second lid member 120, and the appearance is a columnar shape.
- a case having a cylindrical appearance with a cylindrical case body as in this example is preferable.
- the appearance is not limited to a cylindrical case, and may be, for example, a polygonal columnar case including a polygonal cylindrical case body.
- a cylindrical first port 122 that communicates with the inside of the case body 116 is provided at a portion of the case body 116 near the first opening end 116 a so as to protrude outward from the outer peripheral surface of the case body 116.
- the shape of the 1st port 122 is not limited to a cylindrical shape, For example, a polygonal cylinder shape etc. may be sufficient.
- the first lid member 118 includes a circular flat plate portion 118a, a cylindrical portion 118b provided so as to protrude from the outer peripheral edge of the flat plate portion 118a to the case main body 116 side, and outward from the central portion of the flat plate portion 118a. And a second port 118c provided so as to protrude.
- a first end 117 a of the case main body 116 is fitted into the cylindrical portion 118 b, and the first lid member 118 is attached to the case main body 116.
- the second port 118c is located on the central axis L11 in the case 112.
- the second port 118c is cylindrical and functions as a gas outflow port through which gas flows out of the case 112 or a gas inflow port through which gas flows.
- the shape of the second port 118c is not limited to a cylindrical shape, and may be, for example, a polygonal cylindrical shape.
- the second lid member 120 includes a circular flat plate portion 120a, a cylindrical portion 120b provided so as to protrude from the outer peripheral edge of the flat plate portion 120a to the case main body 116 side, and an outer side from the central portion of the flat plate portion 120a. And a cylindrical third port 120c provided so as to protrude.
- the second end 117b of the case main body 116 is fitted into the cylindrical portion 120b, and the second lid member 120 is attached to the case main body 116.
- the third port 120c is located on the central axis L11 in the case 112.
- the shape of the third port 120c is not limited to a cylindrical shape, and may be, for example, a polygonal cylindrical shape.
- the flat plate portion 120a may have a tapered shape in order to improve the efficiency of air bubbles in the case 112.
- the first port 122 is provided near the first opening end 116 a of the case main body 116, and is installed on the second opening end 116 b side of the case main body 116.
- a second port 120 c is provided in the second lid member 120.
- the first port 122 is a liquid inflow port
- the third port 120c is a liquid outflow port.
- the liquid to be treated that flows in from the first port 122 flows in one direction in the length direction of the case 112 toward the third port 120 c, so that the flow does not change in the reverse direction in the case 112.
- the first port 122 may be the liquid outflow port and the third port 120c may be the liquid inflow port to allow one-way water flow in which the liquid flow is reversed.
- the size of the case 112 can be set as appropriate.
- the outer diameter and length of the case body 116 can be appropriately changed.
- the outer diameter of the case body 116 can be 3 to 15 cm and the length can be 5 to 50 cm.
- the material forming the case 112 is preferably a material that can ensure sufficient mechanical strength and durability.
- a material that can ensure sufficient mechanical strength and durability for example, polycarbonate, polysulfone, polyolefin, PVC (polyvinyl chloride), acrylic resin, ABS resin, modified PPE (polyphenylene) Ether) and the like.
- PVC polyvinyl chloride
- acrylic resin acrylic resin
- ABS resin polyvinyl chloride
- modified PPE polyphenylene
- the hollow fiber membrane bundle 110 is formed by bundling a plurality of aligned hollow fiber membranes 111 in a cylindrical shape.
- the plurality of hollow fiber membranes 111 forming the hollow fiber membrane bundle 110 are bundled in a state of being folded in a U shape at the center in the length direction.
- the form of the hollow fiber membrane bundle 110 is not limited to a columnar shape, and may be, for example, a form bundled in a cylindrical shape with a cavity disposed in the center.
- the hollow fiber membrane bundle 110 is accommodated in the case 112, and the first end portion 110 a in the length direction of the hollow fiber membrane bundle 110 is fixed in the case 112 by the potting portion 124 in a state of being restrained by the restraining ring 123.
- the open ends 111a on both sides of each hollow fiber membrane 111 folded in a U shape are in an open state at the end surface 124a on the first lid member 118 side of the potting portion 124.
- a second end portion 110b made of a U-turn portion of each hollow fiber membrane 111 located on the opposite side of the first end portion 110a in the hollow fiber membrane bundle 110 is not fixed to the case 112 and becomes a free end. ing.
- a plurality of hollow fiber membranes are bundled in a state of being folded in a U-shape at the center in the length direction, and open ends on both sides of each hollow fiber membrane. It is preferable to be fixed in the case by the potting portion while maintaining the open state. Since the hollow fiber membranes are bundled in such a state, it becomes easy to sufficiently increase the filling rate of the hollow fiber membrane bundle even with a small number of hollow fiber membranes, and the production efficiency is improved. In addition, to maintain the self-supporting state of the hollow fiber membrane bundle and make it easy for the liquid to be treated to spread between the hollow fiber membranes throughout the entire hollow fiber membrane bundle, use a knitted fabric of a plurality of bundles. Thus, it is preferable to form an assembly of small bundles of hollow fiber membranes, thereby improving the efficiency of deaeration or air supply.
- the first opening end 116a of the case body 116 is closed by the potting portion 124.
- a space is formed on the first lid member 118 side of the end surface 124a of the potting portion 124 in the case 112, and the space and the space on the second opening end 116b side of the potting portion 124 in the case main body 116 are formed. It is partitioned by a potting unit 124. Since the open ends 111 a on both sides of each hollow fiber membrane 111 are kept open at the first end portion 110 a of the hollow fiber membrane bundle 110, the potting portion 124 in the membrane of each hollow fiber membrane 111 and in the case 112.
- the first lid member 118 is in communication with the space on the first lid member 118 side.
- the hollow fiber membranes 111 are bundled in a state of being connected to each other by the warp 126. Specifically, a plurality of hollow fiber membranes 111 are warp 126 in a direction near the U-turn portion in each hollow fiber membrane 111 in a direction orthogonal to the central axis L11, that is, a direction orthogonal to the length direction of each hollow fiber membrane 111.
- the hollow fiber membranes 111 are connected to each other.
- it is preferable that the respective hollow fiber membranes are bundled in a state where they are connected to each other by warps.
- An aspect in which a plurality of hollow fiber membranes are connected by warp is not particularly limited, and for example, an aspect of weaving in a chain stitch type can be mentioned.
- the positions of the end portions 111b made of U-turn portions in the respective hollow fiber membranes 111 are substantially flush with each other. That is, the lengths of the portions exposed from the potting portion 124 in each hollow fiber membrane 111 are aligned with each other. That the positions of the end portions 111b of the hollow fiber membranes 111 are substantially flush with each other means that the length of the portion exposed from the potting portion 124 in all the hollow fiber membranes 111 forming the hollow fiber membrane bundle 110 is the same. It means that the error of the length of each hollow fiber membrane 111 with respect to the average value is ⁇ 5%.
- the end portions of the hollow fiber membrane bundles folded in a U-shape are aligned with each other at the second end portion of the hollow fiber membrane bundle.
- the hollow fiber membrane 111 is preferably a hollow fiber membrane having gas permeability that allows gas to pass between the hollow portion in the membrane and the outside of the membrane.
- the hollow fiber membrane 111 is a composite having a gas-permeable homogeneous layer and a porous support layer that supports the homogeneous layer because it has excellent strength and can perform deaeration and supply more efficiently.
- a hollow fiber membrane is more preferable.
- the structure of the composite hollow fiber membrane is preferably a two-layer structure in which a porous support layer is provided inside or outside the homogeneous layer, or a three-layer structure in which a porous support layer is provided both inside and outside the homogeneous layer. A three-layer structure is more preferable in terms of strength, deaeration or supply performance.
- the material for forming the homogeneous layer known materials can be used, and examples thereof include silicon rubber resin, polyolefin resin, fluorine-containing resin, cellulose resin, polyphenylene oxide, poly-4-vinylpyridine, and urethane resin. It is done. These materials may use only 1 type and may combine 2 or more types. Among them, as a material for forming a homogeneous layer, a polyolefin resin is preferable because it has excellent deaeration and supply performance even when the liquid to be treated is perfused at a high flow rate and has excellent chemical resistance. A low density polyethylene resin is more preferred because of its excellent film properties.
- polyolefin resin examples include a copolymer of ethylene and ⁇ -olefin, poly-4-methylpentene-1, metallocene polyethylene, low density polyethylene, high density polyethylene, linear low density polyethylene, linear ultra-low Examples include density polyethylene, polypropylene, ionomer resin, ethylene / vinyl acetate copolymer, ethylene / (meth) acrylic acid copolymer, ethylene / (meth) acrylic acid methyl copolymer, and modified polyolefin.
- a known material can be used, for example, polydimethylsiloxane, silicon rubber resin such as a copolymer of silicon and polycarbonate; poly-4-methylpentene-1, poly-3-methylbutene -1, Polyolefin resins such as high density polyethylene and polypropylene; Fluorine-containing resins such as polyvinylidene fluoride and polytetrafluoroethylene; Cellulosic resins such as ethyl cellulose; Polyphenylene oxide; Poly-4-vinylpyridine; Urethane resins; Polystyrene; Ether ether ketone; polyether ketone and the like.
- These materials may use only 1 type and may combine 2 or more types.
- high-density polyethylene showing an MFR value equivalent to that of the homogeneous layer is used as a material for forming the porous support layer from the viewpoint that it is easy to secure the self-supporting property of the hollow fiber membrane bundle and the film-forming stability is obtained. preferable.
- the pore size of the porous support layer is preferably 0.01 to 1 ⁇ m.
- the porosity of the porous support layer is preferably 30 to 80% by volume. When the porosity is equal to or higher than the lower limit of the above range, the performance of deaeration or supply is excellent. When the porosity is not more than the upper limit of the above range, the mechanical strength such as pressure resistance of the hollow fiber membrane is improved.
- the outer diameter of the hollow fiber membrane 111 is preferably 350 ⁇ m or less, more preferably 150 to 330 ⁇ m, and even more preferably 200 to 300 ⁇ m. If the outer diameter of the hollow fiber membrane 111 is within the above range, a more efficient flow path can be formed between the hollow fiber membranes 111 in the case 112.
- the inner diameter of the hollow fiber membrane 111 is preferably 100 ⁇ m or more, more preferably 120 to 250 ⁇ m, and further preferably 130 to 200 ⁇ m. When the inner diameter of the hollow fiber membrane 111 is within the above range, a sufficient number of hollow fiber membranes 111 can be accommodated in the case 112, and the performance and durability of deaeration or air supply can be easily maintained.
- the thickness of the hollow fiber membrane 111 is preferably 20 to 70 ⁇ m, and more preferably 25 to 55 ⁇ m. If the film thickness of the hollow fiber membrane 111 is equal to or less than the above upper limit value, the durability when the inside of the hollow fiber membrane 111 in the case 112 is repeatedly depressurized or pressurized is excellent. If the film thickness of the hollow fiber membrane 111 is equal to or greater than the lower limit of the above range, it is easy to maintain good deaeration or air supply performance.
- the inner diameter and outer diameter of the hollow fiber membrane are measured by the method described in [0062] of International Publication No. 2015/012293.
- the thickness of the homogeneous layer is preferably from 0.3 to 2 ⁇ m, more preferably from 0.5 to 1.2 ⁇ m.
- the thickness of the homogeneous layer and the porous support layer is measured by the method described in [0077] of WO2015 / 012293.
- the hollow fiber membrane 111 preferably has a breaking strength of 0.5 N / fil or more, a breaking elongation of 50% or more, and a breaking strength of 0.8 to 5 N from the viewpoint of handling at the time of module production. More preferably, the breaking elongation is 70 to 400%, the breaking strength is 1 to 4 N / fil, and the breaking elongation is 140 to 300%.
- breaking strength means the value which fractures
- N / fil is the strength required to break one hollow fiber membrane (1 filament) in Newton (N).
- the elongation at break means the elongation shown until the break when it is stretched while applying a tensile load in the longitudinal direction of the hollow fiber membrane.
- the breaking strength and breaking elongation are measured by the method described in [0081] of International Publication No. 2015/012293.
- one hollow fiber membrane is held by the chuck portion of the tester so that the length is 2 cm, and a tensile load is applied to give a breaking strength and breaking elongation of 3 Measure once and obtain the average value.
- the Gurley bending resistance of the hollow fiber membrane is preferably 15 mN or more, more preferably 15 to 30 mN, and even more preferably 18 to 25 mN. If the Gurley bending resistance of the hollow fiber membrane is equal to or higher than the lower limit of the above range, it is easy to ensure the self-supporting property of the hollow fiber membrane bundle, and it is easy to suppress a reduction in the efficiency of deaeration or air supply. If the Gurley bending resistance of the hollow fiber membrane is less than or equal to the upper limit of the above range, there is little membrane disruption associated with the increase in membrane length when the membrane bundle is formed, and the module can be formed in an aligned state. It becomes possible.
- the Gurley bending resistance of the hollow fiber membrane was determined by using a sample consisting of seven bundles of hollow fiber membranes (width: about 25 to 26 mm) in which the hollow fiber membranes were folded back in units of 32 (32 fil). JIS L1096 A Method Measured according to the bending resistance (Gurley) method.
- Gurley stiffness of the hollow fiber membrane can be controlled by adjusting the material, outer diameter, etc. of the hollow fiber membrane.
- the inner surface 116 c of the case body 116 and the hollow fiber membrane bundle 110 are partially separated, and a gap 128 is provided between the case 112 and the hollow fiber membrane bundle 110 around the hollow fiber membrane bundle 110. Is formed.
- the filling rate of the hollow fiber membrane bundle 110 in the case 112 in a cross section obtained by cutting the case 112 in a direction perpendicular to the length direction of the hollow fiber membrane bundle 110 is preferably 20 to 50%, more preferably 30 to 45%. . If the filling rate of the hollow fiber membrane is equal to or higher than the lower limit value, it is easy to suppress the occurrence of drift of the liquid to be treated in the case. If the filling rate of the hollow fiber membrane is not more than the upper limit value, the filling of the hollow fiber membrane becomes easy, the pressure loss becomes low, and the performance of deaeration or air supply is improved.
- the filling rate is defined by each hollow forming the filled hollow fiber membrane bundle 110 with respect to a cross-sectional area inside the case 112 in a cross section obtained by cutting the case 112 in a direction perpendicular to the length direction of the hollow fiber membrane bundle 110. It is measured as a ratio (%) of the sum total of the cross-sectional areas of the thread film 111.
- an annular short path prevention body 114 is fitted into the case main body 116 of the case 112 so as to protrude from the inner surface 116 c of the case main body 116 of the case 112. Is provided.
- the short path preventing body 114 may be formed integrally with the inner surface 116c during molding.
- the shape of the short path prevention body 114 is a protrusion that circulates on the inner surface 116c of the case body 116 of the case 112.
- the short path prevention body 114 is provided on the downstream side of the first port 122 in the case 112, and plays a role of blocking the flow of the liquid to be processed in the gap 128 between the hollow fiber membrane bundle 110 and the case 112.
- a part of the liquid to be treated that has flowed into the case 112 from the first port 122 enters the hollow fiber membrane bundle 110, and the remaining part forms a gap 128 between the hollow fiber membrane bundle 110 and the case 112. It tries to flow downstream.
- the short path prevention body 114 since the flow of the liquid to be processed passing through the gap 128 between the hollow fiber membrane bundle 110 and the case 112 is blocked by the short path prevention body 114, the direction is changed to the inside in the radial direction, and the hollow fiber membrane bundle 110 is changed.
- the liquid to be processed that passes through the gap 128 between the hollow fiber membrane bundle 110 and the case 112 is guided to the inside of the hollow fiber membrane bundle 110 by the short path prevention body 114, so that the liquid to be processed is contained in the case 112. Is prevented from flowing out from the third port 120c without being sufficiently processed.
- the short path prevention body 114 is provided on the first port 122 side with respect to the second end portion 110b located on the downstream side in the hollow fiber membrane bundle 110 in the direction along the central axis L11 of the case 112.
- the first port 122 is provided as much as possible on the downstream side of the first port 122. It is more preferable to provide the short path preventing body 114 at a position close to.
- d12 / d11 is preferably 0.01 to 0.2, and more preferably 0.03 to 0.1. If d12 / d11 is less than or equal to the upper limit value, it is possible to eliminate a short-circuit flow passing only outside the hollow fiber membrane bundle. If d12 / d11 is not less than the lower limit value, the liquid to be treated can be brought into contact with the hollow fiber membrane 111 more efficiently, and the processing capacity of the module 11 is improved.
- the module 11 may be configured such that the short path prevention body 114 and the case 112 are manufactured separately, and the short path prevention body 114 is fitted in the case 112, and the case 112 and the short path prevention body 114 are integrated.
- the aspect formed in this may be sufficient.
- the short path preventing body 114 of this example is an annular shape surrounding the entire circumference of the hollow fiber membrane bundle 110.
- pass prevention body 114 is not limited to this aspect, You may provide intermittently around the hollow fiber membrane bundle 110.
- the cross-sectional shape of the short path preventing body 114 is rectangular in this example, but is not limited to a rectangular shape, and may be a triangular shape, a semicircular shape, or the like.
- the width D1 (FIG. 2) in the direction along the central axis L11 of the short path preventing body 114 is preferably 1 to 10 mm, and more preferably 2 to 7 mm. If the width D1 is equal to or greater than the lower limit value, a short-circuit flow that passes outside the membrane bundle can be prevented. If the width D1 is equal to or less than the upper limit value, the liquid to be treated can be introduced into the membrane bundle more efficiently.
- the short path preventing body 114 needs to be in contact with the hollow fiber membrane bundle 110 in that the liquid to be treated can be brought into contact with the hollow fiber membrane 111 more efficiently.
- the protrusion height H1 (FIG. 2) of the short path preventing body 114 from the inner surface 116c of the case body 116 of the case 112 is preferably 1 to 10 mm, and more preferably 2 to 7 mm. If the projection height H1 is equal to or greater than the lower limit, the liquid to be treated can be brought into contact with the hollow fiber membrane 111 more efficiently, and the processing capacity of the module 11 is improved. If the protrusion height H1 is equal to or less than the upper limit value, the hollow fiber membrane bundle 110 can be easily inserted into the short path prevention body 114.
- the number of short path prevention bodies 114 is one in this example, but is not limited to one and may be two or more.
- the number of short path prevention bodies 114 may be set according to the length of the case 112.
- the short path preventing body 114 is provided every 50 to 200 mm in the direction along the central axis L11 of the case 112 because the effect of suppressing the short path of the liquid to be treated in the case 112 is higher. preferable.
- the material for forming the short path prevention body 114 is not particularly limited, and examples thereof include polycarbonate, polysulfone, polyolefin, polyvinyl chloride, acrylic resin, ABS resin, and modified polyphenylene ether. Especially, the material which forms the short path
- the short path prevention body 114 is formed integrally with the case 112, the material forming the short path prevention body 114 is the same as the material forming the case 112.
- a material for forming the short path preventing body 114 one type may be used alone, or two or more types may be used in combination.
- the manufacturing method of the module 11 is not specifically limited, For example, the following method is mentioned.
- the long hollow fiber membranes 111 ⁇ / b> A are alternately repeated a plurality of times in the opposite direction and folded back into a U shape to form a strip-shaped hollow fiber membrane sheet 113.
- the hollow fiber membrane 111A is knitted in the length direction of the sheet by the warp 126, and the portions extending in the width direction of the hollow fiber membrane 111A are connected to each other.
- the hollow fiber membrane sheet 113 is wound into a columnar shape so that the width direction of the hollow fiber membrane sheet 113 is the axial direction.
- FIG. 3 the long hollow fiber membranes 111 ⁇ / b> A are alternately repeated a plurality of times in the opposite direction and folded back into a U shape to form a strip-shaped hollow fiber membrane sheet 113.
- the hollow fiber membrane 111A is knitted in the length direction of the sheet by the warp 126, and the portions extending in the width direction of the hollow fiber
- the hollow fiber membrane sheet 113 wound in a columnar shape is inserted into the case body 116 provided with the short path prevention body 114 and the restraining ring 123.
- One end of the hollow fiber membrane sheet 113 is fixed to the first opening end 116 a side of the case body 116 by the potting resin 130 using a known method such as a centrifugal method.
- the U-turn portion of the hollow fiber membrane 111 ⁇ / b> A on the side of the hollow fiber membrane sheet 113 fixed by the potting resin 130 and a part of the potting resin 130 are projected from the case body 116.
- seat 113 and the potting resin 130 is excised by the plane X1 in alignment with the 1st opening end 116a of the case main body 116.
- FIG. Thereby, the cylindrical hollow fiber membrane bundle 110 fixed to the case main body 116 by the potting portion 124 is formed while the open state of the open end 111a of each hollow fiber membrane 111 folded in the U shape is maintained.
- the module 11 is obtained by attaching the first lid member 118 and the second lid member 120 to both ends of the case main body 116.
- the liquid to be processed flows into the case body 116 of the case 112 from the first port 122, and the liquid to be processed flows out from the third port 120c.
- the configuration for allowing the liquid to be treated to flow into the case 112 from the first port 122 is not particularly limited, and the first port 122 may be connected to a pump to pump the liquid, and the third port 120c may be The structure which draws in a to-be-processed liquid by connecting with a pump may be sufficient.
- the second port 118c when the second port 118c is connected to a vacuum pump and evacuated, the dissolved gas of the liquid to be processed passing between the hollow fiber membranes 111 is taken into the membrane of the hollow fiber membranes 111, and the second port 118c.
- the liquid to be processed is deaerated.
- the gas by connecting the second port 118 c to the air supply pump, the gas can be supplied to the liquid to be processed that passes between the hollow fiber membranes 111 through the hollow fiber membranes 111.
- the liquid to be treated that has flowed in from the first port 122 wraps around the opposite side of the hollow fiber membrane bundle 110 to the opposite side of the first port 122 through the gap 128 between the hollow fiber membrane bundle 110 and the case 112 in the case 112, thereby It flows into the inside of the thread membrane bundle 110.
- the liquid to be treated that flows downstream through the gap 128 between the hollow fiber membrane bundle 110 and the case 112 is blocked by the short path prevention body 114, and the flow direction changes to the inside of the hollow fiber membrane bundle 110. It is guided. Then, the liquid to be treated passes between the hollow fiber membranes 111 in the hollow fiber membrane bundle 110 and flows out from the third port 120c.
- the short-pass prevention body 114 can prevent the liquid to be processed from short-passing the gap 128 outside the hollow fiber membrane bundle 110 in the case 112. Therefore, the liquid to be treated can be efficiently brought into contact with the hollow fiber membrane 111, and the liquid to be treated can be sufficiently processed, so that a module having a high processing capacity is obtained.
- the short path prevention body is provided on the downstream side of the liquid inflow port in the case. Short-passing of the liquid to be processed through the gap outside the membrane bundle is suppressed. Therefore, even when the size is increased for the purpose of processing at a high flow rate, the liquid to be treated can be efficiently guided to the inside of the hollow fiber membrane bundle and brought into contact with the hollow fiber membrane. can get. In addition, high processing capacity can be obtained regardless of the direction of the liquid to be processed, which flows in the vertical direction or the horizontal direction. In addition, the external perfusion type hollow fiber membrane module according to the first aspect of the present invention is easy to manufacture because a high throughput can be obtained simply by providing a short path prevention body in the case.
- the external perfusion type hollow fiber membrane module according to the first aspect of the present invention is not limited to the module 11 described above.
- the external perfusion-type hollow fiber membrane module according to the first aspect of the present invention is a module in which both the first end and the second end in the length direction of the hollow fiber membrane bundle are fixed to the case by the potting portion. It may be.
- the external perfusion-type hollow fiber membrane module of the first aspect of the present invention may be the external perfusion-type hollow fiber membrane module 12 illustrated in FIG. 6 (hereinafter also referred to as “module 12”). Good.
- module 12 illustrated in FIG. 6
- FIG. 6 the same parts as those in FIG.
- the module 12 includes a hollow fiber membrane bundle 110A, a case 112A, and short path prevention bodies 114A and 114B.
- the case 112A is provided on the cylindrical case main body 116A, the first lid member 118 provided on the first opening end 116a side in the length direction of the case main body 116A, and the second opening end 116b side of the case main body 116A.
- a second lid member 120 is provided.
- a first port 122 is provided near the first opening end 116a of the case body 116A, and a fourth port 132 that functions as a liquid outflow port or a liquid inflow port is provided near the second opening end 116b.
- the second lid member 120 is provided with a ventilation port 120d instead of the third port 120c.
- the first port 122 is a liquid inflow port and the fourth port 132 is a liquid outflow port.
- the liquid to be treated that flows in from the first port 122 flows in one direction in the length direction of the case 112A toward the fourth port 132, and the flow does not change in the reverse direction in the case 112A.
- the first port 122 may be the liquid outflow port
- the fourth port 132 may be the liquid inflow port
- the liquid flow may be reversed in one direction.
- the hollow fiber membrane bundle 110A is formed by bundling a plurality of hollow fiber membranes 111 into a columnar shape in a state of being aligned in one direction.
- the hollow fiber membrane bundle 110A is accommodated in the case 112A, and the first end portion 110a and the second end portion 110b in the length direction of the hollow fiber membrane bundle 110A are restrained by restraining rings 123A and 123B, respectively. It is fixed in the case 112A by potting portions 124A and 124B.
- the first port 122 and the fourth port 132 are located between the potting portion 124A and the potting portion 124B in the case 112A.
- the first opening end 116a of the case body 116A is blocked by the potting portion 124A, and the second opening end 116b of the case body 116A is blocked by the potting portion 124B.
- the open state of one open end 111c of each hollow fiber membrane 111 is maintained.
- the open state of the other open end 111d of each hollow fiber membrane 111 is maintained.
- the inner surface 116c of the case main body 116A and the hollow fiber membrane bundle 110A are partially separated, and a gap 128 is formed outside the hollow fiber membrane bundle 110A in the case 112A.
- short path preventing bodies 114 ⁇ / b> A and 114 ⁇ / b> B are provided on the downstream side of the first port 122 and the upstream side of the fourth port 132 in the case 112 ⁇ / b> A.
- the short path prevention body 114A is provided near the first port 122
- the short path prevention body 114B is provided near the fourth port 132.
- the liquid to be processed flows into the case 112 ⁇ / b> A from the first port 122, and the liquid to be processed flows out from the fourth port 132.
- the liquid to be processed that passes between the hollow fiber membranes 111 can be degassed by connecting the second port 118c and the vent port 120d with a vacuum pump and evacuating. Further, by supplying the gas by connecting the second port 118c and the ventilation port 120d with an air supply pump, it is possible to supply air to the liquid to be processed that passes between the hollow fiber membranes 111.
- the liquid to be processed flowing downstream in the gap 128 between the hollow fiber membrane bundle 110A and the case 112A in the case 112A is blocked by the short path preventing bodies 114A and 114B, and the flow direction is changed. Guided into the hollow fiber membrane bundle 110A. In this way, since the liquid to be treated is prevented from short-passing through the gap 128 outside the hollow fiber membrane bundle 110A in the case 112A, the liquid to be treated efficiently contacts the hollow fiber membrane 111, and the processing capacity is improved. Get higher.
- each hollow fiber membrane forming the hollow fiber membrane bundle is not folded back in a U shape, and the second end portion is made of resin or the like at the open end. It may be a free end in a state of being buried and closed.
- the external perfusion-type hollow fiber membrane module according to the second aspect of the present invention includes a hollow fiber membrane bundle in which a plurality of hollow fiber membranes are bundled, and a case in which the hollow fiber membrane bundle is accommodated. At least one end in the length direction of the hollow fiber membrane bundle is fixed in the case by a potting portion with the end face of each hollow fiber membrane open.
- a hollow fiber membrane having a Gurley bending resistance of 15 mN or more is used.
- the external perfusion-type hollow fiber membrane module according to the second aspect of the present invention is a hollow fiber membrane module for removing gas from the liquid to be treated or supplying gas to the liquid to be treated.
- the external perfusion type hollow fiber membrane module according to the second aspect of the present invention can be used as a deaeration module that removes gas dissolved in the liquid to be treated which is perfused outside the membrane of the hollow fiber membrane.
- the use of the external perfusion-type hollow fiber membrane module of the second aspect of the present invention is not particularly limited, and examples thereof include an inkjet discharge device such as an inkjet printer and a color filter manufacturing apparatus.
- the external perfusion-type hollow fiber membrane module 21 (hereinafter also referred to as “module 21”) of this embodiment includes a hollow fiber membrane bundle 210 and a case 214 as shown in FIG.
- the hollow fiber membrane bundle 210 is accommodated in the case 214, and the first end portion 210 a in the length direction of the hollow fiber membrane bundle 210 is fixed in the case 214 by the potting portion 216.
- the second end 210b opposite to the first end 210a in the hollow fiber membrane bundle 210 is a free end.
- the case 214 is provided on the cylindrical case main body 218, the first lid member 220 provided on the first opening end 218 a side in the length direction of the case main body 218, and the second opening end 218 b side of the case main body 218. And a second lid member 222.
- the case 214 forms a cylindrical appearance with the case body 218, the first lid member 220, and the second lid member 222.
- a case having a columnar appearance provided with a cylindrical case body as in this example is preferable.
- the appearance is not limited to a cylindrical case, and may be a polygonal columnar case provided with a polygonal cylindrical case body, for example.
- a first port 224 that communicates with the inside of the case body 218 is provided at a portion of the case body 218 near the first opening end 218 a so as to protrude outward from the outer peripheral surface of the case body 218.
- the first port 224 has a cylindrical shape and functions as a liquid inflow port through which the liquid to be processed flows into the case main body 218.
- the shape of the first port 224 is not limited to a cylindrical shape, and may be, for example, a polygonal cylindrical shape.
- the first lid member 220 includes a circular flat plate portion 220a, a cylindrical portion 220b provided so as to protrude from the outer peripheral edge of the flat plate portion 220a to the case body 218 side, and an outer side from the central portion of the flat plate portion 220a. And a second port 220c provided so as to protrude.
- the first end 219a of the case main body 218 is fitted into the cylindrical portion 220b, and the first lid member 220 is attached to the case main body 218.
- the second port 220c is located on the central axis L21 in the case 214.
- the second port 220c has a cylindrical shape, and functions as a gas outflow port through which gas flows out from the case 214 or a gas inflow port through which gas flows in.
- the shape of the second port 220c is not limited to a cylindrical shape, and may be, for example, a polygonal cylindrical shape.
- the second lid member 222 includes a circular flat plate portion 222a, a cylindrical portion 222b provided so as to protrude from the outer peripheral edge of the flat plate portion 222a to the case body 218 side, and an outer side from the central portion of the flat plate portion 222a. And a third port 222c provided so as to protrude.
- the second end 219b of the case main body 218 is fitted into the cylindrical portion 222b, and the second lid member 222 is attached to the case main body 218.
- the third port 222c is located on the central axis L21 in the case 214.
- the third port 222 c has a cylindrical shape and functions as a liquid outflow port through which the liquid to be processed flows out from the case 214.
- the shape of the third port 222c is not limited to a cylindrical shape, and may be, for example, a polygonal cylindrical shape.
- the flat plate portion 222a may be tapered so that bubbles in the case 214 can be easily removed.
- the material for forming the case 214 is preferably a material that can ensure sufficient mechanical strength and durability, and examples thereof include the same materials as those described in the case 112 of the first aspect.
- a material for forming the case 214 one type may be used alone, or two or more types may be used in combination.
- the hollow fiber membrane bundle 210 is formed by bundling a plurality of hollow fiber membranes 211 in a cylindrical shape.
- the form of the hollow fiber membrane bundle 210 is not limited to a columnar shape, and may be, for example, a form bundled in a cylindrical shape with a central tube arranged at the center.
- the hollow fiber membrane bundle 210 is accommodated in the case main body 218 in the case 214, and the first end 210a in the length direction of the hollow fiber membrane bundle 210 is at the end of the case main body 218 on the first opening end 218a side. It is fixed by a potting part 216.
- the plurality of hollow fiber membranes 211 forming the hollow fiber membrane bundle 210 are bundled in a state of being folded in a U shape at the center in the length direction, and end surfaces 211a on both sides of each hollow fiber membrane 211. Is embedded and fixed in the potting part 216 in a state in which is opened.
- a plurality of hollow fiber membranes are bundled in a state of being folded in a U shape at the center in the length direction, and the end faces on both sides of each hollow fiber membrane are It is preferable to be fixed in the case by the potting part in the opened state. Since the hollow fiber membranes are bundled in such a state, it becomes easy to sufficiently increase the filling rate of the hollow fiber membrane bundle even with a small number of hollow fiber membranes, and the production efficiency is improved. Moreover, since it becomes easy to maintain the self-supporting state of the hollow fiber membrane bundle, the liquid to be treated is easily distributed between the hollow fiber membranes throughout the hollow fiber membrane bundle, and the deaeration efficiency is improved.
- a second end portion 210b made of a U-turn portion of each hollow fiber membrane 211 located on the opposite side of the first end portion 210a in the hollow fiber membrane bundle 210 is not fixed to the case 214 and becomes a free end. ing.
- the liquid to be treated is easily distributed between the hollow fiber membranes 211 throughout the entire hollow fiber membrane bundle 210, so that the liquid to be treated can be degassed with high efficiency.
- the first opening end 218a of the case body 218 is closed by the potting portion 216.
- the end surface 216a on the first lid member 220 side of the potting portion 216 is flush with the first opening end 218a of the case body 218.
- end surfaces 211a on both sides of each hollow fiber membrane 211 are provided at the end surface 216a of the potting portion 216. Is open.
- a space is formed on the first lid member 220 side of the end surface 216 a of the potting portion 216 in the case 214, and the second end portion of the hollow fiber membrane bundle 210 than the potting portion 216 in the case main body 218.
- a space on the 210b side is partitioned by a potting portion 216.
- each hollow fiber membrane 211 Since the end surfaces 211 a on both sides of each hollow fiber membrane 211 are in an open state, the inside of each hollow fiber membrane 211 communicates with the space on the first lid member 220 side of the potting portion 216 in the case 214. It is in the state.
- the second port 220c and the third port 222c are both located on the central axis L21 in the case 214. Further, the inner wall surface of the case main body 218 and the hollow fiber membrane bundle 210 are separated from each other, and a space 226 is formed outside the hollow fiber membrane bundle 210 in the case 214.
- the hollow fiber membranes 211 are bundled in a state where they are connected to each other by warps 228. Specifically, a plurality of hollow fiber membranes 211 are warps 228 in a direction near the U-turn portion in each hollow fiber membrane 211 in a direction orthogonal to the central axis L21, that is, a direction orthogonal to the length direction of each hollow fiber membrane 211.
- the hollow fiber membranes 211 are connected to each other.
- it is preferable that the hollow fiber membranes are bundled in such a state that they are connected to each other by warps.
- each hollow fiber membrane 211 which forms the hollow fiber membrane bundle 210 spreads, and it becomes easy to hold
- the viscosity of the liquid to be perfused is high, the hollow fiber membranes 211 are particularly likely to be scattered, and it is difficult to ensure the self-supporting property of the hollow fiber membrane bundle 210. Therefore, the mode in which the hollow fiber membranes are connected by warp is particularly effective when the liquid to be treated to be perfused has a high viscosity, for example, when the liquid to be treated is ink or the like.
- An aspect in which a plurality of hollow fiber membranes are connected by warp is not particularly limited, and for example, an aspect of weaving in a chain stitch type can be mentioned.
- the positions of the end portions 211b made of U-turn portions in the hollow fiber membranes 211 are aligned with each other in the direction of the central axis L21 of the case 214. That is, the length of the part exposed from the potting part 216 in each hollow fiber membrane 211 is mutually aligned. That the positions of the end portions 211b of the hollow fiber membranes 211 are aligned with respect to the average value of the lengths of the portions exposed from the potting portions 216 in all the hollow fiber membranes 211 forming the hollow fiber membrane bundle 210, It means that the error of the length of each hollow fiber membrane 211 is ⁇ 5%.
- the ends of the hollow fiber membrane bundles are aligned with each other at the second end of the hollow fiber membrane bundle.
- the hollow fiber membrane bundle is easily prevented from being deformed, and the liquid to be treated is easily spread throughout the hollow fiber membrane bundle, thereby improving the deaeration efficiency.
- the outer diameter of the hollow fiber membrane 211 is preferably 350 ⁇ m or less, more preferably 150 to 330 ⁇ m, and even more preferably 200 to 300 ⁇ m. If the outer diameter of the hollow fiber membrane 211 is not more than the upper limit of the above range, more hollow fiber membranes can be filled in the case, and the contact with the liquid to be treated becomes more efficient. Further, an efficient flow path can be formed between the hollow fiber membranes 211 in the case 214. If the outer diameter of the hollow fiber membrane 211 is equal to or greater than the lower limit of the above range, it is easy to maintain a suitable bending resistance.
- the inner diameter of the hollow fiber membrane 211 is preferably 100 ⁇ m or more, more preferably 120 to 250 ⁇ m, and even more preferably 130 to 200 ⁇ m. If the inner diameter of the hollow fiber membrane 211 is within the above range, a sufficient number of hollow fiber membranes 211 can be accommodated in the case 214, and it is easy to maintain deaeration performance and durability.
- the thickness of the hollow fiber membrane 211 is preferably 20 to 70 ⁇ m, and more preferably 25 to 55 ⁇ m. If the film thickness of the hollow fiber membrane 211 is equal to or less than the above upper limit value, the durability when the pressure inside the hollow fiber membrane 211 inside the case 214 is repeatedly reduced is excellent. If the thickness of the hollow fiber membrane 211 is equal to or greater than the lower limit of the above range, the deaeration performance is easily maintained.
- the method for calculating the film thickness of the hollow fiber membrane and the method for measuring the inner diameter and outer diameter of the hollow fiber membrane are as described in the first aspect.
- the Gurley bending resistance of the hollow fiber membrane 211 is preferably 15 mN or more, and more preferably 18 to 25 mN. If the Gurley bending resistance of the hollow fiber membrane 211 is equal to or greater than the lower limit of the above range, it is easy to ensure the shape retention of the hollow fiber membrane bundle, and the shape of the hollow fiber membrane bundle is disturbed and the deaeration efficiency is reduced. Can be suppressed. If the Gurley bending resistance of the hollow fiber membrane is less than or equal to the upper limit of the above range, the handleability at the time of module creation is also suitable. The method for measuring the Gurley stiffness of the hollow fiber membrane is as described in the first aspect.
- the hollow fiber membrane 211 preferably has a breaking strength of 0.5 N / fil or more, a breaking elongation of 50% or more, and a breaking strength of 0.8 to 5 N from the viewpoint of handling at the time of module production. More preferably, the breaking elongation is 70 to 400%, the breaking strength is 1 to 4 N / fil, and the breaking elongation is 140 to 300%.
- the measuring method of breaking strength and breaking elongation is as described in the first aspect.
- the hollow fiber membrane 211 is preferably a hollow fiber membrane having gas permeability that allows gas to pass between the hollow portion in the membrane and the outside of the membrane.
- the hollow fiber membrane 211 has a gas-permeable homogeneous layer and a porous material that supports the homogeneous layer because it is excellent in strength and can be more efficiently degassed while suppressing leakage of the liquid to be treated.
- a composite hollow fiber membrane having a support layer is more preferable.
- the structure of the composite hollow fiber membrane is preferably a two-layer structure in which a porous support layer is provided inside or outside the homogeneous layer, or a three-layer structure in which a porous support layer is provided both inside and outside the homogeneous layer. From the viewpoint of strength, deaeration performance, a three-layer structure is more preferable.
- the material for forming the homogeneous layer is as described in the first embodiment.
- the material for forming the homogeneous layer in the second aspect is a polyolefin-based material because it is excellent in deaeration performance even when the liquid to be treated is perfused at a high flow rate and it is easy to ensure the shape retention of the hollow fiber membrane bundle. Resins are preferred, and polyethylene is more preferred.
- the polyolefin resin forming the homogeneous layer in the second aspect preferably has high gas permeability and chemical resistance, and more preferably metallocene polyethylene.
- the material for forming the porous support layer is as described in the first embodiment. From the viewpoint of easily securing the shape retention of the hollow fiber membrane bundle, the material for forming the porous support layer in the second embodiment is a melt flow index (MFR) equivalent to that of the homogeneous layer for the stability of membrane formation. Polyethylene having a high strength is preferable.
- the pore size of the porous support layer is preferably 0.01 to 1 ⁇ m.
- the porosity of the porous support layer is preferably 30 to 80% by volume. When the porosity is equal to or higher than the lower limit of the above range, the deaeration performance is excellent.
- the porosity is not more than the upper limit of the above range, the mechanical strength such as pressure resistance of the hollow fiber membrane is improved.
- the filling rate of the hollow fiber membrane bundle 210 in the case 214 in a cross section obtained by cutting the case 214 in a direction perpendicular to the length direction of the hollow fiber membrane bundle 210 is preferably 20 to 50%, more preferably 30 to 45%. . If the filling rate of the hollow fiber membrane is equal to or higher than the lower limit value, it is easy to suppress the occurrence of drift of the liquid to be treated in the case. If the filling rate of the hollow fiber membrane is not more than the upper limit value, the filling of the hollow fiber membrane becomes easy and the deaeration performance is improved.
- the filling rate is defined by each hollow forming the filled hollow fiber membrane bundle 210 with respect to a cross-sectional area inside the case 214 in a cross section obtained by cutting the case 214 in a direction perpendicular to the length direction of the hollow fiber membrane bundle 210. It is measured as a ratio (%) of the sum total of the cross-sectional areas of the thread membrane 211.
- the liquid to be processed is caused to flow into the case body 218 of the case 214 from the first port 224, and the liquid to be processed is caused to flow out from the third port 222c.
- the liquid to be treated is perfused outside the membrane of each hollow fiber membrane 211 in the region on the second end portion 210b side of the hollow fiber membrane bundle 210 relative to the potting portion 216 in the case 214.
- the configuration in which the liquid to be processed flows from the first port 224 and flows out from the third port 222c is not particularly limited.
- the liquid to be processed is pumped by connecting the first port 224 to a pump.
- the third port 222c may be connected to a pump to draw the liquid to be processed.
- the liquid to be treated that flows from the first port 224 passes through the space 226 between the hollow fiber membrane bundle 210 and the inner wall surface of the case body 218 in the case 214 to the opposite side of the first port 224 in the hollow fiber membrane bundle 210. While going around, it advances between the hollow fiber membranes 211 toward the center of the hollow fiber membrane bundle 210 and moves toward the third port 222c.
- the second port 220c of the first lid member 220 is connected to a vacuum pump and evacuated, so that the dissolved gas of the liquid to be processed that passes between the hollow fiber membranes 211 is taken into the membrane of the hollow fiber membranes 211. As a result, the liquid to be processed can be degassed.
- a hollow fiber membrane bundle 210 is formed by bundling hollow fiber membranes 211 having an outer diameter of 350 ⁇ m or less and a Gurley stiffness of 15 mN or more.
- the hollow fiber membrane 211 excellent in rigidity below a specific outer diameter is bundled, so that the shape retention of the hollow fiber membrane bundle 210 is excellent. Therefore, even if the module is enlarged and the hollow fiber membrane 211 is elongated, and the flow rate of the liquid to be processed is increased, the hollow fiber membrane bundle 210 is not easily deformed and the shape is not easily disturbed, so that the deaeration performance is reduced. It is suppressed.
- the manufacturing method of the module 21 is not specifically limited, For example, the following method is mentioned.
- the long hollow fiber membrane 211A is alternately repeated a plurality of times in the opposite direction and folded back into a U shape to form a belt-like hollow fiber membrane sheet 213.
- the hollow fiber membrane 211A is knitted in the length direction of the sheet with the warp yarns 228, and the portions of the hollow fiber membrane 211A extending in the width direction are connected to each other.
- the hollow fiber membrane sheet 213 is wound into a columnar shape so that the width direction of the hollow fiber membrane sheet 213 is the axial direction.
- FIG. 9 the long hollow fiber membrane 211A is alternately repeated a plurality of times in the opposite direction and folded back into a U shape to form a belt-like hollow fiber membrane sheet 213.
- the hollow fiber membrane 211A is knitted in the length direction of the sheet with the warp yarns 228, and the portions of the hollow fiber membrane 211A extending in the width direction are connected to each other.
- the hollow fiber membrane sheet 213 wound in a columnar shape is inserted into the case main body 218, and the hollow fiber membrane sheet 213 is made with a potting resin 252 using a known method such as a centrifugal method. Is fixed to the first opening end 218a side of the case body 218. At this time, the U-turn portion of the hollow fiber membrane 211A on the hollow fiber membrane sheet 213 fixed to the potting resin 252 and a part of the potting resin 252 are projected from the case body 218.
- the module 21 is obtained by attaching the first lid member 220 and the second lid member 222 to both ends of the case body 218.
- hollow fiber membrane bundles are formed by bundling hollow fiber membranes having a Gurley stiffness of 15 mN or more.
- the external perfusion type hollow fiber membrane module according to the second aspect of the present invention is not limited to the module 21 described above.
- the external perfusion-type hollow fiber membrane module according to the second aspect of the present invention includes a first end portion in which each hollow fiber membrane forming a hollow fiber membrane bundle is not folded back in a U shape and is fixed by a potting portion.
- the second end on the opposite side may be a free end with its open end closed with resin or the like.
- both ends of the hollow fiber membrane bundle in the length direction may be fixed to the case by a potting portion.
- the external perfusion-type hollow fiber membrane module of the second aspect of the present invention may be the external perfusion-type hollow fiber membrane module 22 illustrated in FIG. 12 (hereinafter also referred to as “module 22”).
- module 22 includes a hollow fiber membrane bundle 210A and a case 214A.
- the hollow fiber membrane bundle 210A is accommodated in the case 214A, and the potting portions 216A and 216B enter the case 214A at the first end portion 210a and the second end portion 210b in the length direction of the hollow fiber membrane bundle 210A. It is fixed.
- the case 214A is provided on the cylindrical case body 218A, the first lid member 220 provided on the first opening end 218a side in the length direction of the case body 218A, and the second opening end 218b side of the case body 218A. And a second lid member 222.
- the case 214A forms a columnar appearance with the case main body 218A, the first lid member 220, and the second lid member 222.
- a portion of the case 214A near the first opening end 218a of the case main body 218A is connected to the inside of the case main body 218A so as to protrude outward from the outer peripheral surface of the case main body 218A, similar to the case 214. Is provided. Further, a portion of the case 214A near the second opening end 218b in the case main body 218A is connected to the inside of the case main body 218A so as to protrude from the outer peripheral surface of the case main body 218A to the side opposite to the first port 224.
- a port 230 is provided.
- the shape of the fourth port 230 is not particularly limited, and examples thereof include a cylindrical shape and a polygonal cylindrical shape.
- the hollow fiber membrane bundle 210A is formed by bundling a plurality of hollow fiber membranes 211 into a columnar shape in a state where the hollow fiber membranes 211 are aligned in one direction.
- the first opening end 218a of the case main body 218A is closed by the potting portion 216A, and the first end portion 210a in the length direction of the hollow fiber membrane bundle 210A is embedded in the potting portion 216A so as to be in the case main body 218A. It is being fixed to the part by the side of the 1st opening end 218a inside.
- the end surface 216a on the first lid member 220 side of the potting portion 216A is flush with the first opening end 218a of the case body 218A, and the first opening end of each hollow fiber membrane 211 on the end surface 216a of the potting portion 216A.
- the end surface 211a on the 218a side is in an open state. Since the end surface 211a on the first opening end 218a side of each hollow fiber membrane 211 is in an open state, the inside of each hollow fiber membrane 211 and the first lid member 220 side of the potting portion 216A in the case 214A It is in a state of communication with the space.
- the second opening end 218b of the case body 218A is closed by the potting portion 216B, and the second end portion 210b of the hollow fiber membrane bundle 210A is embedded in the potting portion 216B so that the inside of the case body 218A is It is fixed to a portion on the second opening end 218b side.
- the end surface 216b on the second lid member 222 side of the potting portion 216B is flush with the second opening end 218b of the case body 218A, and the second opening end of each hollow fiber membrane 211 is formed on the end surface 216b of the potting portion 216B.
- the end surface 211c on the 218b side is in an open state.
- each hollow fiber membrane 211 Since the end face 211c on the second opening end 218b side of each hollow fiber membrane 211 is in an open state, the inside of each hollow fiber membrane 211 and the second lid member 222 side of the potting portion 216B in the case 214A It is in a state of communication with the space.
- the inner wall surface of the case main body 218A and the hollow fiber membrane bundle 210A are separated from each other, and a space 226 is formed outside the hollow fiber membrane bundle 210A in the case 214A.
- the liquid to be processed is caused to flow into the case body 218 ⁇ / b> A of the case 214 ⁇ / b> A from the first port 224, and the liquid to be processed is caused to flow out from the fourth port 230.
- the liquid to be treated is perfused outside the membrane of each hollow fiber membrane 211 in the region between the potting portion 216A and the potting portion 216B in the case 214A.
- the second port 220c of the first lid member 220 and the third port 222c of the second lid member 222 are connected to a vacuum pump and evacuated so that the liquid to be treated that passes between the hollow fiber membranes 211 can be obtained. Since the dissolved gas is taken into the membrane of the hollow fiber membrane 211 and flows out from the second port 220c and the third port 222c, the liquid to be treated can be degassed.
- hollow fiber membrane bundles 210A are formed by bundling hollow fiber membranes 211 having a Gurley stiffness of 15 mN or more. As described above, the hollow fiber membranes 211 having excellent rigidity below a specific outer diameter are bundled, so that the shape retention of the hollow fiber membrane bundle 210A is excellent. Therefore, the hollow fiber membrane bundle 210A is less likely to lose its shape during manufacturing and use, and the shape is less likely to be disturbed.
- the external perfusion-type hollow fiber membrane module includes a hollow fiber membrane bundle in which a plurality of hollow fiber membranes are bundled in a cylindrical shape so that a hollow portion is formed inside, and the hollow fiber membrane bundle And a case in which is housed.
- the first end in the length direction of the hollow fiber membrane bundle is fixed in the case by the potting portion with the end face of each hollow fiber membrane open, and the second end opposite to the first end in the hollow fiber membrane bundle.
- the end is a free end.
- only the hollow fiber membrane bundle is provided in the region between the potting portion and the second end portion of the hollow fiber membrane bundle in the case.
- the external perfusion-type hollow fiber membrane module according to the third aspect of the present invention is a module for degassing that removes gas dissolved in liquid to be externally perfused or for supplying gas to liquid to be externally perfused.
- the use of the external perfusion-type hollow fiber membrane module of the third aspect of the present invention is not particularly limited, and examples thereof include an inkjet discharge apparatus such as an inkjet printer and a color filter manufacturing apparatus.
- the external perfusion-type hollow fiber membrane module 31 (hereinafter also referred to as “module 31”) of the third aspect of the present embodiment includes a hollow fiber membrane bundle 310 and a case 314, as shown in FIG. ing.
- the hollow fiber membrane bundle 310 is accommodated in the case 314, and the first end portion 310 a in the length direction of the hollow fiber membrane bundle 310 is fixed in the case 314 by the potting portion 316.
- the second end 310b opposite to the first end 310a in the hollow fiber membrane bundle 310 is a free end.
- the case 314 is provided on the cylindrical case body 318, the first lid member 320 provided on the first opening end 318 a side in the length direction of the case body 318, and the second opening end 318 b side of the case body 318. And a second lid member 322.
- the case 314 forms a columnar appearance with the case body 318, the first lid member 320, and the second lid member 322.
- the case in the external perfusion type hollow fiber membrane module of the third aspect of the present invention is preferably a cylindrical case having a cylindrical case body as in this example.
- the appearance is not limited to a cylindrical case, and may be, for example, a polygonal columnar case provided with a polygonal cylindrical case body.
- a first port 324 that communicates with the inside of the case main body 318 is provided at a portion of the case main body 318 near the first opening end 318a so as to protrude outward from the outer peripheral surface of the case main body 318.
- the first port 324 has a cylindrical shape and functions as a liquid inflow / outflow port through which liquid flows in / out of the case main body 318.
- the shape of the first port 324 is not limited to a cylindrical shape, and may be, for example, a polygonal cylindrical shape.
- the first lid member 320 includes a circular flat plate portion 320a, a cylindrical portion 320b provided so as to protrude from the outer peripheral edge of the flat plate portion 320a to the case body 318 side, and an outer side from the central portion of the flat plate portion 320a. And a second port 320c provided so as to protrude.
- the first end 319a of the case main body 318 is fitted into the cylindrical portion 320b, and the first lid member 320 is attached to the case main body 318.
- the second port 320c is located on the central axis L31 in the case 314.
- the second port 320c has a cylindrical shape and functions as a gas outflow port through which gas flows out from the case 314 or a gas inflow port through which gas flows in.
- the shape of the second port 320c is not limited to a cylindrical shape, and may be, for example, a polygonal cylindrical shape.
- the second lid member 322 includes a circular flat plate portion 322a, a cylindrical portion 322b provided so as to protrude from the outer peripheral edge of the flat plate portion 322a to the case main body 318 side, and the central portion of the flat plate portion 322a. And a third port 322c provided so as to protrude.
- the second end 319b of the case main body 318 is fitted into the cylindrical portion 322b, and the second lid member 322 is attached to the case main body 318.
- the third port 322c is located on the central axis L31 in the case 314.
- the third port 322c has a cylindrical shape and functions as a liquid inflow / outflow port through which liquid flows in / out of the case 314.
- the shape of the third port 322c is not limited to a cylindrical shape, and may be, for example, a polygonal cylindrical shape.
- the flat plate portion 322a may have a tapered shape in order to improve bubble removal in the case 314.
- the size of the case 314 can be set as appropriate.
- the outer diameter of the case body 318 can be 3 to 15 cm and the length can be 5 to 50 cm.
- the outer diameter and length of the case body 318 can be changed as appropriate. .
- the material for forming the case 314 is preferably a material that can ensure sufficient mechanical strength and durability, and examples thereof include the same materials as those described in the case 112 of the first aspect.
- a material for forming the case 314 one type may be used alone, or two or more types may be used in combination.
- the hollow fiber membrane bundle 310 is formed by bundling a plurality of hollow fiber membranes 311 into a cylindrical shape so that a hollow portion 312 is formed inside.
- the shape of the hollow fiber membrane bundle 310 is preferably cylindrical as in this example.
- the shape of the hollow fiber membrane bundle 310 is not limited to a cylindrical shape, and may be an elliptical cylindrical shape, a square shape, or the like.
- the hollow fiber membrane bundle 310 is accommodated in the case main body 318 of the case 314, and the first end 310a in the length direction of the hollow fiber membrane bundle 310 is at the end of the case main body 318 on the first opening end 318a side. It is fixed by a potting part 316.
- the plurality of hollow fiber membranes 311 forming the hollow fiber membrane bundle 310 are bundled in a state of being folded in a U shape at the center in the length direction, and end faces 311a on both sides of each hollow fiber membrane 311. Is embedded and fixed in the potting portion 316 in a state in which is opened.
- a plurality of hollow fiber membranes are bundled in a state of being folded in a U shape at the center in the length direction, and the end faces on both sides of each hollow fiber membrane are It is preferable to be fixed in the case by the potting part in the opened state. Since the hollow fiber membranes are bundled in such a state, it becomes easy to sufficiently increase the filling rate of the hollow fiber membrane bundle even with a small number of hollow fiber membranes, and the production efficiency is improved. Moreover, since it becomes easy to maintain the self-supporting state of the hollow fiber membrane bundle, the liquid easily spreads between the hollow fiber membranes throughout the hollow fiber membrane bundle, and the efficiency of deaeration or air supply is improved.
- the second end portion 310b made of the U-turn portion of each hollow fiber membrane 311 located on the opposite side to the first end portion 310a in the hollow fiber membrane bundle 310 is not fixed to the case 314 but becomes a free end. ing. Thereby, since the liquid easily spreads between the hollow fiber membranes 311 throughout the entire hollow fiber membrane bundle 310, the liquid can be deaerated or supplied with high efficiency.
- the first opening end 318a of the case body 318 is closed by the potting portion 316.
- the end surface 316a of the potting portion 316 on the first lid member 320 side is flush with the first opening end 318a of the case body 318.
- the end surface 316a of the potting portion 316 has end surfaces 311a on both sides of each hollow fiber membrane 311. Is open.
- a space is formed on the first lid member 320 side of the end surface 316 a of the potting portion 316 in the case 314, and the second end portion of the hollow fiber membrane bundle 310 than the potting portion 316 in the case main body 318.
- a space on the 310b side is partitioned by a potting portion 316. Since the end surfaces 311a on both sides of each hollow fiber membrane 311 are open, the inside of each hollow fiber membrane 311 communicates with the space on the first lid member 320 side of the potting portion 316 in the case 314. It is in the state.
- each hollow fiber membrane 311 is bundled in a cylindrical shape so as to surround the center axis L ⁇ b> 31 of the case 314, and a cylindrical shape is formed inside the hollow fiber membrane bundle 310.
- a cavity 312 is formed.
- the hollow portion 312, the second port 320c, and the third port 322c are all located on the central axis L31 in the case 314. Further, the inner wall surface of the case body 318 and the hollow fiber membrane bundle 310 are separated from each other, and a space 326 is formed outside the hollow fiber membrane bundle 310 in the case 314.
- the hollow fiber membrane bundle 310 is formed in a region between the end surface 316 b on the second end portion 310 b side of the hollow fiber membrane bundle 310 of the potting portion 316 and the second end portion 310 b of the hollow fiber membrane bundle 310 in the case 314. Only provided. That is, nothing is arranged in the hollow portion 312 inside the cylindrical hollow fiber membrane bundle 310. Accordingly, the hollow fiber membrane bundle 310 is passed between the hollow fiber membranes 311 between the space 326 outside the cylindrical hollow fiber membrane bundle 310 and the hollow portion 312 inside the hollow fiber membrane bundle 310 over the entire hollow fiber membrane bundle 310. The moving liquid moves without being blocked.
- the hollow fiber membranes 311 may be bundled in a state of being connected to each other by warp yarns 328.
- a plurality of hollow fiber membranes 311 are warp yarns 328 in a direction near the U-turn portion in each hollow fiber membrane 311 in a direction orthogonal to the central axis L31, that is, a direction orthogonal to the length direction of each hollow fiber membrane 311.
- the hollow fiber membranes 311 are connected to each other.
- it is preferable that the hollow fiber membranes are bundled in such a state that they are connected to each other by warps.
- each hollow fiber membrane 311 which forms the hollow fiber membrane bundle 310 spreads, and it becomes easy for the hollow fiber membrane bundle 310 to hold
- the viscosity of the liquid to be perfused is high, in particular, the hollow fiber membrane 311 is likely to be scattered, and it becomes difficult to ensure the self-supporting property of the hollow fiber membrane bundle 310. Therefore, the mode in which the hollow fiber membranes are connected by warp is particularly effective when the viscosity of the liquid to be perfused is high, for example, when the liquid is ink or the like.
- An aspect in which a plurality of hollow fiber membranes are connected by warp is not particularly limited, and for example, an aspect of weaving in a chain stitch type can be mentioned.
- the positions of the end portions 311b made of U-turn portions in the hollow fiber membranes 311 are aligned with each other in the direction of the central axis L31 of the case 314. That is, the length of the part exposed from the potting part 316 in each hollow fiber membrane 311 is mutually aligned.
- the average value of the lengths of the portions exposed from the potting portions 316 in all the hollow fiber membranes 311 forming the hollow fiber membrane bundle 310 is It means that the error of the length of each hollow fiber membrane 311 is ⁇ 5%.
- the end portions of the hollow fiber membrane bundles are aligned with each other at the second end portion of the hollow fiber membrane bundle.
- the hollow fiber membrane bundle is easily prevented from losing its shape, and the liquid easily spreads over the entire hollow fiber membrane bundle, thereby improving the efficiency of deaeration or air supply.
- the hollow fiber membrane 311 is preferably a hollow fiber membrane having gas permeability that allows gas to pass between the hollow portion in the membrane and the outside of the membrane. Moreover, from the point which is excellent in intensity
- the structure of the composite hollow fiber membrane is preferably a two-layer structure in which a porous support layer is provided inside or outside the homogeneous layer, or a three-layer structure in which a porous support layer is provided both inside and outside the homogeneous layer. A three-layer structure is more preferable in terms of strength, deaeration or supply performance.
- the material for forming the homogeneous layer is as described in the first embodiment.
- the material for forming the homogeneous layer in the third aspect is preferably a polyolefin-based resin from the viewpoint of excellent deaeration and air supply performance even when a liquid is perfused at a high flow rate and excellent chemical resistance.
- a low density polyethylene resin is more preferred because of its excellent film properties.
- the material for forming the porous support layer is as described in the first embodiment.
- the material for forming the homogeneous layer in the third aspect is preferably high-density polyethylene showing an MFR value equivalent to that of the homogeneous layer.
- the pore size of the porous support layer is preferably 0.01 to 1 ⁇ m.
- the porosity of the porous support layer is preferably 30 to 80% by volume. When the porosity is equal to or higher than the lower limit of the above range, the performance of deaeration or supply is excellent. When the porosity is not more than the upper limit of the above range, the mechanical strength such as pressure resistance of the hollow fiber membrane is improved.
- the outer diameter of the hollow fiber membrane 311 is preferably 350 ⁇ m or less, more preferably 150 to 330 ⁇ m, and even more preferably 200 to 300 ⁇ m. If the outer diameter of the hollow fiber membrane 311 is within the above range, an efficient flow path can be formed between the hollow fiber membranes 311 in the case 314.
- the inner diameter of the hollow fiber membrane 311 is preferably 100 ⁇ m or more, more preferably 120 to 250 ⁇ m, still more preferably 130 to 200 ⁇ m.
- the inner diameter of the hollow fiber membrane 311 is within the above range, a sufficient number of hollow fiber membranes 311 can be accommodated in the case 314, and it is easy to maintain the deaeration or supply performance and durability.
- the film thickness of the hollow fiber membrane 311 is preferably 20 to 70 ⁇ m, more preferably 25 to 55 ⁇ m. If the film thickness of the hollow fiber membrane 311 is equal to or less than the above upper limit value, the durability when the inside of the hollow fiber membrane 311 in the case 314 is repeatedly depressurized and pressurized is excellent. If the thickness of the hollow fiber membrane 311 is equal to or greater than the lower limit of the above range, it is easy to maintain the deaeration or supply performance satisfactorily.
- the method for calculating the film thickness of the hollow fiber membrane and the method for measuring the inner diameter and outer diameter of the hollow fiber membrane are as described in the first aspect.
- the thickness of the homogeneous layer is preferably from 0.3 to 2 ⁇ m, more preferably from 0.5 to 1.2 ⁇ m.
- the method for measuring the thickness of the homogeneous layer and the porous support layer is as described in the first embodiment.
- the hollow fiber membrane 311 preferably has a breaking strength of 0.5 N / fil or more, a breaking elongation of 50% or more, and a breaking strength of 0.8 to 5 N from the viewpoint of handling at the time of module production. More preferably, the breaking elongation is 70 to 400%, the breaking strength is 1 to 4 N / fil, and the breaking elongation is 140 to 300%.
- the measuring method of breaking strength and breaking elongation is as described in the first aspect.
- the filling rate of the hollow fiber membrane bundle 310 in the case 314 in a cross section obtained by cutting the case 314 in the direction perpendicular to the length direction of the hollow fiber membrane bundle 310 is preferably 20 to 50%, more preferably 30 to 45%. . If the filling rate of the hollow fiber membrane is equal to or higher than the lower limit, it is easy to suppress the occurrence of liquid drift in the case. If the filling rate of a hollow fiber membrane is below an upper limit, filling of a hollow fiber membrane will become easy and the performance of deaeration or air supply will improve.
- the filling rate is defined by each hollow forming the filled hollow fiber membrane bundle 310 with respect to a cross-sectional area inside the case 314 in a cross section obtained by cutting the case 314 in a direction perpendicular to the length direction of the hollow fiber membrane bundle 310. It is measured as a ratio (%) of the total cross-sectional area of the thread membrane 311.
- the Gurley bending resistance of the hollow fiber membrane is preferably 10 mN or more, more preferably 15 to 30 mN, and even more preferably 18 to 25 mN. If the Gurley bending resistance of the hollow fiber membrane is equal to or higher than the lower limit of the above range, it is easy to ensure the self-supporting property of the hollow fiber membrane bundle, and it is easy to suppress a reduction in the efficiency of deaeration or supply. If the Gurley bending resistance of the hollow fiber membrane is less than or equal to the upper limit of the above range, there is little membrane disruption associated with the increase in membrane length when the membrane bundle is formed, and the module can be formed in an aligned state. It becomes possible.
- the method for measuring the Gurley stiffness of the hollow fiber membrane is as described in the first aspect.
- the manufacturing method of the module 31 is not specifically limited, For example, the following method is mentioned.
- a long hollow fiber membrane 311A is alternately repeated a plurality of times in the opposite direction and folded back into a U-shape to form a belt-like hollow fiber membrane sheet 313.
- the hollow fiber membrane 311A is knitted in the length direction of the sheet with the warp yarns 328, and the portions extending in the width direction of the hollow fiber membrane 311A are connected to each other.
- the hollow fiber membrane sheet 313 is wound around a cylindrical core rod 350. As shown in FIG.
- the hollow fiber membrane sheet 313 wound around the core rod 350 is inserted into the case body 318, the core rod 350 is pulled out, and then potting is performed using a known method such as a centrifugal method.
- One end of the hollow fiber membrane sheet 313 is fixed to the first opening end 318 a side of the case body 318 by the resin 352.
- the U-turn portion of the hollow fiber membrane 311A on the side fixed by the potting resin 352 in the hollow fiber membrane sheet 313 and a part of the potting resin 352 are projected from the case body 318.
- the end surface 311a of each hollow fiber membrane 311 folded back in a U shape is formed.
- a cylindrical hollow fiber membrane bundle 310 is formed which is fixed to the case main body 318 by the potting portion 316 and has a hollow portion 312 formed inside.
- the module 31 is obtained by attaching the first lid member 320 and the second lid member 322 to both ends of the case body 318.
- the module 31 can be used as follows, for example.
- the liquid is caused to flow into the case body 318 of the case 314 from the first port 324, and the liquid is caused to flow out from the third port 322c.
- the liquid is perfused outside the membrane of each hollow fiber membrane 311 in the region on the second end portion 310b side of the hollow fiber membrane bundle 310 relative to the potting portion 316 in the case 314.
- the configuration in which the liquid flows in from the first port 324 and flows out from the third port 322c may be such that the first port 324 is connected to a pump and the liquid is pumped.
- the configuration may be such that the three ports 322c are connected to a pump to draw liquid.
- the liquid flowing in from the first port 324 wraps around the opposite side of the hollow fiber membrane bundle 310 to the first port 324 through the space 326 between the hollow fiber membrane bundle 310 and the inner wall surface of the case body 318 in the case 314.
- the hollow fiber membrane bundle 310 passes between the hollow fiber membranes 311 from the outer side toward the inner cavity 312.
- the second port 320c of the first lid member 320 is connected to a vacuum pump and evacuated
- dissolved liquid gas passing between the hollow fiber membranes 311 is taken into the membrane of the hollow fiber membranes 311. Since the liquid flows out from the second port 320c, the liquid can be deaerated.
- the gas is supplied to the liquid passing between the hollow fiber membranes 311 through the hollow fiber membranes 311 by supplying the gas by connecting the second port 320c of the first lid member 320 to the air supply pump. can do.
- the hollow fiber membrane bundle 310 is provided in the region between the potting portion 316 and the second end portion 310 b of the hollow fiber membrane bundle 310 in the case 314, and the inside of the cylindrical hollow fiber membrane bundle 310 is provided.
- Nothing is arranged in the hollow portion 312 of the above.
- the liquid passing between the hollow fiber membranes 311 is not blocked from the outer space 326 of the hollow fiber membrane bundle 310 to the inner cavity 312 over the entire hollow fiber membrane bundle 310. Can move smoothly. Therefore, even when the flow rate of the liquid to be perfused is increased by increasing the size of the module, the liquid tends to flow from the outer space 326 of the hollow fiber membrane bundle 310 toward the inner cavity 312 over the entire hollow fiber membrane bundle 310. From this, in the case 314, it can suppress that the liquid flows unevenly through the part of the space 326, so that it is possible to suppress the efficiency of deaeration and supply of air from decreasing.
- the external perfusion-type hollow fiber membrane module of the third aspect of the present invention only the hollow fiber membrane bundle is present in the region between the potting portion and the second end of the hollow fiber membrane bundle in the case. Is provided.
- the liquid which passes between each hollow fiber membrane can move without being interrupted between the outside of the cylindrical hollow fiber membrane bundle and the hollow portion inside the hollow fiber membrane bundle over the entire hollow fiber membrane bundle. Therefore, even if the flow rate of the liquid to be perfused is increased by increasing the size of the module, it is possible to prevent the liquid from flowing unevenly in the case and to prevent the efficiency of deaeration and air supply from decreasing.
- the external perfusion type hollow fiber membrane module according to the third aspect of the present invention is not limited to the module 31 described above.
- the external perfusion-type hollow fiber membrane module according to the third aspect of the present invention includes a first end portion in which each hollow fiber membrane forming the hollow fiber membrane bundle is not folded back in a U shape and is fixed by a potting portion.
- the second end portion on the opposite side may be a free end in a state where the open end is filled with resin or the like and closed.
- the external perfusion type hollow fiber membrane module of the present invention may be a combination of the first aspect and the second aspect, may be a combination of the first aspect and the third aspect, and the second aspect.
- the third aspect may be combined, or the first aspect, the second aspect, and the third aspect may be combined.
- MFR Melt flow index
- Gurley stiffness Using a Gurley type bending resistance tester, the Gurley bending resistance of the hollow fiber membrane was measured in accordance with JIS L 1096A method. Seven bundles of hollow fiber membranes in which the hollow fiber membranes were folded back in units of 32 (32 fil) were used as measurement samples, and the measurement sample size was 25 to 26 mm in width and 51 mm in length.
- Example A1 An external perfusion type hollow fiber membrane module having the same mode as the module 11 illustrated in FIG. 1 was produced.
- the hollow fiber membrane 111 is formed of a high density polyethylene resin (MFR: 1.35 g / 10 min) on the inside and outside of a homogeneous layer formed of a metallocene low density polyethylene resin (MFR: 1.0 g / 10 min).
- MFR high density polyethylene resin
- MFR metallocene low density polyethylene resin
- a three-layer composite hollow fiber membrane provided with a porous support layer was used.
- the composite hollow fiber membrane had an outer diameter of 197 ⁇ m, an inner diameter of 133 ⁇ m, and a film thickness of 32 ⁇ m.
- the Gurley bending resistance of the composite hollow fiber membrane was 5 mN.
- the inner diameter of the case main body 116 in the case 112 was 52 mm.
- the hollow fiber membrane bundle 110 was fixed in the case 112 by the potting portion 124 so that the effective membrane area was 1.42 m 2 .
- the filling rate of the hollow fiber membrane bundle 110 in the case 112 in a cross section obtained by cutting the case 112 in a direction perpendicular to the length direction of the hollow fiber membrane bundle 110 was 30%.
- As the short path preventing body 114 a ring having a rectangular cross section with a width D1 in the direction along the central axis L11 of 5 mm, an inner diameter of 46 mm, and a protruding height H1 of 3 mm was used.
- the distance d12 from the position of the central axis L12 of the first port 122 to the short path prevention body 114 was 9 mm, and d12 / d11 was 0.075.
- Example A2 The outer diameter of the composite hollow fiber membrane is 283 ⁇ m, the inner diameter is 199 ⁇ m, the Gurley stiffness is changed to 20 mN, and the hollow fiber membrane bundle 110 is placed in the case 112 by the potting part 124 so that the effective membrane area becomes 1.15 m 2 .
- the outer perfusion type hollow fiber membrane module was produced in the same manner as in Example A1 except that the filling rate of the hollow fiber membrane bundle 110 in the case 112 was 30%.
- Example A3 An external perfusion-type hollow fiber membrane module was produced in the same manner as in Example A1, except that the short path prevention body was not provided in the case.
- Example A4 An external perfusion-type hollow fiber membrane module was produced in the same manner as in Example A2 except that the short path preventer was not provided in the case.
- Example A5 The inner diameter of the case body 116 is 48 mm, the inner diameter of the short path prevention body 114 is 46 mm, the protruding height H1 is 3 mm, the effective membrane area of the hollow fiber membrane bundle 110 is 1.63 m 2, and d12 / d11 is 0.060. Except that, an external perfusion-type hollow fiber membrane module was produced in the same manner as in Example A1.
- Example A6 Except for changing the outer diameter of the composite hollow fiber membrane to 283 ⁇ m, the inner diameter to 199 ⁇ m, the Gurley stiffness to 20 mN, and the effective membrane area of the hollow fiber membrane bundle 110 to 1.21 m 2 , the same as Example A5 An external perfusion type hollow fiber membrane module was fabricated.
- Example A7 An external perfusion-type hollow fiber membrane module was produced in the same manner as in Example A5 except that the short path preventer was not provided in the case.
- Example A8 An external perfusion-type hollow fiber membrane module was produced in the same manner as in Example A6 except that the short path preventer was not provided in the case.
- the dissolved oxygen removal rate of the treated water is high compared to the module of Example A7 in which the pass prevention body is not provided and the Gurley stiffness of the hollow fiber membrane is less than 15 mN.
- Deaeration performance was high, and the difference in the dissolved oxygen removal rate by each test method was small.
- the deaeration performance was high both when the liquid to be processed flows in the vertical direction and in the horizontal direction.
- Example B1 The module 21 illustrated in FIG. 8 was produced.
- the hollow fiber membrane 211 the composite hollow fiber membrane B was used.
- the inner diameter of the case main body 218 was 30 mm, a cylindrical hollow fiber membrane bundle 210 having a height of 135 mm and an effective membrane area of 0.46 m 2 was filled at a filling rate of 30% and fixed in the case 214.
- Example B2 The hollow fiber membrane 211 is changed to a composite hollow fiber membrane C, and a cylindrical hollow fiber membrane bundle 210 having a height of 135 mm and an effective membrane area of 0.43 m 2 is filled at a filling rate of 30% and fixed in the case 214 Produced an external perfusion-type hollow fiber membrane module in the same manner as in Example B1.
- Examples B3 to B5 Except that the hollow fiber membrane 211 was changed to the composite hollow fiber membrane A and the diameter, height, effective membrane area and filling rate of the hollow fiber membrane bundle 210 were changed as shown in Table 2, the same as in Example B1, the external A perfusion type hollow fiber membrane module was fabricated.
- Examples B6 to B7 Except that the hollow fiber membrane 211 was changed to the composite hollow fiber membrane D, and the diameter, height, effective membrane area and filling rate of the hollow fiber membrane bundle 210 were changed as shown in Table 2, the same as in Example B1, the external A perfusion type hollow fiber membrane module was fabricated.
- the Gurley stiffness is less than 15 mN.
- the dissolved oxygen removal rate was high and the deaeration performance was excellent even when the flow rate of the water to be treated was high.
- Example C1 A module 31 illustrated in FIG. 14 was produced.
- a composite hollow fiber membrane (product name “MHF130EPE”) manufactured by Mitsubishi Chemical Corporation was used.
- the inner diameter of the case main body 318 was 52 mm.
- a core rod 350 having a diameter of 10 mm a cylindrical hollow fiber membrane bundle 310 having a cylindrical hollow portion 312 having a diameter of 10 mm formed therein is formed, and a potting portion 316 has an effective membrane area of 1.45 m 2.
- the filling rate of the hollow fiber membrane bundle 310 in the case 314 in the cross section obtained by cutting the case 314 in the direction perpendicular to the length direction of the hollow fiber membrane bundle 310 was 28%.
- Example C2 The external perfusion-type hollow fiber membrane module 3101 illustrated in FIG. 20 is the same as the module 31 of Example C1 except that the hollow fiber membrane bundle is changed from a cylindrical shape to a columnar shape and no hollow portion is formed inside. Was made.
- the filling rate of the hollow fiber membrane bundle 3110 in the case 3114 in the cross section obtained by cutting the case 3114 in the direction perpendicular to the length direction of the hollow fiber membrane bundle 3110 was the same as the filling rate of Example C1.
- Example C3 The case body 318 has an inner diameter of 48 mm, a hollow fiber membrane having an outer diameter of 283 ⁇ m, an inner diameter of 199 ⁇ m and a Gurley stiffness of 20 mN.
- An external perfusion-type hollow fiber membrane module was produced in the same manner as in Example C1 except that the hollow fiber membrane bundle had an effective membrane area of 1.21 m 2 and the filling rate of the hollow fiber membrane bundle was 30%.
- Example C4 The case body 318 has an inner diameter of 48 mm, a hollow fiber membrane having an outer diameter of 283 ⁇ m, an inner diameter of 199 ⁇ m, and a Gurley stiffness of 20 mN.
- An external perfusion-type hollow fiber membrane module was produced in the same manner as in Example C1, except that the filling rate of the cylindrical hollow fiber membrane bundle formed inside was 30%.
- Example C5 The case body 318 has an inner diameter of 48 mm, a hollow fiber membrane having an outer diameter of 197 ⁇ m, an inner diameter of 133 ⁇ m, and a Gurley stiffness of 5 mN.
- An external perfusion-type hollow fiber membrane module was produced in the same manner as in Example C1, except that the hollow fiber membrane bundle had an effective membrane area of 1.63 m 2 and the filling rate of the hollow fiber membrane bundle was 30%.
- a hollow fiber membrane bundle having a hollow portion formed inside is provided, and only the hollow fiber membrane bundle is provided in a region between the potting portion and the second end portion of the hollow fiber membrane bundle in the case.
- the treated water is dissolved in comparison with the external perfusion type hollow fiber membrane module of Example C2 provided with a hollow fiber membrane bundle that is cylindrical and has no hollow portion formed inside.
- the oxygen removal rate was high and the deaeration performance was high.
- the hollow fiber membrane has a Gurley stiffness of 15 mN or more and no hollow portion in the hollow fiber membrane bundle, and the hollow fiber membrane has a Gurley stiffness of 15 mN or more and hollow in the hollow fiber membrane bundle.
- the dissolved oxygen removal rate of treated water is higher than the module of Example C5 in which the Gurley stiffness of the hollow fiber membrane is less than 15 mN and the hollow fiber membrane bundle does not have a cavity, The performance was high.
- first port 124, 216, 216A, 216B, 316 ... potting part, 128 ... gap 220c ... second port, 222c ... third port, 230 ... fourth port, 312 ... cavity, 320c ... second port , 322c ... the third port.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Supply & Treatment (AREA)
- Artificial Filaments (AREA)
Abstract
Description
本願は、2017年6月14日に日本に出願された特願2017-116620号、2017年6月14日に日本に出願された特願2017-117077号、及び2017年9月8日に日本に出願された特願2017-173041号に基づき優先権を主張し、その内容をここに援用する。
そのため、一般にケース内に中空糸膜を充填しすぎないように調整される。ケース内に導入された被処理液は、中空糸膜束内に適宜取り込まれて処理される形となるが、特に高流量での処理の場合には、膜束内に導入されるよりも膜束外をショートパスして充分な処理がされずにケース外に流出する被処理液の量が多くなる。
しかし、モジュールを大型化して中空糸膜が長尺化し、被処理液の流量を速くした場合に、中空糸膜の外径が小さく、剛性が低いと、ケース内で中空糸膜束の形状を保持しにくくなり、中空糸膜束の形状が乱れて脱気効率が低下しやすい。
[1]被処理液から気体を除去する、又は被処理液に気体を供給するための中空糸膜モジュールであって、
引き揃えられた複数の中空糸膜で形成される中空糸膜束と、前記中空糸膜束が収容されたケースと、前記中空糸膜束と前記ケースとの間の間隙における前記被処理液の流れを遮るショートパス防止体とを備え、
前記中空糸膜束の長さ方向の少なくとも第1端部が、各中空糸膜の開口端の開口状態を保ったままポッティング部により前記ケース内に固定され、
前記ショートパス防止体が、前記ケース内の前記中空糸膜の周囲に被処理液を流入させる液流入ポートの下流側に、前記ケースの内表面から突き出るように設けられている、外部潅流型中空糸膜モジュール。
[2]前記中空糸膜のガーレー剛軟度が15mN以上である、[1]に記載の外部潅流型中空糸膜モジュール。
[3]前記ケース内の長さ方向において前記被処理液が一方向に流れ、かつ前記ケース内に、前記ショートパス防止体の他に前記被処理液の流れを変える仕切りが設けられていない、[1]又は[2]に記載の外部潅流型中空糸膜モジュール。
[4]被処理液から気体を除去する、又は被処理液に気体を供給するための中空糸膜モジュールであって、
引き揃えられた複数の中空糸膜で形成される中空糸膜束と、前記中空糸膜束が収容されたケースとを備え、
前記中空糸膜束の長さ方向の少なくとも第1端部が、各中空糸膜の開口端の開口状態を保ったままポッティング部により前記ケース内に固定され、
前記中空糸膜のガーレー剛軟度が15mN以上である、外部潅流型中空糸膜モジュール。
[5]前記ショートパス防止体が、前記中空糸膜束の周囲を全周にわたって囲う環状である、[1]~[3]のいずれかに記載の外部潅流型中空糸膜モジュール。
[6]前記中空糸膜が、気体透過性を有する均質層と、前記均質層を支持する多孔質支持層とを備える複合中空糸膜である、[1]~[5]のいずれかに記載の外部潅流型中空糸膜モジュール。
[7]前記中空糸膜の外径が350μm以下である、[1]~[6]のいずれかに記載の外部潅流型中空糸膜モジュール。
[8]前記中空糸膜の破断強度が0.5N/fil以上であり、破断伸度が50%以上である、[1]~[7]のいずれかに記載の外部潅流型中空糸膜モジュール。
[9]前記ケースを前記中空糸膜束の長さ方向に垂直な方向に切断した断面における、前記ケース内の前記中空糸膜束の充填率が、20~50%である、[1]~[8]のいずれかに記載の外部潅流型中空糸膜モジュール。
[10]前記の複数の中空糸膜がそれぞれ長さ方向の中央部でU字状に折り返された状態で束ねられ、前記第1端部において各中空糸膜の両側の開口端が開口状態を保ったまま前記ポッティング部により前記ケース内に固定されている、[1]~[9]のいずれかに記載の外部潅流型中空糸膜モジュール。
[11]前記中空糸膜束の前記第1端部と反対側の第2端部において、各中空糸膜のU字状に折り返された端部の位置が略同一平面で揃っている、[10]に記載の外部潅流型中空糸膜モジュール。
[12]複数の中空糸膜が一方向に引き揃えられて形成された前記中空糸膜束の前記第1端部と、
前記第1端部と反対側の第2端部の両方が、それぞれポッティング部で前記ケース内に固定されている、[1]~[9]のいずれかに記載の外部潅流型中空糸膜モジュール。
[13]複数の中空糸膜が内側に空洞部が形成されるように筒状に束ねられた中空糸膜束と、前記中空糸膜束が収容されたケースと、を備え、
前記中空糸膜束の長さ方向の第1端部が、各中空糸膜の端面が開口した状態でポッティング部により前記ケース内に固定され、
前記中空糸膜束における前記第1端部と反対側の第2端部が自由端とされ、
前記ケース内の前記ポッティング部よりも前記第2端部側における各中空糸膜の膜外に液体が潅流される外部潅流型中空糸膜モジュールであって、
前記ケース内における前記ポッティング部と前記第2端部の間の領域に前記中空糸膜束のみが設けられている、外部潅流型中空糸膜モジュール。
[14]複数の前記中空糸膜が経糸により互いに連結された状態で束ねられている、[1]~[13]のいずれかに記載の外部潅流型中空糸膜モジュール。
[A1]被処理液から気体を除去する、又は被処理液に気体を供給するための中空糸膜モジュールであって、
引き揃えられた複数の中空糸膜で形成される中空糸膜束と、前記中空糸膜束が収容されたケースと、前記中空糸膜束と前記ケースとの間の間隙における前記被処理液の流れを遮るショートパス防止体とを備え、
前記中空糸膜束の長さ方向の少なくとも第1端部が、各中空糸膜の開口端の開口状態を保ったままポッティング部により前記ケース内に固定され、
前記ショートパス防止体が、前記ケース内の前記中空糸膜の周囲に被処理液を流入させる液流入ポートの下流側に、前記ケースの内表面から突き出るように設けられている、外部潅流型中空糸膜モジュール。
[A2]前記ショートパス防止体が、前記中空糸膜束の周囲を全周にわたって囲う環状である、[A1]に記載の外部潅流型中空糸膜モジュール。
[A3]前記中空糸膜が、気体透過性を有する均質層と、前記均質層を支持する多孔質支持層とを備える複合中空糸膜である、[A1]又は[A2]に記載の外部潅流型中空糸膜モジュール。
[A4]前記中空糸膜の外径が350μm以下である、[A1]~[A3]のいずれかに記載の外部潅流型中空糸膜モジュール。
[A5]前記中空糸膜の破断強度が0.5N/fil以上であり、破断伸度が50%以上である、[A1]~[A4]のいずれかに記載の外部潅流型中空糸膜モジュール。
[A6]前記ケースを前記中空糸膜束の長さ方向に垂直な方向に切断した断面における、前記ケース内の前記中空糸膜束の充填率が、20~50%である、[A1]~[A5]のいずれかに記載の外部潅流型中空糸膜モジュール。
[A7]前記の複数の中空糸膜がそれぞれ長さ方向の中央部でU字状に折り返された状態で束ねられ、前記第1端部において各中空糸膜の両側の開口端が開口状態を保ったまま前記ポッティング部により前記ケース内に固定されている、[A1]~[A6]のいずれかに記載の外部潅流型中空糸膜モジュール。
[A8]前記中空糸膜束の前記第1端部と反対側の第2端部において、各中空糸膜のU字状に折り返された端部の位置が揃っている、[A7]に記載の外部潅流型中空糸膜モジュール。
[A9]複数の中空糸膜が一方向に引き揃えられて形成された前記中空糸膜束の前記第1端部と、前記第1端部と反対側の第2端部の両方が、それぞれポッティング部で前記ケース内に固定されている、[A1]~[A6]のいずれかに記載の外部潅流型中空糸膜モジュール。
[A10]複数の前記中空糸膜が経糸により互いに連結された状態で束ねられている、[A1]~[A9]のいずれかに記載の外部潅流型中空糸膜モジュール。
[B1]複数の中空糸膜が束ねられた中空糸膜束と、前記中空糸膜束が収容されたケースと、を備え、
前記中空糸膜束の長さ方向の少なくとも一方の端部が、各中空糸膜の端面が開口した状態でポッティング部により前記ケース内に固定され、
前記中空糸膜の外径が350μm以下であり、
前記中空糸膜のガーレー剛軟度が15mN以上である、気液分離中空糸膜モジュール。
[B2]前記ケース内の各中空糸膜の膜外に被処理液が潅流される外部潅流型である、[B1]に記載の気液分離中空糸膜モジュール。
[B3]前記中空糸膜が、気体透過性を有する均質層と、前記均質層を支持する多孔質支持層とを備える複合中空糸膜である、[B1]又は[B2]に記載の気液分離中空糸膜モジュール。
[B4]前記中空糸膜の破断強度が0.5N/fil以上であり、破断伸度が50%以上である、[B1]~[B3]のいずれかに記載の気液分離中空糸膜モジュール。
[B5]前記ケースを前記中空糸膜束の長さ方向に垂直な方向に切断した断面における、前記ケース内の前記中空糸膜束の充填率が、20~50%である、[B1]~[B4]のいずれかに記載の気液分離中空糸膜モジュール。
[B6]前記の複数の中空糸膜がそれぞれ長さ方向の中央部でU字状に折り返された状態で束ねられて前記中空糸膜束が形成され、
前記中空糸膜束における各中空糸膜のUターン部と反対側の第1端部が、各中空糸膜の両側の端面が開口した状態で前記ポッティング部により前記ケース内に固定されている、[B1]~[B5]のいずれかに記載の気液分離中空糸膜モジュール。
[B7]前記中空糸膜束の前記第1端部と反対側の第2端部において各中空糸膜の端部の位置が揃っている、[B6]に記載の気液分離中空糸膜モジュール。
[B8]複数の前記中空糸膜が経糸により互いに連結された状態で束ねられている、[B1]~[B7]のいずれかに記載の気液分離中空糸膜モジュール。
[C1]複数の中空糸膜が内側に空洞部が形成されるように筒状に束ねられた中空糸膜束と、前記中空糸膜束が収容されたケースと、を備え、
前記中空糸膜束の長さ方向の第1端部が、各中空糸膜の端面が開口した状態でポッティング部により前記ケース内に固定され、
前記中空糸膜束における前記第1端部と反対側の第2端部が自由端とされ、
前記ケース内の前記ポッティング部よりも前記第2端部側における各中空糸膜の膜外に液体が潅流される外部潅流型中空糸膜モジュールであって、
前記ケース内における前記ポッティング部と前記第2端部の間の領域に前記中空糸膜束のみが設けられている、外部潅流型中空糸膜モジュール。
[C2]前記中空糸膜が、気体透過性を有する均質層と、前記均質層を支持する多孔質支持層とを備える複合中空糸膜である、[C1]に記載の外部潅流型中空糸膜モジュール。
[C3]前記中空糸膜の外径が350μm以下である、[C1]又は[C2]に記載の外部潅流型中空糸膜モジュール。
[C4]前記中空糸膜のガーレー剛軟度が3mN以上である、[C1]~[C3]のいずれかに記載の外部潅流型中空糸膜モジュール。
[C5]前記中空糸膜の破断強度が0.5N/fil以上であり、破断伸度が50%以上である、[C1]~[C4]のいずれかに記載の外部潅流型中空糸膜モジュール。
[C6]前記ケースを前記中空糸膜束の長さ方向に垂直な方向に切断した断面における、前記ケース内の前記中空糸膜束の充填率が、20~50%である、[C1]~[C5]のいずれかに記載の外部潅流型中空糸膜モジュール。
[C7]前記の複数の中空糸膜がそれぞれ長さ方向の中央部でU字状に折り返された状態で束ねられ、各中空糸膜の両側の端面が開口した状態で前記ポッティング部により前記ケース内に固定されている、[C1]~[C6]のいずれかに記載の外部潅流型中空糸膜モジュール。
[C8]前記中空糸膜束の前記第2端部において各中空糸膜の端部の位置が揃っている、[C1]~[C7]のいずれかに記載の外部潅流型中空糸膜モジュール。
[C9]複数の前記中空糸膜が経糸により互いに連結された状態で束ねられている、[C1]~[C8]のいずれかに記載の外部潅流型中空糸膜モジュール。
本発明の第1の態様の外部潅流型中空糸膜モジュールは、被処理液から気体を除去する、又は被処理液に気体を供給するための中空糸膜モジュールである。本発明の第1の態様の外部潅流型中空糸膜モジュールは、例えば、インクジェットプリンタ、カラーフィルタ製造装置等のインクジェット吐出装置等に使用できる。
以下、本発明の第1の態様の外部潅流型中空糸膜モジュールの一例を示して説明する。なお、以下の説明において例示される図の寸法等は一例であって、本発明の第1の態様はそれらに必ずしも限定されるものではなく、その要旨を変更しない範囲で適宜変更して実施することが可能である。
第2ポート118cは、円筒状であり、ケース112内から気体を流出させる気体流出ポート、又は気体を流入させる気体流入ポートとして機能する。第2ポート118cの形状は、円筒状には限定されず、例えば、多角筒状等であってもよい。
第3ポート120cの形状は、円筒状には限定されず、例えば、多角筒状等であってもよい。
また、平板部120aは、ケース112内の気泡の抜けを効率化するためテーパー形状としてもよい。
中空糸膜束110における第1端部110aと反対側に位置する、各中空糸膜111のUターン部からなる第2端部110bは、ケース112には固定されておらず、自由端になっている。これにより、中空糸膜束110の全体わたって各中空糸膜111間に被処理液が行き渡りやすくなるため、高い効率で被処理液の脱気又は給気を行うことができる。
複数の中空糸膜を経糸で連結する態様としては、特に限定されず、例えば、チェーンステッチ型で織り込む態様が挙げられる。
複合中空糸膜の構造としては、均質層の内側又は外側に多孔質支持層が設けられた二層構造、均質層の内側と外側の両方に多孔質支持層が設けられた三層構造が好ましく、強度、及び、脱気又は給気の性能の点から三層構造がより好ましい。
多孔質支持層の空孔率は、30~80体積%が好ましい。空孔率が前記範囲の下限値以上であれば、脱気又は給気の性能に優れる。空孔率が前記範囲の上限値以下であれば、中空糸膜の耐圧性等の機械的強度が向上する。
中空糸膜111の膜厚が前記上限値以下であれば、ケース112内における中空糸膜111の内側を繰り返し減圧したり加圧したりした際の耐久性に優れる。中空糸膜111の膜厚が前記範囲の下限値以上であれば、脱気又は給気の性能を良好に維持しやすい。
中空糸膜の膜厚=(中空糸膜の外径-中空糸膜の内径)/2 ・・・(1)
中空糸膜の内径及び外径は、国際公開第2015/012293号の[0062]に記載の方法で測定される。
均質層及び多孔質支持層の厚さは、国際公開第2015/012293号の[0077]に記載の方法で測定される。
破断強度及び破断伸度は、国際公開第2015/012293号の[0081]に記載の方法で測定される。具体的には、テンシロン型引張試験器を用い、1本の中空糸膜を長さが2cmとなるように試験機のチャック部に把持させ、引張荷重をかけて破断強度及び破断伸度を3回測定し、平均値を求める。
なお、中空糸膜のガーレー剛軟度は、中空糸膜が32本(32fil)単位で折り返された7束の中空糸膜束(幅:約25~26mm)からなる試料を用い、JIS L1096 A法 剛軟度(ガーレ)法に準じて測定される。中空糸膜のガーレー剛軟度は、中空糸膜の材質、外径等を調節することで制御できる。
なお、前記充填率は、ケース112を中空糸膜束110の長さ方向に垂直な方向に切断した断面における、ケース112内部の断面積に対する、充填された中空糸膜束110を形成する各中空糸膜111の断面積の総和の割合(%)として測定される。
この例のショートパス防止体114は、中空糸膜束110の周囲を全周にわたって囲う円環状である。なお、ショートパス防止体114はこの態様には限定されず、中空糸膜束110の周囲に断続的に設けられていてもよい。本発明の第1の態様では、ケース内での被処理液のショートパスを抑制する効果がより高い点から、ショートパス防止体は中空糸膜束の周囲を全周にわたって囲う環状になっていることが好ましい。
ショートパス防止体114の中心軸線L11に沿った方向の幅D1(図2)は、1~10mmが好ましく、2~7mmがより好ましい。幅D1が前記下限値以上であれば、膜束の外を通る短絡流を防ぐことができる。幅D1が前記上限値以下であれば、より効率良く被処理液を膜束の中に導入できる。
ケース112のケース本体116の内表面116cからのショートパス防止体114の突出高さH1(図2)は、1~10mmが好ましく、2~7mmがより好ましい。突出高さH1が前記下限値以上であれば、被処理液をより効率良く中空糸膜111と接触させることができ、モジュール11の処理能力が向上する。突出高さH1が前記上限値以下であれば、中空糸膜束110をショートパス防止体114の内側に挿入しやすい。
ケース112内での被処理液のショートパスを抑制する効果がより高い点から、ケース112の中心軸線L11に沿った方向において、50~200mm毎にショートパス防止体114が設けられていることが好ましい。
図3に示すように、長尺の中空糸膜111Aを交互に反対方向に複数回繰り返してU字状に折り返して帯状の中空糸膜シート113とする。中空糸膜シート113における幅方向の両方の端部側で、経糸126によりシートの長さ方向に中空糸膜111Aを編み、中空糸膜111Aにおける幅方向に延在する部分同士を連結する。次いで、図4に示すように、中空糸膜シート113の幅方向が軸方向となるように中空糸膜シート113を巻いて円柱状にする。次いで、図5に示すように、ショートパス防止体114及び拘束リング123を設けたケース本体116内に、円柱状に巻いた状態の中空糸膜シート113を挿入する。遠心法等の公知の方法を利用してポッティング樹脂130により中空糸膜シート113の一端をケース本体116の第1開口端116a側に固定する。このとき、中空糸膜シート113におけるポッティング樹脂130で固定される側の中空糸膜111AのUターン部と、ポッティング樹脂130の一部がケース本体116から突出するようにする。そして、ケース本体116の第1開口端116aに沿う平面X1で中空糸膜シート113及びポッティング樹脂130の突出部分を切除する。これにより、U字状に折り返された各中空糸膜111の開口端111aの開口状態が保たれたまま、ポッティング部124によりケース本体116に固定された円柱状の中空糸膜束110が形成される。次いで、ケース本体116の両端部に第1蓋部材118及び第2蓋部材120を取り付けることでモジュール11が得られる。
図6における図1と同じ部分は同符号を付して説明を省略する。
ケース112Aは、円筒状のケース本体116Aと、ケース本体116Aの長さ方向の第1開口端116a側に設けられた第1蓋部材118と、ケース本体116Aの第2開口端116b側に設けられた第2蓋部材120と、備えている。ケース本体116Aにおける第1開口端116a寄りの部分に第1ポート122が設けられ、第2開口端116b寄りの部分に液流出ポート又は液流入ポートとして機能する第4ポート132が設けられている。ケース112Aでは、第2蓋部材120に第3ポート120cの代わりに通気ポート120dが設けられている。
モジュール12では、ケース112A内の第1ポート122の下流側、かつ第4ポート132の上流側にショートパス防止体114A,114Bが設けられている。ケース112Aの中心軸線L11に沿った方向において、ショートパス防止体114Aは第1ポート122寄りに設けられ、ショートパス防止体114Bは第4ポート132寄りに設けられている。
また、本発明の第1の態様の外部潅流型中空糸膜モジュールは、中空糸膜束を形成する各中空糸膜がU字状に折り返されず、第2端部がその開口端が樹脂等で埋められて閉じられた状態で自由端とされたものであってもよい。
本発明の第2の態様の外部潅流型中空糸膜モジュールは、複数の中空糸膜が束ねられた中空糸膜束と、前記中空糸膜束が収容されたケースとを備えている。中空糸膜束の長さ方向の少なくとも一方の端部は、各中空糸膜の端面が開口した状態でポッティング部によりケース内に固定されている。本発明の第2の態様の外部潅流型中空糸膜モジュールにおいては、ガーレー剛軟度が15mN以上である中空糸膜を用いる。
本実施形態の外部潅流型中空糸膜モジュール21(以下、「モジュール21」ともいう。)は、図8に示すように、中空糸膜束210と、ケース214と、を備えている。中空糸膜束210はケース214内に収容されており、中空糸膜束210の長さ方向の第1端部210aが、ポッティング部216によりケース214内に固定されている。中空糸膜束210における第1端部210aと反対側の第2端部210bは自由端とされている。
本発明の第2の態様の外部潅流型中空糸膜モジュールにおけるケースとしては、この例のように円筒状のケース本体を備える円柱状の外観のケースが好ましい。なお、本発明の第2の態様では、外観が円柱状のケースには限定されず、例えば、多角筒状のケース本体を備える多角柱状の外観のケースであってもよい。
第2ポート220cは、円筒状であり、ケース214内から気体を流出させる気体流出ポート、又は流入させる気体流入ポートとして機能する。第2ポート220cの形状は、円筒状には限定されず、例えば、多角筒状等であってもよい。
第3ポート222cは、円筒状であり、ケース214内から被処理液を流出させる液流出ポートとして機能する。第3ポート222cの形状は、円筒状には限定されず、例えば、多角筒状等であってもよい。また、平板部222aは、ケース214内の気泡が抜けやすいようにテーパー状となっていてもよい。
複数の中空糸膜を経糸で連結する態様としては、特に限定されず、例えば、チェーンステッチ型で織り込む態様が挙げられる。
中空糸膜211の膜厚が前記上限値以下であれば、ケース214内における中空糸膜211の内側を繰り返し減圧した際の耐久性に優れる。中空糸膜211の膜厚が前記範囲の下限値以上であれば、脱気性能を良好に維持しやすい。
なお、中空糸膜のガーレー剛軟度の測定方法は、第1の態様で説明したとおりである。
破断強度及び破断伸度の測定方法は、第1の態様で説明したとおりである。
複合中空糸膜の構造としては、均質層の内側又は外側に多孔質支持層が設けられた二層構造、均質層の内側と外側の両方に多孔質支持層が設けられた三層構造が好ましく、強度、及び、脱気性能の点から三層構造がより好ましい。
多孔質支持層の空孔率は、30~80体積%が好ましい。空孔率が前記範囲の下限値以上であれば、脱気性能に優れる。空孔率が前記範囲の上限値以下であれば、中空糸膜の耐圧性等の機械的強度が向上する。
均質層及び多孔質支持層の厚さの測定方法は、第1の態様で説明したとおりである。
なお、前記充填率は、ケース214を中空糸膜束210の長さ方向に垂直な方向に切断した断面における、ケース214内部の断面積に対する、充填された中空糸膜束210を形成する各中空糸膜211の断面積の総和の割合(%)として測定される。
例えば、図9に示すように、長尺の中空糸膜211Aを交互に反対方向に複数回繰り返してU字状に折り返して帯状の中空糸膜シート213とし、中空糸膜シート213における幅方向の両方の端部側で、経糸228によりシートの長さ方向に中空糸膜211Aを編み、中空糸膜211Aにおける幅方向に延在する部分同士を連結する。次いで、図10に示すように、中空糸膜シート213の幅方向が軸方向となるように中空糸膜シート213を巻いて円柱状にする。次いで、図11に示すように、円柱状に巻いた状態の中空糸膜シート213をケース本体218内に挿入し、遠心法等の公知の方法を利用してポッティング樹脂252により中空糸膜シート213の一端をケース本体218の第1開口端218a側に固定する。このとき、中空糸膜シート213におけるポッティング樹脂252で固定される側の中空糸膜211AのUターン部と、ポッティング樹脂252の一部がケース本体218から突出するようにする。そして、ケース本体218の第1開口端218aに沿う平面X2で中空糸膜シート213及びポッティング樹脂252の突出部分を切除することで、U字状に折り返された各中空糸膜211の端面211aが開口した状態でポッティング部216によりケース本体218に固定された円柱状の中空糸膜束210が形成される。次いで、ケース本体218の両端部に第1蓋部材220及び第2蓋部材222を取り付けることでモジュール21が得られる。
モジュール22は、中空糸膜束210Aと、ケース214Aと、を備えている。中空糸膜束210Aはケース214A内に収容されており、中空糸膜束210Aの長さ方向の第1端部210aと第2端部210bのそれぞれにおいて、ポッティング部216A,216Bによりケース214A内に固定されている。
第4ポート230の形状は、特に限定されず、例えば、円筒状、多角筒状等が挙げられる。
ケース本体218Aの第1開口端218aはポッティング部216Aにより塞がれた状態になっており、中空糸膜束210Aの長さ方向の第1端部210aがポッティング部216Aに埋設されてケース本体218A内の第1開口端218a側の部分に固定されている。ポッティング部216Aの第1蓋部材220側の端面216aはケース本体218Aの第1開口端218aと面一になっており、そのポッティング部216Aの端面216aにおいて、各中空糸膜211の第1開口端218a側の端面211aが開口した状態になっている。各中空糸膜211の第1開口端218a側の端面211aが開口した状態になっていることで、各中空糸膜211の膜内と、ケース214A内におけるポッティング部216Aの第1蓋部材220側の空間とが連通した状態になっている。
ケース本体218Aの内壁面と中空糸膜束210Aとは離間しており、ケース214A内における中空糸膜束210Aの外側には空間226が形成されている。
本発明の第3の態様の外部潅流型中空糸膜モジュールは、複数の中空糸膜が内側に空洞部が形成されるように筒状に束ねられた中空糸膜束と、前記中空糸膜束が収容されたケースと、を備えている。中空糸膜束の長さ方向の第1端部は、各中空糸膜の端面が開口した状態でポッティング部によりケース内に固定され、中空糸膜束における第1端部と反対側の第2端部は自由端とされている。本発明の第3の態様の外部潅流型中空糸膜モジュールにおいては、ケース内におけるポッティング部と中空糸膜束の第2端部の間の領域に中空糸膜束のみが設けられている。
本実施形態の第3の態様の外部潅流型中空糸膜モジュール31(以下、「モジュール31」ともいう。)は、図14に示すように、中空糸膜束310と、ケース314と、を備えている。中空糸膜束310はケース314内に収容されており、中空糸膜束310の長さ方向の第1端部310aが、ポッティング部316によりケース314内に固定されている。中空糸膜束310における第1端部310aと反対側の第2端部310bは自由端とされている。
本発明の第3の態様の外部潅流型中空糸膜モジュールにおけるケースとしては、この例のように円筒状のケース本体を備える円柱状の外観のケースが好ましい。なお、本発明の第3の態様では、外観が円柱状のケースには限定されず、例えば、多角筒状のケース本体を備える多角柱状の外観のケースであってもよい。
第2ポート320cは、円筒状であり、ケース314内から気体を流出させる気体流出ポート、又は流入させる気体流入ポートとして機能する。第2ポート320cの形状は、円筒状には限定されず、例えば、多角筒状等であってもよい。
第3ポート322cは、円筒状であり、ケース314内から液体を流出入させる液体流出入ポートとして機能する。第3ポート322cの形状は、円筒状には限定されず、例えば、多角筒状等であってもよい。平板部322aは、ケース314内の気泡抜けをよくするためテーパー形状としてもよい。
複数の中空糸膜を経糸で連結する態様としては、特に限定されず、例えば、チェーンステッチ型で織り込む態様が挙げられる。
複合中空糸膜の構造としては、均質層の内側又は外側に多孔質支持層が設けられた二層構造、均質層の内側と外側の両方に多孔質支持層が設けられた三層構造が好ましく、強度、及び、脱気又は給気の性能の点から三層構造がより好ましい。
多孔質支持層の空孔率は、30~80体積%が好ましい。空孔率が前記範囲の下限値以上であれば、脱気又は給気の性能に優れる。空孔率が前記範囲の上限値以下であれば、中空糸膜の耐圧性等の機械的強度が向上する。
均質層及び多孔質支持層の厚さの測定方法は、第1の態様で説明したとおりである。
破断強度及び破断伸度の測定方法は、第1の態様で説明したとおりである。
なお、前記充填率は、ケース314を中空糸膜束310の長さ方向に垂直な方向に切断した断面における、ケース314内部の断面積に対する、充填された中空糸膜束310を形成する各中空糸膜311の断面積の総和の割合(%)として測定される。
なお、中空糸膜のガーレー剛軟度の測定方法は、第1の態様で説明したとおりである。
例えば、図16に示すように、長尺の中空糸膜311Aを交互に反対方向に複数回繰り返してU字状に折り返して帯状の中空糸膜シート313とし、中空糸膜シート313における幅方向の両方の端部側で、経糸328によりシートの長さ方向に中空糸膜311Aを編み、中空糸膜311Aにおける幅方向に延在する部分同士を連結する。次いで、図17に示すように、中空糸膜シート313を円柱状の芯棒350に巻き付ける。図18に示すように、芯棒350に巻き付けられた状態の中空糸膜シート313をケース本体318内に挿入し、芯棒350を引き抜いた後、遠心法等の公知の方法を利用してポッティング樹脂352により中空糸膜シート313の一端をケース本体318の第1開口端318a側に固定する。このとき、中空糸膜シート313におけるポッティング樹脂352で固定される側の中空糸膜311AのUターン部と、ポッティング樹脂352の一部がケース本体318から突出するようにする。そして、ケース本体318の第1開口端318aに沿う平面X3で中空糸膜シート313及びポッティング樹脂352の突出部分を切除することで、U字状に折り返された各中空糸膜311の端面311aが開口した状態でポッティング部316によりケース本体318に固定され、内側に空洞部312が形成された円筒状の中空糸膜束310が形成される。次いで、ケース本体318の両端部に第1蓋部材320及び第2蓋部材322を取り付けることでモジュール31が得られる。
モジュール31では、第1ポート324から、ケース314のケース本体318内に液体を流入させ、第3ポート322cから前記液体を流出させる。これにより、ケース314内のポッティング部316よりも中空糸膜束310の第2端部310b側の領域において、各中空糸膜311の膜外に液体が潅流される。
液体を第1ポート324から流入させて第3ポート322cから流出させる構成としては、特に限定されず、例えば、第1ポート324をポンプと接続して液体を圧送する構成であってもよく、第3ポート322cをポンプと接続して液体を引き込む構成であってもよい。
[メルトフローインデックス(MFR)]
樹脂のMFRは、ASTM D1238のE条件に従い、試験温度190℃、試験荷重21.18Nで測定した。
ガーレ式剛軟度試験機を用いて、JIS L 1096A法に準拠して中空糸膜のガーレー剛軟度を測定した。中空糸膜が32本(32fil)単位で折り返された7束の中空糸膜束を測定試料とし、測定試料のサイズは、幅25~26mm、長さ51mmとした。
図1に例示したモジュール11と同じ態様の外部潅流型中空糸膜モジュールを作製した。
中空糸膜111としては、メタロセン低密度ポリエチレン樹脂(MFR:1.0g/10分)で形成された均質層の内側と外側に、高密度ポリエチレン樹脂(MFR:1.35g/10分)で形成された多孔質支持層を備える三層構造の複合中空糸膜を用いた。複合中空糸膜の外径は197μm、内径は133μm、膜厚は32μmとした。複合中空糸膜のガーレー剛軟度は5mNであった。
ケース112におけるケース本体116の内径は52mmとした。中空糸膜束110は、有効膜面積が1.42m2となるようにポッティング部124によりケース112内に固定した。ケース112を中空糸膜束110の長さ方向に垂直な方向に切断した断面における、ケース112内の中空糸膜束110の充填率は30%であった。
ショートパス防止体114としては、中心軸線L11に沿った方向の幅D1が5mmであり、内径が46mmであり、突出高さH1が3mmである断面形状が矩形状のリングを用いた。第1ポート122の中心軸L12の位置からショートパス防止体114までの距離d12は9mmとし、d12/d11を0.075とした。
複合中空糸膜の外径を283μm、内径を199μmとし、ガーレー剛軟度を20mNに変更し、中空糸膜束110を有効膜面積が1.15m2となるようにポッティング部124によりケース112内に固定し、ケース112内の中空糸膜束110の充填率を30%とした以外は、例A1と同様にして外部潅流型中空糸膜モジュールを作製した。
ケース内にショートパス防止体を設けなかった以外は、例A1と同様にして外部潅流型中空糸膜モジュールを作製した。
ケース内にショートパス防止体を設けなかった以外は、例A2と同様にして外部潅流型中空糸膜モジュールを作製した。
各例の外部潅流型中空糸膜モジュールに対して、第1ポート(液流入ポート)から水が流入し、第3ポート(液流出ポート)から水が流出するように通水し、第2ポート(通気ポート)を真空ポンプと接続して真空度-88kPaにて減圧して脱気を実施した。水の温度は25℃とした。外部潅流させる水の流量は250、500、750、1000、1250、1500mL/分で変化させ、それぞれの流量における脱気後の処理水中の溶存酸素除去率を測定した。
溶存酸素除去率は、脱気処理前の原水の溶存酸素量M1(mg/L)と、脱気処理後の処理水の溶存酸素量M2(mg/L)とをそれぞれ光学式DOメーターFD 0925(セントラル科学)により測定し、下式(2)から求めた。
溶存酸素除去率(%)=[(M1-M2)/M1]×100 ・・・(2)
結果を図7に示す。
ケース本体116の内径を48mmとし、ショートパス防止体114の内径を46mmとして突出高さH1を3mmとし、中空糸膜束110の有効膜面積を1.63m2とし、d12/d11を0.060とする以外は、例A1と同様にして外部潅流型中空糸膜モジュールを作製した。
複合中空糸膜の外径を283μm、内径を199μmとし、ガーレー剛軟度を20mNに変更し、中空糸膜束110の有効膜面積を1.21m2とする以外は、例A5と同様にして外部潅流型中空糸膜モジュールを作製した。
ケース内にショートパス防止体を設けなかった以外は、例A5と同様にして外部潅流型中空糸膜モジュールを作製した。
ケース内にショートパス防止体を設けなかった以外は、例A6と同様にして外部潅流型中空糸膜モジュールを作製した。
各例の外部潅流型中空糸膜モジュールに対して、液流入ポートから水が流入し、液流出ポートから水が流出するように通水し、第2ポート(通気ポート)を真空ポンプと接続して真空度-88kPaにて減圧して脱気を実施した。水の温度は25℃とした。外部潅流させる水の流量は1500mL/分とした。通水態様を以下のようにした試験(i)~(iv)において、それぞれ流量における脱気後の処理水中の溶存酸素除去率を測定した。溶存酸素除去率は、前記式(2)から求めた。
試験(ii):第3ポート120cが下側、第1ポート122が上側となるようにモジュールを縦置きした状態で、第3ポート120cを液流入ポート、第1ポート122を液流出ポートとして通水した(アップフロー、キャップイン)。
試験(iii):第1ポート122と第3ポート120cがともに水平方向となるようにモジュールを横置きした状態で、第1ポート122を液流入ポート、第3ポート120cを液流出ポートとして通水した(サイドフロー、サイドイン)。
試験(iv):第1ポート122と第3ポート120cがともに水平方向となるようにモジュールを横置きした状態で、第3ポート120cを液流入ポート、第1ポート122を液流出ポートとして通水した(サイドフロー、キャップイン)。
結果を図21に示す。
均質層を形成する材料としてメタロセン低密度ポリエチレン(MFR:1.0g/10分)、多孔質支持層を形成する材料として高密度ポリエチレン(MFR:1.35g/10分)を使用して、均質層の内側と外側の両方に多孔質支持層を備える三層構造の複合中空糸膜Aを製造した。複合中空糸膜の外径は197μm、内径は133μm、膜厚は32μmとした。得られた複合中空糸膜Aのガーレー剛軟度は5mNであった。
均質層及び多孔質支持層を形成する材料、並びに中空糸膜の外径、内径及び膜厚を表1に示す通りに変更した以外は、製造例B1と同様にして複合中空糸膜B~Cを製造した。得られた複合中空糸膜B、Cのガーレー剛軟度を表1に示す。
均質層を形成する材料として線状低密度ポリエチレン(MFR:18.5g/10分)、多孔質支持層を形成する材料として高密度ポリエチレン(MFR:5.2g/10分)を使用して、均質層の内側と外側の両方に多孔質支持層を備える三層構造の複合中空糸膜Dを製造した。複合中空糸膜Dの外径は284μm、内径は206μm、膜厚は39μmとした。得られた複合中空糸膜Dのガーレー剛軟度は12mNであった。
図8に例示したモジュール21を作製した。中空糸膜211としては、複合中空糸膜Bを用いた。ケース本体218の内径は30mmとし、高さ135mm、有効膜面積0.46m2の円柱状の中空糸膜束210を充填率30%で充填してケース214内に固定した。
中空糸膜211を複合中空糸膜Cに変更し、高さ135mm、有効膜面積0.43m2の円柱状の中空糸膜束210を充填率30%で充填してケース214内に固定した以外は、例B1と同様にして外部潅流型中空糸膜モジュールを作製した。
中空糸膜211を複合中空糸膜Aに変更し、中空糸膜束210の直径、高さ、有効膜面積及び充填率を表2に示すように変更した以外は、例B1と同様にして外部潅流型中空糸膜モジュールを作製した。
中空糸膜211を複合中空糸膜Dに変更し、中空糸膜束210の直径、高さ、有効膜面積及び充填率を表2に示すように変更した以外は、例B1と同様にして外部潅流型中空糸膜モジュールを作製した。
各例の外部潅流型中空糸膜モジュールに対して、第1ポートから水が流入し、第3ポートから水が流出するように通水し、第2ポートを真空ポンプと接続して真空度100Torrにて減圧して脱気を実施した。水の温度は25℃とした。外部潅流させる水の流量は100、200、300、400mL/分で変化させ、それぞれの流量における脱気後の処理水中の溶存酸素除去率を測定した。
溶存酸素除去率は、前記式(2)から求めた。
結果を図13に示す。
図14に例示したモジュール31を作製した。中空糸膜311としては、三菱ケミカル社製の複合中空糸膜(製品名「MHF130EPE」)を使用した。ケース本体318の内径は52mmとした。直径10mmの芯棒350を使用し、直径10mmの円柱状の空洞部312が内側に形成された円筒状の中空糸膜束310とし、有効膜面積が1.45m2となるようにポッティング部316によりケース314内に固定した。ケース314を中空糸膜束310の長さ方向に垂直な方向に切断した断面における、ケース314内の中空糸膜束310の充填率は、28%であった。
中空糸膜束を円筒状から円柱状とし、内側に空洞部が形成されない状態とした以外は、例C1のモジュール31と同様の態様である、図20に例示した外部潅流型中空糸膜モジュール3101を作製した。ケース3114を中空糸膜束3110の長さ方向に垂直な方向に切断した断面における、ケース3114内の中空糸膜束3110の充填率は、例C1の充填率と同じとした。
ケース本体318の内径を48mmとし、中空糸膜として外径が283μm、内径が199μm、ガーレー剛軟度が20mNの例A2と同じ複合中空糸膜を用い、内側に空洞部が形成されない円柱状の有効膜面積が1.21m2の中空糸膜束とし、中空糸膜束の充填率を30%とする以外は、例C1と同様にして外部潅流型中空糸膜モジュールを作製した。
ケース本体318の内径を48mmとし、中空糸膜として外径が283μm、内径が199μm、ガーレー剛軟度が20mNの例A2と同じ複合中空糸膜を用い、直径10mmの円柱状の空洞部312が内側に形成された円筒状の中空糸膜束の充填率を30%とする以外は、例C1と同様にして外部潅流型中空糸膜モジュールを作製した。
ケース本体318の内径を48mmとし、中空糸膜として外径が197μm、内径が133μm、ガーレー剛軟度が5mNの例A1と同じ複合中空糸膜を用い、内側に空洞部が形成されない円柱状の有効膜面積が1.63m2の中空糸膜束とし、中空糸膜束の充填率を30%とする以外は、例C1と同様にして外部潅流型中空糸膜モジュールを作製した。
各例の外部潅流型中空糸膜モジュールに対して、第1ポートから水が流入し、第3ポートから水が流出するように通水し、第2ポートを真空ポンプと接続して真空度-88kPaにて減圧して脱気を実施した。水の温度は25℃とした。外部潅流させる水の流量は250、500、750、1000、1250、1500mL/分で変化させ、それぞれの流量における脱気後の処理水中の溶存酸素除去率を測定した。
溶存酸素除去率は、前記式(2)から求めた。
例C1及び例C2の結果を図19に示し、例C3~C5の結果を図22に示す。
Claims (14)
- 被処理液から気体を除去する、又は被処理液に気体を供給するための中空糸膜モジュールであって、
引き揃えられた複数の中空糸膜で形成される中空糸膜束と、前記中空糸膜束が収容されたケースと、前記中空糸膜束と前記ケースとの間の間隙における前記被処理液の流れを遮るショートパス防止体とを備え、
前記中空糸膜束の長さ方向の少なくとも第1端部が、各中空糸膜の開口端の開口状態を保ったままポッティング部により前記ケース内に固定され、
前記ショートパス防止体が、前記ケース内の前記中空糸膜の周囲に被処理液を流入させる液流入ポートの下流側に、前記ケースの内表面から突き出るように設けられている、外部潅流型中空糸膜モジュール。 - 前記中空糸膜のガーレー剛軟度が15mN以上である、請求項1に記載の外部潅流型中空糸膜モジュール。
- 前記ケース内の長さ方向において前記被処理液が一方向に流れ、かつ前記ケース内に、前記ショートパス防止体の他に前記被処理液の流れを変える仕切りが設けられていない、請求項1又は2に記載の外部潅流型中空糸膜モジュール。
- 被処理液から気体を除去する、又は被処理液に気体を供給するための中空糸膜モジュールであって、
引き揃えられた複数の中空糸膜で形成される中空糸膜束と、前記中空糸膜束が収容されたケースとを備え、
前記中空糸膜束の長さ方向の少なくとも第1端部が、各中空糸膜の開口端の開口状態を保ったままポッティング部により前記ケース内に固定され、
前記中空糸膜のガーレー剛軟度が15mN以上である、外部潅流型中空糸膜モジュール。 - 前記ショートパス防止体が、前記中空糸膜束の周囲を全周にわたって囲う環状である、請求項1~3のいずれか一項に記載の外部潅流型中空糸膜モジュール。
- 前記中空糸膜が、気体透過性を有する均質層と、前記均質層を支持する多孔質支持層とを備える複合中空糸膜である、請求項1~5のいずれか一項に記載の外部潅流型中空糸膜モジュール。
- 前記中空糸膜の外径が350μm以下である、請求項1~6のいずれか一項に記載の外部潅流型中空糸膜モジュール。
- 前記中空糸膜の破断強度が0.5N/fil以上であり、破断伸度が50%以上である、請求項1~7のいずれか一項に記載の外部潅流型中空糸膜モジュール。
- 前記ケースを前記中空糸膜束の長さ方向に垂直な方向に切断した断面における、前記ケース内の前記中空糸膜束の充填率が、20~50%である、請求項1~8のいずれか一項に記載の外部潅流型中空糸膜モジュール。
- 前記の複数の中空糸膜がそれぞれ長さ方向の中央部でU字状に折り返された状態で束ねられ、前記第1端部において各中空糸膜の両側の開口端が開口状態を保ったまま前記ポッティング部により前記ケース内に固定されている、請求項1~9のいずれか一項に記載の外部潅流型中空糸膜モジュール。
- 前記中空糸膜束の前記第1端部と反対側の第2端部において、各中空糸膜のU字状に折り返された端部の位置が略同一平面で揃っている、請求項10に記載の外部潅流型中空糸膜モジュール。
- 複数の中空糸膜が一方向に引き揃えられて形成された前記中空糸膜束の前記第1端部と、
前記第1端部と反対側の第2端部の両方が、それぞれポッティング部で前記ケース内に固定されている、請求項1~9のいずれか一項に記載の外部潅流型中空糸膜モジュール。 - 複数の中空糸膜が内側に空洞部が形成されるように筒状に束ねられた中空糸膜束と、前記中空糸膜束が収容されたケースと、を備え、
前記中空糸膜束の長さ方向の第1端部が、各中空糸膜の端面が開口した状態でポッティング部により前記ケース内に固定され、
前記中空糸膜束における前記第1端部と反対側の第2端部が自由端とされ、
前記ケース内の前記ポッティング部よりも前記第2端部側における各中空糸膜の膜外に液体が潅流される外部潅流型中空糸膜モジュールであって、
前記ケース内における前記ポッティング部と前記第2端部の間の領域に前記中空糸膜束のみが設けられている、外部潅流型中空糸膜モジュール。 - 複数の前記中空糸膜が経糸により互いに連結された状態で束ねられている、請求項1~13のいずれか一項に記載の外部潅流型中空糸膜モジュール。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211275103.XA CN115445441A (zh) | 2017-06-14 | 2018-06-14 | 外部灌注型中空纤维膜组件 |
EP18818944.3A EP3639912A4 (en) | 2017-06-14 | 2018-06-14 | HOLLOW FIBER MEMBRANE MODULE WITH EXTERNAL CIRCUIT |
KR1020197037776A KR102323004B1 (ko) | 2017-06-14 | 2018-06-14 | 외부 관류형 중공사막 모듈 |
JP2018535437A JP6788014B2 (ja) | 2017-06-14 | 2018-06-14 | 外部潅流型中空糸膜モジュール |
CN201880038580.XA CN110753576B (zh) | 2017-06-14 | 2018-06-14 | 外部灌注型中空纤维膜组件 |
US16/711,992 US11701620B2 (en) | 2017-06-14 | 2019-12-12 | External circulation-type hollow fiber membrane module |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017-117077 | 2017-06-14 | ||
JP2017117077 | 2017-06-14 | ||
JP2017-116620 | 2017-06-14 | ||
JP2017116620 | 2017-06-14 | ||
JP2017173041 | 2017-09-08 | ||
JP2017-173041 | 2017-09-08 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/711,992 Continuation US11701620B2 (en) | 2017-06-14 | 2019-12-12 | External circulation-type hollow fiber membrane module |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018230631A1 true WO2018230631A1 (ja) | 2018-12-20 |
Family
ID=64660181
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2018/022698 WO2018230631A1 (ja) | 2017-06-14 | 2018-06-14 | 外部潅流型中空糸膜モジュール |
Country Status (6)
Country | Link |
---|---|
US (1) | US11701620B2 (ja) |
EP (1) | EP3639912A4 (ja) |
JP (1) | JP6788014B2 (ja) |
KR (1) | KR102323004B1 (ja) |
CN (2) | CN115445441A (ja) |
WO (1) | WO2018230631A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4117805A4 (en) * | 2020-03-09 | 2024-06-05 | Watersep Bioseparations LLC | PERFUSION FILTRATION SYSTEMS |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102020112224A1 (de) | 2020-05-06 | 2021-11-11 | Fresenius Medical Care Deutschland Gmbh | Entgasungsvorrichtung |
CN112791249B (zh) * | 2020-12-30 | 2023-02-17 | 东莞科威医疗器械有限公司 | 心脏停跳液灌注装置 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55323Y2 (ja) * | 1974-10-04 | 1980-01-08 | ||
JPS55107139U (ja) * | 1979-01-25 | 1980-07-26 | ||
JPH06327905A (ja) | 1993-05-21 | 1994-11-29 | Toray Ind Inc | 脱気膜モジュールおよびその運転方法 |
JPH0999064A (ja) * | 1995-10-04 | 1997-04-15 | Nikkiso Co Ltd | 中空糸型血液浄化器 |
WO2013065293A1 (ja) * | 2011-10-31 | 2013-05-10 | Jfeエンジニアリング株式会社 | 淡水製造方法および装置 |
WO2015012293A1 (ja) | 2013-07-24 | 2015-01-29 | 三菱レイヨン株式会社 | 外部灌流型の中空糸膜モジュール及び前記モジュールを有するインクジェットプリンタ |
WO2015137308A1 (ja) * | 2014-03-10 | 2015-09-17 | 三菱レイヨン株式会社 | 中空糸膜モジュールとその製造方法 |
JP2017116620A (ja) | 2015-12-22 | 2017-06-29 | 株式会社沖データ | クリーニングブレード及び画像形成装置 |
JP2017117077A (ja) | 2015-12-22 | 2017-06-29 | 日本電気株式会社 | 情報取得装置、情報取得方法、プログラム、情報取得システム、サーバ装置 |
JP2017173041A (ja) | 2016-03-22 | 2017-09-28 | Ntn株式会社 | 状態監視装置およびそれを搭載する風力発電設備、ならびに電気的ノイズ除去方法 |
Family Cites Families (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2227888B2 (ja) * | 1972-07-26 | 1976-04-23 | Rhone Poulenc Ind | |
US4367139A (en) * | 1978-11-16 | 1983-01-04 | Monsanto Company | Hollow fiber permeator |
DE2964848D1 (en) | 1978-11-24 | 1983-03-24 | Midland Ross Corp | Composite cushion pad |
US4620965A (en) * | 1982-09-22 | 1986-11-04 | Terumo Corporation | Hollow fiber-type artificial lung |
US4756875A (en) * | 1983-09-29 | 1988-07-12 | Kabushiki Kaisha Toshiba | Apparatus for filtering water containing radioactive substances in nuclear power plants |
US5316724A (en) * | 1989-03-31 | 1994-05-31 | Baxter International Inc. | Multiple blood path membrane oxygenator |
JPH04367714A (ja) * | 1991-06-13 | 1992-12-21 | Mitsubishi Rayon Co Ltd | 多孔質中空糸膜シート状物 |
JPH05161831A (ja) * | 1991-12-16 | 1993-06-29 | Mitsubishi Kasei Corp | 中空糸膜モジュール及びそれを用いた分離方法 |
SE502222C2 (sv) * | 1994-01-17 | 1995-09-18 | Althin Medical Ab | Sätt vid dialys |
JPH09150041A (ja) * | 1995-11-28 | 1997-06-10 | Dainippon Ink & Chem Inc | 外部灌流型気液接触モジュール |
US6558450B2 (en) * | 2001-03-22 | 2003-05-06 | Celgard Inc. | Method for debubbling an ink |
US7297270B2 (en) * | 2003-04-04 | 2007-11-20 | Chf Solutions, Inc. | Hollow fiber filter for extracorporeal blood circuit |
CN2754712Y (zh) * | 2004-12-20 | 2006-02-01 | 天津膜天膜工程技术有限公司 | 外压式中空纤维膜组件 |
WO2007041430A2 (en) * | 2005-10-03 | 2007-04-12 | Emv Technologies, Llc | Apparatus and method for enhanced hemodialysis performance |
WO2008088293A1 (en) * | 2007-01-18 | 2008-07-24 | Hyflux Membrane Manufacturing (S) Pte Ltd | Membrane contactor |
JP5797874B2 (ja) * | 2008-09-12 | 2015-10-21 | 三菱レイヨン株式会社 | 排水処理装置および排水処理方法 |
US9867917B2 (en) * | 2010-12-28 | 2018-01-16 | Toray Industries, Inc. | Medical material and hollow fiber membrane module |
JP5861479B2 (ja) * | 2012-02-03 | 2016-02-16 | 三菱レイヨン株式会社 | 中空糸膜モジュールの製造方法 |
DE102013218188B3 (de) * | 2013-09-11 | 2014-12-04 | membion Gmbh | Membranfilter und Verfahren zum Filtern |
ES2694835T3 (es) * | 2013-12-16 | 2018-12-27 | Asahi Kasei Medical Co., Ltd. | Dispositivo de purificación de sangre de membrana de fibra hueca |
JP6358717B2 (ja) * | 2014-06-06 | 2018-07-18 | 三菱ケミカル株式会社 | 浄水カートリッジ及び浄水器 |
KR20170078735A (ko) * | 2014-12-24 | 2017-07-07 | 디아이씨 가부시끼가이샤 | 중공사 탈기 모듈 및 잉크젯 프린터 |
WO2016143751A1 (ja) * | 2015-03-10 | 2016-09-15 | テルモ株式会社 | 人工肺および人工肺の製造方法 |
JP6777383B2 (ja) * | 2015-08-06 | 2020-10-28 | 旭化成メディカル株式会社 | 中空糸膜モジュール及びその製造方法 |
-
2018
- 2018-06-14 WO PCT/JP2018/022698 patent/WO2018230631A1/ja unknown
- 2018-06-14 EP EP18818944.3A patent/EP3639912A4/en active Pending
- 2018-06-14 CN CN202211275103.XA patent/CN115445441A/zh active Pending
- 2018-06-14 CN CN201880038580.XA patent/CN110753576B/zh active Active
- 2018-06-14 JP JP2018535437A patent/JP6788014B2/ja active Active
- 2018-06-14 KR KR1020197037776A patent/KR102323004B1/ko active IP Right Grant
-
2019
- 2019-12-12 US US16/711,992 patent/US11701620B2/en active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55323Y2 (ja) * | 1974-10-04 | 1980-01-08 | ||
JPS55107139U (ja) * | 1979-01-25 | 1980-07-26 | ||
JPH06327905A (ja) | 1993-05-21 | 1994-11-29 | Toray Ind Inc | 脱気膜モジュールおよびその運転方法 |
JPH0999064A (ja) * | 1995-10-04 | 1997-04-15 | Nikkiso Co Ltd | 中空糸型血液浄化器 |
WO2013065293A1 (ja) * | 2011-10-31 | 2013-05-10 | Jfeエンジニアリング株式会社 | 淡水製造方法および装置 |
WO2015012293A1 (ja) | 2013-07-24 | 2015-01-29 | 三菱レイヨン株式会社 | 外部灌流型の中空糸膜モジュール及び前記モジュールを有するインクジェットプリンタ |
WO2015137308A1 (ja) * | 2014-03-10 | 2015-09-17 | 三菱レイヨン株式会社 | 中空糸膜モジュールとその製造方法 |
JP2017116620A (ja) | 2015-12-22 | 2017-06-29 | 株式会社沖データ | クリーニングブレード及び画像形成装置 |
JP2017117077A (ja) | 2015-12-22 | 2017-06-29 | 日本電気株式会社 | 情報取得装置、情報取得方法、プログラム、情報取得システム、サーバ装置 |
JP2017173041A (ja) | 2016-03-22 | 2017-09-28 | Ntn株式会社 | 状態監視装置およびそれを搭載する風力発電設備、ならびに電気的ノイズ除去方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4117805A4 (en) * | 2020-03-09 | 2024-06-05 | Watersep Bioseparations LLC | PERFUSION FILTRATION SYSTEMS |
Also Published As
Publication number | Publication date |
---|---|
KR102323004B1 (ko) | 2021-11-05 |
CN115445441A (zh) | 2022-12-09 |
US20200114315A1 (en) | 2020-04-16 |
CN110753576A (zh) | 2020-02-04 |
EP3639912A4 (en) | 2020-09-16 |
EP3639912A1 (en) | 2020-04-22 |
KR20200010431A (ko) | 2020-01-30 |
JP6788014B2 (ja) | 2020-11-18 |
CN110753576B (zh) | 2023-02-24 |
JPWO2018230631A1 (ja) | 2019-06-27 |
US11701620B2 (en) | 2023-07-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11701620B2 (en) | External circulation-type hollow fiber membrane module | |
JP6618067B2 (ja) | 外部灌流型の中空糸膜モジュール及び前記モジュールを有するインクジェットプリンタ | |
CN100548450C (zh) | 薄膜接触器及其制造方法 | |
KR20170038646A (ko) | 역삼투압 필터 모듈 | |
US10583664B2 (en) | Hollow fiber membrane module | |
US8449706B2 (en) | Process for manufacturing deaerating hollow fiber module | |
KR20180087381A (ko) | 바이러스 제거막 및 바이러스 제거막의 제조 방법 | |
JPH10298470A (ja) | インクの脱気方法及びインク脱気装置 | |
JP2019181356A (ja) | 外部潅流型中空糸膜モジュール | |
JP7290208B2 (ja) | 中空糸膜モジュール | |
JPH09150041A (ja) | 外部灌流型気液接触モジュール | |
EP3608012A1 (en) | Feed spacer and reverse osmosis filter module including same | |
WO2023127506A1 (ja) | 脱気モジュール及び液体の脱気方法 | |
JP3759976B2 (ja) | 水中溶存有機ハロン除去方法 | |
KR20180034934A (ko) | 역삼투압 필터 모듈 | |
TW202330078A (zh) | 脫氣模組及液體的脫氣方法 | |
CN118161979A (zh) | 反渗透膜结构及反渗透膜组件 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2018535437 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 18818944 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20197037776 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2018818944 Country of ref document: EP Effective date: 20200114 |