External perfusion type hollow fiber membrane module

Abstract

Provided is an externally perfused hollow fiber membrane module with high processing capacity, which can suppress the short-circuit flow path of the liquid to be treated in the housing. Regardless of the direction of flow of the liquid to be treated, such as in the vertical direction or the horizontal direction, the liquid to be treated can be efficiently contacted with the hollow fiber membrane. The externally perfused hollow fiber membrane module (11) includes: a hollow fiber membrane bundle (110), a housing (112), and a short-circuit prevention body (114) that blocks the flow of the liquid to be treated in the gap between the hollow fiber membrane bundle (110) and the housing (112). The first end portion (110a) of the hollow fiber membrane bundle (110) is fixed within the housing (112), and the short-circuit prevention body (114) is provided on the downstream side of the first port (122) of the liquid inlet port within the housing (112) and protrudes from the inner surface of the housing (112).

Description

[0001] This application is a divisional application based on the following Chinese patent application:

[0002] Original filing date: June 14, 2018

[0003] Original application number: 201880038580.X (PCT / JP2018 / 022698)

[0004] Original application title: External perfusion type hollow fiber membrane module Technical Field

[0005] The present invention relates to an external perfusion type hollow fiber membrane module.

[0006] This application claims priority based on Japanese Patent Application No. 2017-116620 filed on June 14, 2017, Japanese Patent Application No. 2017-117077 filed on June 14, 2017, and Japanese Patent Application No. 2017-173041 filed on September 8, 2017, the contents of which are incorporated herein by reference. Background Art

[0007] As gas-liquid separation hollow fiber membrane modules, an internal perfusion type in which the liquid to be treated passes inside the hollow fiber membrane and an external perfusion type in which the liquid to be treated passes outside the hollow fiber membrane have been proposed. For example, as a gas-liquid separation hollow fiber membrane module, an external perfusion type hollow fiber membrane module is known in which the liquid to be treated flows around the hollow fiber membrane inside the housing while a vacuum is drawn inside the hollow fiber membrane to suck the dissolved gas in the liquid to be treated into the membrane for degassing, or gas is supplied to the hollow fiber membrane to cause the liquid to be treated to inhale gas.

[0008] Gas-liquid separation hollow fiber membrane modules, for example, as degassing modules, are installed in inkjet printing devices, pure water manufacturing devices, etc. Among inkjet printing devices, in the case of commercial large-scale inkjet printers, color filter manufacturing devices, etc., since a large amount of chemical liquid is used, a chemical liquid tank is installed on the device body, and when the inkjet printing device is operating, chemicals such as ink and photoresist solution are sent out from the chemical liquid tank. At this time, if the chemical contains bubbles, the jetting accuracy will decrease and quality defects will occur in the printed matter. To prevent this, a gas-liquid separation hollow fiber membrane module is provided. In recent years, with the enlargement and high-speedization of devices, it is preferable to use an external perfusion type hollow fiber membrane module that can perform processing with a lower pressure loss.

[0009] As an external perfusion type hollow fiber membrane module, there are known modules in which only the first end in the length direction of the hollow fiber membrane bundle is fixed by a casting part in the housing, and modules in which both the first end and the second end in the length direction of the hollow fiber membrane bundle in the housing are fixed by a casting part (Patent Documents 1 and 2). By fixing the open ends of the respective hollow fiber membranes at least at the first end while keeping them open, a vacuum can be drawn in the hollow fiber membranes to degas the liquid to be treated, or a gas can be supplied into the hollow fiber membranes to supply gas to the liquid to be treated.

[0010] As a specific example of the external perfusion type hollow fiber membrane module, for example, as Figure 20 shown in the external perfusion type hollow fiber membrane module 3101 (for example, Patent Document 1), one end of a hollow fiber membrane bundle 3110 formed by bundling a plurality of hollow fiber membranes 3111 into a cylindrical shape is fixed in a housing 3114 by a casting part 3116, and the other end of the hollow fiber membrane bundle 3110 is a free end. In the external perfusion type hollow fiber membrane module 3101, a liquid flows in from a first port 3124 provided on a housing body 3118, and the liquid flows out from a third port 3122c provided on a second lid part 3122, and water is passed in this way so that the liquid is perfused outside the respective hollow fiber membranes 3111 of the hollow fiber membrane bundle 3110. In this state, the second port 3120c provided on the first lid part 3120 is connected to a vacuum pump, and the inside of the respective hollow fiber membranes 3111 is decompressed. As a result, the dissolved gas in the externally perfused liquid is sucked in and inhaled into the inside of the respective hollow fiber membranes 3111, and thus degassing can be performed.

[0011] Prior Art Documents

[0012] Patent Documents

[0013] [Patent Document 1] International Publication No. 2015 / 012293

[0014] [Patent Document 2] Japanese Patent Laid-Open No. 6-327905 Summary of the Invention

[0015] Problems to be Solved by the Invention

[0016] In the modules of Patent Documents 1 and 2, if the filling rate of the hollow fiber membranes in the housing is too high, the filling operation of the hollow fiber membranes becomes difficult, the pressure loss becomes high, and the processing efficiency decreases.

[0017] Therefore, generally, adjustments are made so that the housing is not overly filled with hollow fiber membranes. The liquid to be treated introduced into the housing is appropriately sucked into the hollow fiber membrane bundle and treated, but especially in the case of high-flow processing, the amount of the liquid to be treated flowing out of the housing that flows through a short distance outside the membrane bundle and is not sufficiently treated is larger than that introduced into the membrane bundle.

[0018] A first object of the present invention is to provide an externally perfused hollow fiber membrane module with high processing capacity, which can suppress the short-circuit flow path of the liquid to be treated in the housing, and can efficiently bring the liquid to be treated into contact with the hollow fiber membrane regardless of the direction of flow of the liquid to be treated, such as vertical or horizontal directions.

[0019] In addition, in an externally perfused hollow fiber membrane module as generally described in Patent Document 1, a smaller outer diameter of the hollow fiber membrane allows more hollow fiber membranes to be filled in the housing, enabling more efficient contact with the liquid to be treated.

[0020] However, when the module becomes larger, the hollow fiber membrane becomes longer, and the flow rate of the liquid to be treated becomes faster, if the outer diameter of the hollow fiber membrane is small and the rigidity is low, it is difficult for the hollow fiber membrane bundle to maintain its shape in the housing, the shape of the hollow fiber membrane bundle is likely to become disordered, and the degassing efficiency will decrease.

[0021] A second object of the present invention is to provide an externally perfused hollow fiber membrane module that can ensure the shape retention of the hollow fiber membrane bundle even when the module becomes larger, the hollow fiber membrane becomes longer, and the flow rate of the liquid to be treated becomes faster, and can suppress a decrease in degassing efficiency regardless of the direction of flow of the liquid to be treated, such as vertical or horizontal directions.

[0022] In addition, in a conventional externally perfused hollow fiber membrane module such as the externally perfused hollow fiber membrane module 3101, when the module becomes larger and the flow rate of the perfusion liquid becomes faster, the liquid is prone to generate uneven flow and does not pass through the entire hollow fiber membrane bundle in the housing, resulting in a decrease in degassing or gas supply efficiency.

[0023] A third object of the present invention is to provide an externally perfused hollow fiber membrane module that can suppress uneven flow of the liquid in the housing and can suppress a decrease in degassing or gas supply efficiency even when the module becomes larger and the flow rate of the perfusion liquid becomes faster.

[0024] Means for Solving the Problems

[0025] The present invention has the following embodiments.

[0026] [1] An externally perfused hollow fiber membrane module is a hollow fiber membrane module for removing gas from a liquid to be treated or supplying gas to the liquid to be treated,

[0027] comprising: a hollow fiber membrane bundle formed by a plurality of aligned hollow fiber membranes, a housing that houses the hollow fiber membrane bundle, and a short-circuit prevention body that blocks the flow of the liquid to be treated in the gap between the hollow fiber membrane bundle and the housing,

[0028] At least a first end portion in the length direction of the hollow fiber membrane bundle is fixed in the housing by a casting portion while keeping the open ends of the respective hollow fiber membranes open.

[0029] The short-circuit prevention body is disposed on the downstream side of the liquid inflow port and protrudes from the inner surface of the housing, and the liquid inflow port is a port through which the liquid to be treated flows into the periphery of the hollow fiber membrane inside the housing.

[0030] [2] The external perfusion type hollow fiber membrane module according to [1], wherein the Gurley stiffness of the hollow fiber membrane is 15 mN or more.

[0031] [3] The external perfusion type hollow fiber membrane module according to [1] or [2], wherein the liquid to be treated flows unidirectionally in the longitudinal direction inside the housing, and inside the housing, except for the short-circuit prevention body, there is no partition for changing the flow direction of the liquid to be treated.

[0032] [4] An external perfusion type hollow fiber membrane module is a hollow fiber membrane module for removing gas from or supplying gas to a liquid to be treated.

[0033] It includes: a hollow fiber membrane bundle formed by a plurality of aligned hollow fiber membranes, and a housing that houses the hollow fiber membrane bundle.

[0034] At least the first end portion in the longitudinal direction of the hollow fiber membrane bundle is fixed in the housing by a casting portion while the open ends of the respective hollow fiber membranes remain open.

[0035] The Gurley stiffness of the hollow fiber membrane is 15 mN or more.

[0036] [5] The external perfusion type hollow fiber membrane module according to any one of [1] to [3], wherein the short-circuit prevention body is annular around the entire hollow fiber membrane bundle.

[0037] [6] The external perfusion type hollow fiber membrane module according to any one of [1] to [5], wherein the hollow fiber membrane is a composite hollow fiber membrane; the composite hollow fiber membrane includes a homogeneous layer having gas permeability and a porous support layer that supports the homogeneous layer.

[0038] [7] The external perfusion type hollow fiber membrane module according to any one of [1] to [6], wherein the outer diameter of the hollow fiber membrane is 350 μm or less.

[0039] [8] The external perfusion type hollow fiber membrane module according to any one of [1] to [7], wherein the breaking strength of the hollow fiber membrane is 0.5 N / fil or more and the breaking elongation is 50% or more.

[0040] [9] In the external perfusion type hollow fiber membrane module according to any one of [1] to [8], on a cross section obtained by cutting the outer shell in a direction perpendicular to the length direction of the hollow fiber membrane bundle, the filling rate of the hollow fiber membrane bundle in the outer shell is 20 to 50%.

[0041]

[10] In the external perfusion type hollow fiber membrane module according to any one of [1] to [9], the plurality of hollow fiber membranes are bundled in a state of being folded into a U shape at the central portion in the length direction, and at the first end portion, the open ends on both sides of each hollow fiber membrane are kept open and are fixed in the outer shell by the casting portion.

[0042]

[11] In the external perfusion type hollow fiber membrane module according to

[10] , at the second end portion of the hollow fiber membrane bundle on the side opposite to the first end portion, the positions of the U-shaped folded ends of each hollow fiber membrane are aligned to be substantially in the same plane.

[0043]

[12] In the external perfusion type hollow fiber membrane module according to any one of [1] to [9], the first end portion of the hollow fiber membrane bundle formed by aligning a plurality of hollow fiber membranes in one direction, and

[0044] the second end portion on the side opposite to the first end portion are respectively fixed in the outer shell by the casting portion.

[0045]

[13] An external perfusion type hollow fiber membrane module includes: a tubular hollow fiber membrane bundle formed by bundling a plurality of hollow fiber membranes and having a cavity portion formed therein, and an outer shell that houses the hollow fiber membrane bundle.

[0046] The first end portion in the length direction of the hollow fiber membrane bundle is fixed in the outer shell by the casting portion in a state where the end faces of each hollow fiber membrane are open.

[0047] The second end portion of the hollow fiber membrane bundle on the side opposite to the first end portion is a free end.

[0048] A liquid is perfused outside the membranes of each hollow fiber membrane from the casting portion in the outer shell to the second end portion side.

[0049] In the region between the casting portion in the outer shell and the second end portion, only the hollow fiber membrane bundle is provided.

[0050]

[14] In the external perfusion type hollow fiber membrane module according to any one of [1] to

[13] , the plurality of hollow fiber membranes are bundled in a state of being connected to each other by warp yarns.

[0051] Other embodiments of the present invention have the following embodiments.

[0052] [A1]An external perfusion type hollow fiber membrane module is a hollow fiber membrane module for removing gas from a liquid to be treated or supplying gas to the liquid to be treated.

[0053] It includes: a hollow fiber membrane bundle formed by a plurality of aligned hollow fiber membranes, a housing that houses the hollow fiber membrane bundle, and a short-circuit prevention body that blocks the flow of the liquid to be treated in the gap between the hollow fiber membrane bundle and the housing.

[0054] At least the first end in the length direction of the hollow fiber membrane bundle is fixed in the housing by a casting part while the open ends of the respective hollow fiber membranes remain open.

[0055] The short-circuit prevention body is provided on the downstream side of the liquid inlet port and protrudes from the inner surface of the housing. The liquid inlet port is a port through which the liquid to be treated flows into the periphery of the hollow fiber membrane in the housing.

[0056] [A2]The external perfusion type hollow fiber membrane module according to [A1], wherein the short-circuit prevention body is annular around the entire hollow fiber membrane bundle.

[0057] [A3]The external perfusion type hollow fiber membrane module according to [A1] or [A2], wherein the hollow fiber membrane is a composite hollow fiber membrane, and the composite hollow fiber membrane includes a homogeneous layer having gas permeability and a porous support layer that supports the homogeneous layer.

[0058] [A4]The external perfusion type hollow fiber membrane module according to any one of [A1] to [A3], wherein the outer diameter of the hollow fiber membrane is 350 μm or less.

[0059] [A5]The external perfusion type hollow fiber membrane module according to any one of [A1] to [A4], wherein the breaking strength of the hollow fiber membrane is 0.5 N / fil or more and the breaking elongation is 50% or more.

[0060] [A6]The external perfusion type hollow fiber membrane module according to any one of [A1] to [A5], wherein on a cross section obtained by cutting the housing in a direction perpendicular to the length direction of the hollow fiber membrane bundle, the filling rate of the hollow fiber membrane bundle in the housing is 20 to 50%.

[0061] [A7]The external perfusion type hollow fiber membrane module according to any one of [A1] to [A6], wherein the plurality of hollow fiber membranes are respectively bundled in a state of being folded into a U shape at the central part in the length direction, and are fixed in the housing by the casting part while the open ends on both sides of each hollow fiber membrane remain open at the first end.

[0062] [A8]In the external perfusion type hollow fiber membrane module according to [A7], at the second end of the hollow fiber membrane bundle on the side opposite to the first end, the end positions of the U-shaped folds of the respective hollow fiber membranes are aligned.

[0063] [A9]In the external perfusion type hollow fiber membrane module according to any one of [A1] to [A6], the first end of the hollow fiber membrane bundle formed by aligning a plurality of hollow fiber membranes in one direction and the second end on the side opposite to the first end are respectively fixed in the housing by the casting portion.

[0064] [A10]In the external perfusion type hollow fiber membrane module according to any one of [A1] to [A9], a plurality of the hollow fiber membranes are bundled in a state of being interconnected by the warp yarns.

[0065] In addition, other embodiments of the present invention have the following configurations.

[0066] [B1]A gas-liquid separation hollow fiber membrane module includes: a hollow fiber membrane bundle formed by bundling a plurality of hollow fiber membranes, and a housing that houses the hollow fiber membrane bundle,

[0067] At least one end in the longitudinal direction of the hollow fiber membrane bundle is fixed in the housing by the casting portion with the end faces of the respective hollow fiber membranes open,

[0068] The outer diameter of the hollow fiber membrane is 350 μm or less,

[0069] The Gurley stiffness of the hollow fiber membrane is 15 mN or more.

[0070] [B2]In the gas-liquid separation hollow fiber membrane module according to [B1], it is an external perfusion type in which the liquid to be treated is perfused outside the membranes of the respective hollow fiber membranes in the housing.

[0071] [B3]In the gas-liquid separation hollow fiber membrane module according to [B1] or [B2], the hollow fiber membrane is a composite hollow fiber membrane, and the composite hollow fiber membrane includes a homogeneous layer having gas permeability and a porous support layer that supports the homogeneous layer.

[0072] [B4]In the gas-liquid separation hollow fiber membrane module according to any one of [B1] to [B3], the breaking strength of the hollow fiber membrane is 0.5 N / fil or more and the breaking elongation is 50% or more.

[0073] [B5]In the gas-liquid separation hollow fiber membrane module according to any one of [B1] to [B4], on a cross-section obtained by cutting the outer shell in a direction perpendicular to the length direction of the hollow fiber membrane bundle, the filling rate of the hollow fiber membrane bundle in the outer shell is 20 to 50%.

[0074] [B6]In the gas-liquid separation hollow fiber membrane module according to any one of [B1] to [B5], the plurality of hollow fiber membranes are respectively bundled in a state of being folded into a U shape at the central portion in the length direction to form the hollow fiber membrane bundle.

[0075] The first end portion on the side opposite to the folded-back portion of each hollow fiber membrane in the hollow fiber membrane bundle is fixed in the outer shell by the casting portion in a state where both end faces of each hollow fiber membrane are open.

[0076] [B7]In the gas-liquid separation hollow fiber membrane module according to [B6], at the second end portion on the side opposite to the first end portion of the hollow fiber membrane bundle, the end positions of the respective hollow fiber membranes are aligned.

[0077] [B8]In the gas-liquid separation hollow fiber membrane module according to any one of [B1] to [B7], the plurality of hollow fiber membranes are bundled in a state of being connected to each other by warp threads.

[0078] In addition, other embodiments of the present invention have the following configurations.

[0079] [C1]An externally perfused hollow fiber membrane module includes: a tubular hollow fiber membrane bundle formed by bundling a plurality of hollow fiber membranes and having a hollow portion formed therein, and an outer shell housing the hollow fiber membrane bundle.

[0080] The first end portion in the length direction of the hollow fiber membrane bundle is fixed in the outer shell by the casting portion in a state where the end faces of the respective hollow fiber membranes are open.

[0081] The second end portion on the side opposite to the first end portion of the hollow fiber membrane bundle is a free end.

[0082] Liquid is perfused to the outside of the membranes of the respective hollow fiber membranes from the casting portion in the outer shell to the second end portion side.

[0083] In the region between the casting portion and the second end portion in the outer shell, only the hollow fiber membrane bundle is provided.

[0084] [C2]In the externally perfused hollow fiber membrane module according to [C1], the hollow fiber membrane is a composite hollow fiber membrane, and the composite hollow fiber membrane includes a homogeneous layer having gas permeability and a porous support layer supporting the homogeneous layer.

[0085] [C3] The external perfusion type hollow fiber membrane module according to [C1] or [C2], wherein the outer diameter of the hollow fiber membrane is 350 μm or less.

[0086] [C4] The external perfusion type hollow fiber membrane module according to any one of [C1] to [C3], wherein the Gurley stiffness of the hollow fiber membrane is 3 mN or more.

[0087] [C5] The external perfusion type hollow fiber membrane module according to any one of [C1] to [C4], wherein the breaking strength of the hollow fiber membrane is 0.5 N / fil or more and the breaking elongation is 50% or more.

[0088] [C6] The external perfusion type hollow fiber membrane module according to any one of [C1] to [C5], wherein, on a cross section obtained by cutting the outer shell in a direction perpendicular to the length direction of the hollow fiber membrane bundle, the filling rate of the hollow fiber membrane bundle in the outer shell is 20 to 50%.

[0089] [C7] The external perfusion type hollow fiber membrane module according to any one of [C1] to [C6], wherein the plurality of hollow fiber membranes are respectively bundled in a state of being folded into a U shape at the central portion in the length direction, and are fixed in the outer shell by the casting portion in a state where both end faces of each hollow fiber membrane are open.

[0090] [C8] The external perfusion type hollow fiber membrane module according to any one of [C1] to [C7], wherein, at the second end portion of the hollow fiber membrane bundle, the end positions of the respective hollow fiber membranes are aligned.

[0091] [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 yarns.

[0092] Effects of the Invention

[0093] The external perfusion type hollow fiber membrane module of the first embodiment of the present invention having the configuration of [1] can suppress the short-circuit flow path of the liquid to be treated in the outer shell, enable the liquid to be treated to efficiently contact the hollow fiber membrane, and has a high treatment capacity.

[0094] When using the external perfusion type hollow fiber membrane module of the second embodiment of the present invention having the configuration of [3], even if the module becomes larger, the hollow fiber membrane becomes longer, and the flow rate of the liquid to be treated becomes faster, the shape retention of the hollow fiber membrane bundle can be ensured, and a decrease in degassing efficiency can be suppressed.

[0095] When using the external perfusion type hollow fiber membrane module of the third embodiment of the present invention having the

[12] configuration, even if the module becomes larger and the flow rate of the perfusion liquid becomes faster, liquid maldistribution within the housing can be suppressed, and a decrease in the efficiency of degassing or gas supply can be suppressed. BRIEF DESCRIPTION OF THE DRAWINGS

[0096] Figure 1 is a cross-sectional view showing an example of the external perfusion type hollow fiber membrane module of the first embodiment of the present invention.

[0097] Figure 2 Figure 1 is an enlarged side view of the anti-short circuit body setting portion of the external perfusion type hollow fiber membrane module.

[0098] Figure 3 represents Figure 1 a plan view of a step of the manufacturing method of the external perfusion type hollow fiber membrane module.

[0099] Figure 4 represents Figure 1 a side view of a step of the manufacturing method of the external perfusion type hollow fiber membrane module.

[0100] Figure 5 represents Figure 1 a cross-sectional view of a step of the manufacturing method of the external perfusion type hollow fiber membrane module.

[0101] Figure 6 is a cross-sectional view showing another example of the external perfusion type hollow fiber membrane module of the first embodiment of the present invention.

[0102] Figure 7 is a graph showing the dissolved oxygen removal rate with respect to the treatment flow rate in Examples A1 to A4 of the present invention.

[0103] Figure 8 is a cross-sectional view showing an example of the external perfusion type hollow fiber membrane module of the second embodiment of the present invention.

[0104] Figure 9 represents Figure 8 a plan view of a step of the manufacturing method of the external perfusion type hollow fiber membrane module.

[0105] Figure 10 represents Figure 8 a side view of a step of the manufacturing method of the external perfusion type hollow fiber membrane module.

[0106] Figure 11 represents Figure 8 a cross-sectional view of a step of the manufacturing method of the external perfusion type hollow fiber membrane module. ​​​​​​​​​​​​

[0107] Figure 12 represents a cross-sectional view of another example of the external perfusion type hollow fiber membrane module according to the second embodiment of the present invention.

[0108] Figure 13 represents a graph of the dissolved oxygen removal rate with respect to the treatment flow rate in Examples B1 to B7 of the present invention.

[0109] Figure 14 represents a cross-sectional view of an example of the external perfusion type hollow fiber membrane module according to the third embodiment of the present invention.

[0110] Figure 15 represents Figure 14 a side view of the upper part of the hollow fiber membrane bundle in the external perfusion type hollow fiber membrane module of

[0111] Figure 16 represents Figure 14 a plan view of a step in the manufacturing method of the external perfusion type hollow fiber membrane module of

[0112] Figure 17 represents Figure 14 a side view of a step in the manufacturing method of the external perfusion type hollow fiber membrane module of

[0113] Figure 18 represents Figure 14 a cross-sectional view of a step in the manufacturing method of the external perfusion type hollow fiber membrane module of

[0114] Figure 19 represents a graph of the dissolved oxygen removal rate with respect to the treatment flow rate in Examples C1 to C2 of the present invention.

[0115] Figure 20 represents a cross-sectional view of an example of a conventional external perfusion type hollow fiber membrane module.

[0116] Figure 21 represents a graph of the dissolved oxygen removal rate in each water flow direction in Examples A5 to A6 of the present invention.

[0117] Figure 22 represents a graph of the dissolved oxygen removal rate with respect to the treatment flow rate in Examples C3 to C5 of the present invention.

[0118] Reference numeral

[0119] ​​​​​​​​​​​11, 12, 21, 22, 31... External perfusion type hollow fiber membrane module, 110, 110A, 210, 210A, 310... Hollow fiber membrane bundle, 110a, 210a, 310a... First end, 110b, 210b, 310b... Second end, 111, 211, 311... Hollow fiber membrane, 111a, 111c, 111d... Open end, 112, 214, 314... Housing, 114... Anti-short circuit body, 116, 116A, 218, 218A, 318... Housing body, 118, 220, 320... First cover part, 120, 222, 322... Second cover part, 122, 224, 324... First port, 124, 216, 216A, 216B, 316... Pouring part, 128... Gap, 220c... Second port, 222c... Third port, 230... Fourth port, 312... Cavity part, 320c... Second port, 322c... Third port. Detailed implementation mode

[0120] [First implementation mode]

[0121] The external perfusion type hollow fiber membrane module of the first implementation mode 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 of the first implementation mode of the present invention can be used in, for example, inkjet ejection devices such as inkjet printers and color filter manufacturing devices.

[0122] An example of the external perfusion type hollow fiber membrane module of the first implementation mode of the present invention will be described below. In addition, the dimensions of the figures exemplified in the following description are only examples, and the first implementation mode of the present invention is not limited thereto, and appropriate changes can be made within the scope of not changing its main idea.

[0123] The external perfusion type hollow fiber membrane module 11 of the present implementation mode (hereinafter also referred to as "module 11") is as Figure 1 shown, and includes a hollow fiber membrane bundle 110, a housing 112, and an anti-short circuit body 114.

[0124] The housing 112 includes: a cylindrical housing body 116, a first cover part 118 provided on the first open end 116a side in the length direction of the housing body 116, and a second cover part 120 provided on the second open end 116b side of the housing body 116. The housing 112 is composed of the housing body 116, the first cover part 118, and the second cover part 120, and has a cylindrical appearance. As the housing, it is preferably a housing having a cylindrical appearance with a cylindrical housing body as in this example. In addition, in the first implementation mode of the present invention, the housing is not limited to a cylindrical appearance, and may be, for example, a housing having a polygonal columnar appearance with a polygonal tube-shaped housing body.

[0125] On a portion of the housing body 116 of the housing 112 near the first open end 116a, a cylindrical first port 122 communicating with the interior of the housing body 116 is provided and protrudes outward from the outer peripheral surface of the housing body 116. Additionally, the shape of the first port 122 is not limited to a cylindrical shape and can also be, for example, a polygonal tubular shape or the like.

[0126] The first lid portion 118 includes: a circular flat plate portion 118a, a cylindrical portion 118b protruding toward the housing body 116 along the entire outer peripheral edge of the flat plate portion 118a, and a second port 118c protruding outward from the central portion of the flat plate portion 118a. The first end portion 117a of the housing body 116 is inserted into the cylindrical portion 118b, and the first lid portion 118 is mounted on the housing body 116. The second port 118c is located on the central axis L11 of the housing 112.

[0127] The second port 118c is cylindrical and serves as a gas outflow port for allowing gas to flow out of the housing 112 or a gas inflow port for allowing gas to flow in. The shape of the second port 118c is not limited to a cylindrical shape and can also be, for example, a polygonal tubular shape or the like.

[0128] The second lid portion 120 includes: a circular flat plate portion 120a, a cylindrical portion 120b protruding toward the housing body 116 along the entire outer peripheral edge of the flat plate portion 120a, and a cylindrical third port 120c protruding outward from the central portion of the flat plate portion 120a. The second end portion 117b of the housing body 116 is inserted into the cylindrical portion 120b, and the second lid portion 120 is mounted on the housing body 116. The third port 120c is located on the central axis L11 of the housing 112.

[0129] The shape of the third port 120c is not limited to a cylindrical shape and can also be, for example, a polygonal tubular shape or the like.

[0130] In addition, in order to improve the efficiency of removing air bubbles in the housing 112, the flat plate portion 120a can also be conical.

[0131] In the assembly 11, no partition is provided inside the housing 112. A first port 122 is provided near the first open end 116a of the housing body 116, and a third port 120c is provided on the second lid portion 120 provided on the second open end 116b side of the housing body 116. In this example, the first port 122 is a liquid inflow port, and the third port 120c is a liquid outflow port. The liquid to be treated flows in from the first port 122, moves toward the third port 120c, and flows unidirectionally in the longitudinal direction of the housing 112, and the flow direction inside the housing 112 will not reverse. Depending on the installation situation, the first port 122 can also be a liquid outflow port and the third port 120c can be a liquid inflow port, with the liquid flow direction being the opposite unidirectional water flow.

[0132] The size of the outer shell 112 can be appropriately set. For example, the outer diameter and length of the outer shell body 116 can be appropriately changed. In the case of the cylindrical outer shell body 116, the outer diameter of the outer shell body 116 can be 3 to 15 cm, and the length can be 5 to 50 cm.

[0133] As the material for forming the outer shell 112, a material that can preferably ensure sufficient mechanical strength and durability can be cited. For example, polycarbonate, polysulfone, polyolefin, PVC (polyvinyl chloride), acrylic resin, ABS resin, modified PPE (polyphenylene ether), etc. As the material for forming the outer shell 112, one type can be used alone, or two or more types can be used in combination.

[0134] The hollow fiber membrane bundle 110 is formed by bundling a plurality of aligned hollow fiber membranes 111 into a cylindrical shape. The plurality of hollow fiber membranes 111 forming the hollow fiber membrane bundle 110 are bundled in a state where the central portion in the length direction is folded into a U shape. The shape of the hollow fiber membrane bundle 110 is not limited to a cylindrical shape, and can also be, for example, a shape bundled into a cylindrical shape with a hole arranged in the central portion.

[0135] The hollow fiber membrane bundle 110 is housed in the outer shell 112. The first end portion 110a in the length direction of the hollow fiber membrane bundle 110 is restricted by the bundle ring 123, and is fixed in the outer shell 112 by the pouring portion 124 in this state. On the end face 124a on the side of the first cover portion 118 of the pouring portion 124, the open ends 111a on both sides of each hollow fiber membrane 111 folded into a U shape remain open.

[0136] The second end portion 110b of the hollow fiber membrane bundle 110, which is located on the side opposite to the first end portion 110a and is formed by the U-shaped folded-back portions of the respective hollow fiber membranes 111, is not fixed to the outer shell 112 and is a free end. Thus, the liquid to be treated easily enters between the respective hollow fiber membranes 111 of the entire hollow fiber membrane bundle 110, and therefore the degassing or gas supply of the liquid to be treated can be efficiently performed.

[0137] In the first embodiment of the present invention, preferably as in this example, a plurality of hollow fiber membranes are bundled in a state where the central portion in the length direction is folded into a U shape, and the open ends on both sides of each hollow fiber membrane are fixed in the outer shell by the pouring portion while remaining open. By bundling the respective hollow fiber membranes in this state, even if the number of hollow fiber membranes is small, it is easy to sufficiently increase the filling rate of the hollow fiber membrane bundle, and the manufacturing efficiency is improved. In addition, since the hollow fiber membrane bundle maintains a self-supporting state and the liquid to be treated easily enters between the respective hollow fiber membranes of the entire hollow fiber membrane bundle, a multi-bundle woven fabric can be used, and preferably a small bundle aggregate of hollow fiber membranes is used, thereby improving the efficiency of degassing or gas supply.

[0138] Through the pouring part 124, the first open end 116a of the casing body 116 is blocked. A space is formed on the side of the first cover part 118 of the end face 124a of the pouring part 124 in the casing 112, and this space is separated from the space from the pouring part 124 in the casing body 116 to the second open end 116b side by the pouring part 124. Since the open ends 111a on both sides of each hollow fiber membrane 111 at the first end 110a of the hollow fiber membrane bundle 110 remain open, the inside of each hollow fiber membrane 111 is in communication with the space on the side of the first cover part 118 of the pouring part 124 in the casing 112.

[0139] In the hollow fiber membrane bundle 110, each hollow fiber membrane 111 is bundled in a state of being interconnected by the warp yarns 126. Specifically, in a portion near the U-shaped folded-back part of each hollow fiber membrane 111, in a direction perpendicular to the central axis L11, that is, in a direction perpendicular to the length direction of each hollow fiber membrane 111, a plurality of hollow fiber membranes 111 are woven by the warp yarns 126, whereby each hollow fiber membrane 111 is interconnected with each other. In the first embodiment of the present invention, it is preferable to bundle each hollow fiber membrane in a state of being interconnected by the warp yarns in this way. Thereby, even when the liquid to be treated is highly viscous such as ink, it is possible to suppress the dispersion of the hollow fiber membranes forming the hollow fiber membrane bundle, and the hollow fiber membrane bundle is easily maintained in a self-supporting state.

[0140] As a method of connecting a plurality of hollow fiber membranes by warp yarns, there is no particular limitation, and for example, a method of chain stitch type weaving can be cited.

[0141] In the second end 110b of the hollow fiber membrane bundle 110, in the direction of the central axis L11 of the casing 112, the positions of the ends 111b formed by the U-shaped folded-back parts of each hollow fiber membrane 111 are substantially aligned on the same plane. That is, the lengths of the parts of each hollow fiber membrane 111 exposed to the pouring part 124 are aligned with each other. The positions of the ends 111b of each hollow fiber membrane 111 being substantially aligned on the same plane means that the error of this length of each hollow fiber membrane 111 is ±5% with respect to the average value of the lengths of the parts of all the hollow fiber membranes 111 forming the hollow fiber membrane bundle 110 exposed to the pouring part 124.

[0142] In the first embodiment of the present invention, it is preferable that, in the second end of the hollow fiber membrane bundle, the U-shaped folded ends of each hollow fiber membrane bundle are aligned with each other. Thereby, in the casing, it is easy to suppress the local flow deviation of the liquid to be treated. In addition, it is easy to suppress the deformation of the shape of the hollow fiber membrane bundle, the liquid to be treated easily enters the entire hollow fiber membrane bundle, and the efficiency of degassing or air supply is improved.

[0143] As the hollow fiber membrane 111, a gas-permeable hollow fiber membrane that can permeate gas between the hollow part inside the membrane and the outside of the membrane is preferably used. In addition, from the perspective of excellent strength and more efficient degassing or gas supply, as the hollow fiber membrane 111, a composite hollow fiber membrane having a gas-permeable homogeneous layer and a porous support layer supporting the homogeneous layer is more preferably used.

[0144] As the structure of the composite hollow fiber membrane, 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 porous support layers are provided on both the inside and outside of the homogeneous layer is preferably used. From the perspective of strength and degassing or gas supply performance, a three-layer structure is more preferably used.

[0145] As the material for forming the homogeneous layer, known materials can be used, such as silicone rubber-based resins, polyolefin-based resins, fluorine-containing resins, cellulose-based resins, polyphenylene ether, poly(4-vinylpyridine), polyurethane-based resins, etc. These materials can be used alone or in combination of two or more. Among them, as the material for forming the homogeneous layer, a polyolefin-based resin is preferably used from the perspective of excellent degassing or gas supply performance when a high-flow perfusion of the liquid to be treated is performed and excellent drug resistance at the same time, and a low-density polyethylene resin is more preferably used from the perspective of excellent film-forming properties.

[0146] Examples of the polyolefin-based resin include copolymers of ethylene and α-olefins, poly(4-methyl-1-pentene), metallocene polyethylene, low-density polyethylene, high-density polyethylene, linear low-density polyethylene, linear ultra-low-density polyethylene, polypropylene, ionomer resins, ethylene-vinyl acetate copolymers, ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylic acid methyl ester copolymers, modified polyolefins, etc.

[0147] As the material for forming the porous support layer, known materials can be used, such as silicone rubber-based resins such as polydimethylsiloxane and copolymers of silicon and polycarbonate; polyolefin-based resins such as poly(4-methyl-1-pentene), poly(3-methyl-1-butene), high-density polyethylene, and polypropylene; fluorine-containing resins such as polyvinylidene fluoride and polytetrafluoroethylene; cellulose-based resins such as ethyl cellulose; polyphenylene ether; poly(4-vinylpyridine); polyurethane-based resins; polystyrene; polyetheretherketone; polyetherketone, etc. These materials can be used alone or in combination of two or more. Among them, from the perspective of easily ensuring the self-supporting property of the hollow fiber membrane bundle and obtaining film-forming stability, as the material for forming the porous support layer, high-density polyethylene showing an MFR value equivalent to that of the homogeneous layer is preferably used.

[0148] The pore diameter of the porous support layer is preferably 0.01 to 1 μm.

[0149] The porosity of the porous support layer is preferably 30 to 80% by volume. If the porosity is above the lower limit of the said range, the performance of degassing or gas supply is excellent. If the porosity is below the upper limit of the said range, the mechanical strength such as the pressure resistance of the hollow fiber membrane is improved.

[0150] The outer diameter of the hollow fiber membrane 111 is preferably 350 μm or less, more preferably 150 to 330 μm, and further preferably 200 to 300 μm. If the outer diameter of the hollow fiber membrane 111 is within the said range, a more efficient flow path can be formed between the hollow fiber membranes 111 in the outer shell 112.

[0151] The inner diameter of the hollow fiber membrane 111 is preferably 100 μm or more, more preferably 120 to 250 μm, and further preferably 130 to 200 μm. If the inner diameter of the hollow fiber membrane 111 is within the said range, a sufficient number of hollow fiber membranes 111 can be accommodated in the outer shell 112, and it is easy to maintain the performance of degassing or gas supply and durability.

[0152] The membrane thickness of the hollow fiber membrane 111 is preferably 20 to 70 μm, more preferably 25 to 55 μm.

[0153] If the membrane thickness of the hollow fiber membrane 111 is below the upper limit value, the durability is excellent when the inside of the hollow fiber membrane 111 in the outer shell 112 is repeatedly decompressed or pressurized. If the membrane thickness of the hollow fiber membrane 111 is above the lower limit value of the said range, it is easy to maintain good degassing or gas supply performance.

[0154] In addition, the membrane thickness of the hollow fiber membrane is calculated by the following formula (1) based on the difference between the inner diameter and the outer diameter of the hollow fiber membrane.

[0155] Membrane thickness of hollow fiber membrane = (Outer diameter of hollow fiber membrane - Inner diameter of hollow fiber membrane) / 2 ··· (1)

[0156] The inner diameter and the outer diameter of the hollow fiber membrane are measured according to the method described in

[0062] of International Publication No. 2015 / 012293.

[0157] As long as the membrane thickness is within the said range, the thicknesses of the homogeneous layer and the porous support layer can be appropriately set. The thickness of the homogeneous layer is preferably 0.3 to 2 μm, more preferably 0.5 to 1.2 μm.

[0158] The thicknesses of the homogeneous layer and the porous support layer are measured according to the method described in

[0077] of International Publication No. 2015 / 012293.

[0159] In the hollow fiber membrane 111, from the perspective of the operability during component manufacturing, the breaking strength is preferably 0.5 N / fil or more, and the elongation at break is preferably 50% or more. More preferably, the breaking strength is 0.8 - 5 N / fil, and the elongation at break is 70 - 400%. Further preferably, the breaking strength is 1 - 4 N / fil, and the elongation at break is 140 - 300%.

[0160] In addition, the breaking strength refers to the breaking value when a tensile load is applied and the hollow fiber membrane is stretched in the longitudinal direction. "N / fil" means the strength required to break one hollow fiber membrane (1 filament), expressed in newtons (N). The elongation at break refers to the elongation when a tensile load is applied and the hollow fiber membrane is stretched to break in the longitudinal direction.

[0161] The breaking strength and the elongation at break are measured according to the method described in

[0081] of International Publication No. 2015 / 012293. Specifically, using a TENSILON type tensile testing machine, one hollow fiber membrane is clamped in the chuck part of the testing machine, with a length of 2 cm, a tensile load is applied, and the breaking strength and the elongation at break are measured three times, and the average value is obtained.

[0162] The Gurley stiffness of the hollow fiber membrane is preferably 15 mN or more, more preferably 15 - 30 mN, and further preferably 18 - 25 mN. If the Gurley stiffness of the hollow fiber membrane is above the lower limit value 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 the decrease in the efficiency of degassing or gas supply. If the Gurley stiffness of the hollow fiber membrane is below the upper limit value of the above range, there is less membrane distortion generated as the membrane length increases when forming the membrane bundle, and the component can be formed in a straightened state.

[0163] In addition, the Gurley stiffness of the hollow fiber membrane is measured according to the JIS L1096 A method (Gurley method) using a sample composed of 7 bundles of hollow fiber membranes (width: about 25 - 26 mm) folded in units of 32 (32 fil) hollow fiber membranes. The Gurley stiffness of the hollow fiber membrane can be controlled by adjusting the material, outer diameter, etc. of the hollow fiber membrane.

[0164] Inside the housing 112, the inner surface 116c of the housing body 116 is partially separated from the hollow fiber membrane bundle 110, and a gap 128 is formed between the housing 112 and the hollow fiber membrane bundle 110 around the hollow fiber membrane bundle 110.

[0165] On the cross-section obtained by cutting the outer shell 112 in a direction perpendicular to the longitudinal direction of the hollow fiber membrane bundle 110, the filling rate of the hollow fiber membrane bundle 110 in the outer shell 112 is preferably 20 to 50%, more preferably 30 to 45%. If the filling rate of the hollow fiber membrane is above the lower limit, it is easy to suppress the uneven flow of the liquid to be treated in the outer shell. If the filling rate of the hollow fiber membrane is below the upper limit, the filling of the hollow fiber membrane becomes easier, the pressure loss is reduced, and the performance of degassing or air supply is improved.

[0166] In addition, the filling rate is the ratio (%) of the total cross-sectional area of the respective hollow fiber membranes 111 forming the hollow fiber membrane bundle 110 filled with respect to the cross-sectional area inside the outer shell 112, measured on the cross-section obtained by cutting the outer shell 112 in a direction perpendicular to the longitudinal direction of the hollow fiber membrane bundle 110.

[0167] In the module 11, as Figure 1 and Figure 2 shown, an annular anti-channeling body 114 is embedded in the outer shell body 116 of the outer shell 112 and protrudes from the inner surface 116c of the outer shell body 116 of the outer shell 112. The anti-channeling body 114 may also be integrally formed on the inner surface 116c during molding. The shape of the anti-channeling body 114 is a protruding shape that goes around once on the inner surface 116c of the outer shell body 116 of the outer shell 112.

[0168] The anti-channeling body 114 is provided on the downstream side of the first port 122 of the outer shell 112 and functions to block the flow of the liquid to be treated in the gap 128 between the hollow fiber membrane bundle 110 and the outer shell 112. In the module 11, a part of the liquid to be treated flowing into the outer shell 112 from the first port 122 enters the inside of the hollow fiber membrane bundle 110, and the remaining part flows toward the downstream side in the gap 128 between the hollow fiber membrane bundle 110 and the outer shell 112. However, since the anti-channeling body 114 blocks the flow direction of the liquid to be treated in the gap 128 between the hollow fiber membrane bundle 110 and the outer shell 112, the flow direction becomes toward the inner side in the radial direction, and then flows toward the downstream side after entering the inside of the hollow fiber membrane bundle 110. In this way, the liquid to be treated flowing in the gap 128 between the hollow fiber membrane bundle 110 and the outer shell 112 is introduced into the inside of the hollow fiber membrane bundle 110 by the anti-channeling body 114, so that it is possible to suppress the short-circuit flow of the liquid to be treated in the outer shell 112 and prevent it from flowing out from the third port 120c without being sufficiently treated.

[0169] The short-circuit prevention body 114 is preferably disposed in the direction along the central axis L11 of the housing 112, and is closer to the first port 122 side than the second end 110b located on the downstream side of the hollow fiber membrane bundle 110. In addition, based on the angle of further improving the suppression of the short-circuit flow of the liquid to be treated in the gap 128 between the hollow fiber membrane bundle 110 and the housing 112, it is more preferable to dispose the short-circuit prevention body 114 at a position as close as possible to the first port 122 on the downstream side of the first port 122.

[0170] The distance from the position of the central axis L12 of the first port 122 to the second end 110b of the hollow fiber membrane bundle 110 is set as d11 (mm), and the distance from the position of the central axis L12 of the first port 122 to the short-circuit prevention body 114 is set as d12 (mm). When the first port 122 is the liquid inlet port, d12 / d11 is preferably 0.01 to 0.2, and more preferably 0.03 to 0.1. If d12 / d11 is below the upper limit, the short-circuit flow only through the outside of the hollow fiber membrane bundle can be avoided. If d12 / d11 is above the lower limit, the liquid to be treated can contact the hollow fiber membrane 111 more efficiently, improving the treatment capacity of the module 11.

[0171] The module 11 can be in a form where the short-circuit prevention body 114 and the housing 112 are separately manufactured and the short-circuit prevention body 114 is embedded in the housing 112, or in a form where the housing 112 and the short-circuit prevention body 114 are integrally formed.

[0172] The short-circuit prevention body 114 in this example is circular around the entire hollow fiber membrane bundle 110. In addition, the short-circuit prevention body 114 is not limited to this form and can also be intermittently provided around the hollow fiber membrane bundle 110. In the first embodiment of the present invention, based on the angle of higher short-circuit flow suppression effect of the liquid to be treated in the housing, it is preferable that the short-circuit prevention body is circular around the entire hollow fiber membrane bundle.

[0173] The cross-sectional shape of the short-circuit prevention body 114 is rectangular in this example, but is not limited to rectangular, and can also be triangular, semi-circular, etc.

[0174] The width D1 ( Figure 2 ) in the direction along the central axis L11 of the short-circuit prevention body 114 is preferably 1 to 10 mm, and more preferably 2 to 7 mm. If the width D1 is above the lower limit, the short-circuit flow through the outside of the membrane bundle can be prevented. If the width D1 is below the upper limit, the liquid to be treated can be introduced into the membrane bundle more efficiently.

[0175] Based on the angle of making the liquid to be treated contact the hollow fiber membrane 111 more efficiently, the short-circuit prevention body 114 must contact the hollow fiber membrane bundle 110.

[0176] The protruding height H1 of the short-circuit prevention body 114 from the inner surface 116c of the housing body 116 of the housing 112( Figure 2 ), preferably 1 to 10 mm, more preferably 2 to 7 mm. If the protruding height H1 is above the lower limit value, the liquid to be treated can contact the hollow fiber membrane 111 more efficiently, improving the processing capacity of the module 11. If the protruding height H1 is below the upper limit value, it is easy to insert the hollow fiber membrane bundle 110 into the inside of the short-circuit prevention body 114.

[0177] The number of the short-circuit prevention bodies 114 is one in this example, but is not limited to one, and may be two or more. The number of the short-circuit prevention bodies 114 can be set according to the length of the housing 112.

[0178] From the perspective of a higher effect of suppressing the short-circuit flow of the liquid to be treated in the housing 112, it is preferable to provide the short-circuit prevention bodies 114 at intervals of 50 to 200 mm in the direction along the central axis L11 of the housing 112.

[0179] The material for forming the short-circuit prevention body 114 is not particularly limited, and examples thereof include polycarbonate, polysulfone, polyolefin, polyvinyl chloride, acrylic resin, ABS resin, modified polyphenylene ether, etc. Among them, from the perspective of having mechanical strength and chemical resistance, the material for forming the short-circuit prevention body 114 is preferably polyolefin. When the short-circuit prevention body 114 is integrally formed with the housing 112, the material for forming the short-circuit prevention body 114 is the same as the material for forming the housing 112. As the material for forming the short-circuit prevention body 114, one kind can be used alone, or two or more kinds can be used in combination.

[0180] The manufacturing method of the module 11 is not particularly limited, and for example, the following methods can be cited.

[0181] As shown in Figure 3 , the long strip-shaped hollow fiber membrane 111A is repeatedly folded in the opposite direction multiple times into a U shape to form a strip-shaped hollow fiber membrane sheet 113. At both end sides in the width direction of the hollow fiber membrane sheet 113, the hollow fiber membrane 111A is woven in the length direction of the sheet by the warp 126 to connect the portions extending in the width direction of the hollow fiber membrane 111A to each other. Then, as shown in Figure 4 , with the width direction of the hollow fiber membrane sheet 113 as the axis, the hollow fiber membrane sheet 113 is wound into a cylindrical shape. Then, as shown in Figure 5As shown, a hollow fiber membrane sheet 113 rolled into a cylindrical shape is inserted into a housing body 116 provided with a short-range prevention body 114 and a bundle ring 123. By a known method such as centrifugation, one end of the hollow fiber membrane sheet 113 is fixed to the side of the first opening end 116a of the housing body 116 by pouring resin 130. At this time, the U-shaped folded-back portion of the hollow fiber membrane 111A on the side of the hollow fiber membrane sheet 113 fixed by the poured resin 130 and a part of the poured resin 130 protrude from the housing body 116. Then, the protruding portions of the hollow fiber membrane sheet 113 and the poured resin 130 are cut along the plane X1 of the first opening end 116a of the housing body 116. Thus, a cylindrical hollow fiber membrane bundle 110 is formed in which the open ends 111a of the respective hollow fibers 111 folded into a U shape are fixed to the housing body 116 by the pouring portion 124 while keeping the openings. Next, a first cover portion 118 and a second cover portion 120 are attached to both end portions of the housing body 116, thereby obtaining an assembly 11.

[0182] In the assembly 11, a liquid to be treated is caused to flow into the housing body 116 of the housing 112 from the first port 122 and the liquid to be treated flows out from the third port 120c. The structure for causing the liquid to be treated to flow into the housing 112 from the first port 122 is not particularly limited, and it may be a structure in which a pump is connected to the first port 122 to pump the liquid, or a structure in which a pump is connected to the third port 120c to suck the liquid to be treated.

[0183] For example, by connecting a vacuum pump to the second port 118c to evacuate, the dissolved gas of the liquid to be treated passing between the respective hollow fibers 111 is sucked into the membrane of the hollow fiber 111 and flows out from the second port 118c, and the liquid to be treated is degassed. In addition, by connecting a gas supply pump to the second port 118c to supply gas, gas can be supplied to the liquid to be treated flowing between the respective hollow fibers 111 through the respective hollow fibers 111.

[0184] The liquid to be treated flowing in from the first port 122 flows into the interior of the hollow fiber membrane bundle 110 while flowing through the gap 128 between the hollow fiber membrane bundle 110 and the housing 112 within the housing 112 and going around to the opposite side of the first port 122 of the hollow fiber membrane bundle 110. In addition, the liquid to be treated flowing in the gap 128 between the hollow fiber membrane bundle 110 and the housing 112 toward the downstream side is blocked by the anti-channeling body 114, and after the flow direction is changed, it is introduced into the interior of the hollow fiber membrane bundle 110. Then, the liquid to be treated flows through between the respective hollow fiber membranes 111 of the hollow fiber membrane bundle 110 and flows out from the third port 120c. Thus, in the assembly 11, the anti-channeling body 114 can inhibit the liquid to be treated from flowing short in the outer gap 128 of the hollow fiber membrane bundle 110 within the housing 112. Therefore, the liquid to be treated can be brought into efficient contact with the hollow fiber membrane 111, and the liquid to be treated can be sufficiently treated. Therefore, it is an assembly with high processing capacity.

[0185] As described above, in the external perfusion type hollow fiber membrane assembly according to the first embodiment of the present invention, since the anti-channeling body is provided on the downstream side of the liquid inlet port within the housing, the liquid to be treated is inhibited from flowing short in the outer gap of the hollow fiber membrane bundle within the housing. Therefore, even in the case of increasing the size of the device for high-flow processing, the liquid to be treated can be efficiently introduced into the interior of the hollow fiber membrane bundle and brought into contact with the hollow fiber membrane, and a high processing capacity can be obtained. In addition, regardless of whether the liquid to be treated flows in any direction such as the vertical direction or the horizontal direction, a high processing capacity can be obtained. In addition, the external perfusion type hollow fiber membrane assembly according to the first embodiment of the present invention only needs to provide the anti-channeling body within the housing to obtain a high processing capacity, so the manufacturing is also simple.

[0186] In addition, the external perfusion type hollow fiber membrane assembly according to the first embodiment of the present invention is not limited to the above-described assembly 11. For example, the external perfusion type hollow fiber membrane assembly according to the first embodiment of the present invention may also be an assembly in which both the first end portion and the second end portion in the longitudinal direction of the hollow fiber membrane bundle are fixed to the housing by the casting portion. Specifically, the external perfusion type hollow fiber membrane assembly according to the first embodiment of the present invention may also be Figure 6 the exemplified external perfusion type hollow fiber membrane assembly 12 (hereinafter also referred to as "assembly 12").

[0187] Figure 6 In which, the symbols of the Figure 1 same parts are the same, and the description thereof is omitted.

[0188] Assembly 12 includes: a hollow fiber membrane bundle 110A, a housing 112A, and anti-channeling bodies 114A and 114B.

[0189] The housing 112A includes: a cylindrical housing body 116A, a first lid portion 118 provided on the side of the first opening end 116a in the longitudinal direction of the housing body 116A, and a second lid portion 120 provided on the side of the second opening end 116b of the housing body 116A. A first port 122 is provided on the housing body 116A near the first opening end 116a, and a fourth port 132 serving as a liquid outflow port or a liquid inflow port is provided near the second opening end 116b. In the housing 112A, a ventilation port 120d replacing the third port 120c is provided on the second lid portion 120.

[0190] In this example, the first port 122 is a liquid inflow port, and the fourth port 132 is a liquid outflow port. The liquid to be treated flows in from the first port 122, moves toward the fourth port 132, and flows unidirectionally in the longitudinal direction of the housing 112A, and the flow direction inside the housing 112A will not reverse. Depending on the installation situation, the first port 122 can also be a liquid outflow port, the fourth port 132 can be a liquid inflow port, and the liquid flow direction can be in the opposite unidirectional water flow.

[0191] The hollow fiber membrane bundle 110A is formed by bundling a plurality of hollow fiber membranes 111 into a cylindrical shape in a state where they are aligned in one direction. The hollow fiber membrane bundle 110A is housed in the housing 112A. The first end portion 110a and the second end portion 110b in the longitudinal direction of the hollow fiber membrane bundle 110A are respectively constrained by collar rings 123A and 123B, and are fixed in the housing 112A by casting portions 124A and 124B in this state. The first port 122 and the fourth port 132 are located between the casting portion 124A and the casting portion 124B of the housing 112A.

[0192] The first opening end 116a of the housing body 116A is blocked by the casting portion 124A, and the second opening end 116b of the housing body 116A is blocked by the casting portion 124B. On the end face 124b on the side of the first lid portion 118 of the casting portion 124A, one opening end 111c of each hollow fiber membrane 111 remains open. On the end face 124c on the side of the second lid portion 120 of the casting portion 124B, the other opening end 111d of each hollow fiber membrane 111 remains open.

[0193] The inner surface 116c of the housing body 116A is partially separated from the hollow fiber membrane bundle 110A, and a gap 128 is formed outside the hollow fiber membrane bundle 110A in the housing 112A.

[0194] In the component 12, anti-short circuit members 114A and 114B are provided on the downstream side of the first port 122 and the upstream side of the fourth port 132 within the outer shell 112A. In the direction along the central axis L11 of the outer shell 112A, the position of the anti-short circuit member 114A is close to the first port 122, and the anti-short circuit member 114B is close to the fourth port 132.

[0195] In the component 12, the liquid to be processed flows into the outer shell 112A from the first port 122, and the liquid to be processed flows out from the fourth port 132. For example, by connecting a vacuum pump to the second port 118c and the vent port 120d to evacuate, the liquid to be processed passing between the hollow fiber membranes 111 can be degassed. In addition, by connecting a gas supply pump to the second port 118c and the vent port 120d to supply gas, gas can be supplied to the liquid to be processed passing between the hollow fiber membranes 111.

[0196] In the component 12, the liquid to be processed flowing downstream in the gap 128 between the hollow fiber membrane bundle 110A and the outer shell 112A within the outer shell 112A is also blocked by the anti-short circuit members 114A and 114B, the flow direction changes, and it is guided to the inside of the hollow fiber membrane bundle 110A. Thus, it is possible to suppress the short circuit flow of the liquid to be processed in the gap 128 outside the hollow fiber membrane bundle 110A within the outer shell 112A. Therefore, the liquid to be processed comes into efficient contact with the hollow fiber membranes 111, and the processing capacity is improved.

[0197] In addition, in the external perfusion type hollow fiber membrane module of the first embodiment of the present invention, the open ends 111d of the respective hollow fiber membranes 111 in the component 12 may also be in a state of being buried in casting resin or the like and blocked.

[0198] In addition, in the external perfusion type hollow fiber membrane module of the first embodiment of the present invention, the respective hollow fiber membranes forming the hollow fiber membrane bundle may not be folded into a U shape, and the open ends of the second ends may be free ends in a state of being buried in resin or the like and blocked.

[0199] [Second Embodiment]

[0200] The external perfusion type hollow fiber membrane module of the second embodiment of the present invention includes: a hollow fiber membrane bundle bundling a plurality of hollow fiber membranes, and an outer shell housing the hollow fiber membrane bundle. At least one end in the length direction of the hollow fiber membrane bundle is fixed in the outer shell by a casting portion with the end faces of the respective hollow fiber membranes open. In the external perfusion type hollow fiber membrane module of the second embodiment of the present invention, a hollow fiber membrane having a Gurley stiffness of 15 mN or more is used.

[0201] The external perfusion type hollow fiber membrane module according to the second embodiment 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 second embodiment of the present invention can be used as a degassing module to remove gas from the liquid to be treated that is perfused outside the membrane of the hollow fiber membrane. As the use of the external perfusion type hollow fiber membrane module according to the second embodiment of the present invention, there is no particular limitation, and examples include inkjet ejection devices such as inkjet printers and color filter manufacturing devices.

[0202] An example of the external perfusion type hollow fiber membrane module according to the second embodiment of the present invention will be described below. In addition, the dimensions and the like of the figures illustrated in the following description are merely examples, and the second embodiment of the present invention is not limited thereto, and appropriate changes can be made within the scope of not changing its gist.

[0203] The external perfusion type hollow fiber membrane module 21 (hereinafter also referred to as "module 21") of the present embodiment, as Figure 8 shown, includes a hollow fiber membrane bundle 210 and a housing 214. The hollow fiber membrane bundle 210 is housed in the housing 214, and the first end portion 210a in the longitudinal direction of the hollow fiber membrane bundle 210 is fixed in the housing 214 by a casting portion 216. The second end portion 210b of the hollow fiber membrane bundle 210 on the side opposite to the first end portion 210a is a free end.

[0204] The housing 214 includes: a cylindrical housing body 218, a first lid portion 220 provided on the side of the first open end 218a in the longitudinal direction of the housing body 218, and a second lid portion 222 provided on the side of the second open end 218b of the housing body 218. The housing 214 is formed into a cylindrical appearance by the housing body 218, the first lid portion 220, and the second lid portion 222.

[0205] As the housing in the external perfusion type hollow fiber membrane module according to the second embodiment of the present invention, preferably as in this example, it is a housing having a cylindrical appearance with a cylindrical housing body. In addition, in the second embodiment of the present invention, it is not limited to a housing having a cylindrical appearance, and it can also be, for example, a housing having a polygonal columnar appearance with a polygonal cylindrical housing body.

[0206] On a portion of the housing body 218 of the housing 214 close to the first open end 218a, a first port 224 communicating with the inside of the housing body 218 is provided and protrudes outward from the outer peripheral surface of the housing body 218. The first port 224 is cylindrical and serves as a liquid inlet port for the liquid to be treated to flow into the housing body 218. The shape of the first port 224 is not limited to a cylindrical shape, and it can also be, for example, a polygonal cylindrical shape or the like.

[0207] The first lid portion 220 includes: a circular flat plate portion 220a, a cylindrical portion 220b protruding from the entire outer peripheral edge of the flat plate portion 220a toward the housing body 218, and a second port 220c protruding outward from the central portion of the flat plate portion 220a. The first end portion 219a of the housing body 218 is embedded in the cylindrical portion 220b, and the first lid portion 220 is mounted on the housing body 218. The second port 220c is located on the central axis L21 of the housing 214.

[0208] The second port 220c is cylindrical and serves as a gas outflow port for allowing gas to flow out of the housing 214 or a gas inflow port for allowing gas to flow in. The shape of the second port 220c is not limited to a cylindrical shape, and for example, it may also be a polygonal cylindrical shape or the like.

[0209] The second lid portion 222 includes: a circular flat plate portion 222a, a cylindrical portion 222b protruding from the entire outer peripheral edge of the flat plate portion 222a toward the housing body 218, and a third port 222c protruding outward from the central portion of the flat plate portion 222a. The second end portion 219b of the housing body 218 is embedded in the cylindrical portion 222b, and the second lid portion 222 is mounted on the housing body 218. The third port 222c is located on the central axis L21 of the housing 214.

[0210] The third port 222c is cylindrical and serves as a liquid outflow port for allowing the liquid to be treated to flow out of the housing 214. The shape of the third port 222c is not limited to a cylindrical shape, and for example, it may also be a polygonal cylindrical shape or the like. In addition, the flat plate portion 222a may be conical to facilitate the removal of air bubbles in the housing 214.

[0211] As the material for forming the housing 214, a material that can ensure sufficient mechanical strength and durability is preferred. For example, the same materials as those listed for the housing 112 in the first embodiment can be cited. As the material for forming the housing 214, one type can be used alone, or two or more types can be used in combination.

[0212] The hollow fiber membrane bundle 210 is formed by bundling a plurality of hollow fiber membranes 211 into a cylindrical shape. In addition, the shape of the hollow fiber membrane bundle 210 is not limited to a cylindrical shape, and for example, it may also be a shape in which a central tube is arranged in the center and bundled into a cylindrical shape.

[0213] The hollow fiber membrane bundle 210 is housed in the housing body 218 of the housing 214. The first end portion 210a in the length direction of the hollow fiber membrane bundle 210 is fixed to the end portion on the side of the first opening end 218a of the housing body 218 by the casting portion 216. The plurality of hollow fiber membranes 211 forming the hollow fiber membrane bundle 210 are bundled in a state where the central portions in their respective length directions are folded into a U shape, and are buried in the casting portion 216 and fixed in a state where the two end faces 211a of each hollow fiber membrane 211 are open.

[0214] In the second embodiment of the present invention, preferably as in this example, a plurality of hollow fiber membranes are bundled in a state where the central portions in the longitudinal direction are folded into a U shape, and are fixed in the housing by the casting portion in a state where both end faces of each hollow fiber membrane are open. By bundling the hollow fiber membranes in such a state, even if the number of hollow fiber membranes is small, it is easy to sufficiently increase the packing rate of the hollow fiber membrane bundle, and the manufacturing efficiency is improved. In addition, since it is easy to maintain the self-supporting state of the hollow fiber membrane bundle, the liquid to be treated easily enters between the hollow fiber membranes of the entire hollow fiber membrane bundle, and the degassing efficiency is improved.

[0215] The second end portion 210b, which is located on the side opposite to the first end portion 210a of the hollow fiber membrane bundle 210 and is formed by the U-shaped folded-back portions of the respective hollow fiber membranes 211, is not fixed to the housing 214 and is a free end. Thus, the liquid to be treated easily enters between the hollow fiber membranes 211 of the entire hollow fiber membrane bundle 210, and the degassing of the liquid to be treated can be performed efficiently.

[0216] The first open end 218a of the housing body 218 is blocked by the casting portion 216. The end face 216a of the casting portion 216 on the side of the first cover portion 220 is flush with the first open end 218a of the housing body 218, and at the end face 216a of the casting portion 216, both end faces 211a of each hollow fiber membrane 211 are in an open state. A space is formed on the side of the first cover portion 220 of the end face 216a of the casting portion 216 in the housing 214, and the space from the casting portion 216 in the housing body 218 to the second end portion 210b side of the hollow fiber membrane bundle 210 is separated by the casting portion 216. By both end faces 211a of each hollow fiber membrane 211 being in an open state, the inside of the membrane of each hollow fiber membrane 211 communicates with the space on the side of the first cover portion 220 of the casting portion 216 in the housing 214.

[0217] Both the second port 220c and the third port 222c are located on the central axis L21 of the housing 214. In addition, the inner wall surface of the housing body 218 is separated from the hollow fiber membrane bundle 210, and a space 226 is formed outside the hollow fiber membrane bundle 210 in the housing 214.

[0218] In the hollow fiber membrane bundle 210, the hollow fiber membranes 211 are bundled in a connected state by the warp yarns 228. Specifically, in the vicinity of the U-shaped folded-back portion on each hollow fiber membrane 211, in a direction perpendicular to the central axis L21, that is, in a direction perpendicular to the length direction of each hollow fiber membrane 211, a plurality of hollow fiber membranes 211 are woven by the warp yarns 228, whereby the respective hollow fiber membranes 211 are connected to each other. In the second embodiment of the present invention, it is preferable to bundle the respective hollow fiber membranes in a state of being connected to each other by the warp yarns. Thereby, it is possible to suppress the dispersion of the hollow fiber membranes 211 that form the hollow fiber membrane bundle 210, and the hollow fiber membrane bundle 210 is easily maintained in a self-supporting state. When the viscosity of the liquid to be treated being perfused is high, the hollow fiber membranes 211 are particularly likely to disperse, and it is difficult to ensure the self-supporting property of the hollow fiber membrane bundle 210. Therefore, the method of connecting the hollow fiber membranes to each other by the warp yarns is particularly effective even when the viscosity of the liquid to be treated being perfused is high, for example, when the liquid to be treated is ink or the like.

[0219] As a method of connecting a plurality of hollow fiber membranes by warp yarns, there is no particular limitation, and for example, a method of knitting in a chain stitch pattern can be cited.

[0220] In the second end portion 210b of the hollow fiber membrane bundle 210, in the direction of the central axis L21 of the housing 214, the positions of the end portions 211b formed by the U-shaped folded-back portions of the respective hollow fiber membranes 211 are aligned with each other. That is, the lengths of the portions of the respective hollow fiber membranes 211 exposed to the pouring portion 216 are aligned with each other. The alignment of the positions of the end portions 211b of the respective hollow fiber membranes 211 means that the error of the length of each hollow fiber membrane 211 with respect to the average value of the lengths of the portions of all the hollow fiber membranes 211 that form the hollow fiber membrane bundle 210 and are exposed to the pouring portion 216 is ±5%.

[0221] In the second embodiment of the present invention, it is preferable that, in the second end portion of the hollow fiber membrane bundle, the end portions of the respective hollow fiber membrane bundles are aligned with each other. Thereby, in the housing, it is easy to suppress the local flow deviation of the liquid to be treated. In addition, it is easy to suppress the deformation of the shape of the hollow fiber membrane bundle, the liquid to be treated easily enters the entire hollow fiber membrane bundle, and the degassing efficiency is improved.

[0222] The outer diameter of the hollow fiber membrane 211 is preferably 350 μm or less, more preferably 150 to 330 μm, and still more preferably 200 to 300 μm. If the outer diameter of the hollow fiber membrane 211 is below the upper limit value of the above range, more hollow fiber membranes can be filled in the housing, and the contact with the liquid to be treated is more efficient. In addition, a more efficient flow path can be formed between the hollow fiber membranes 211 in the housing 214. If the outer diameter of the hollow fiber membrane 211 is above the lower limit value of the above range, it is easy to maintain an appropriate stiffness.

[0223] The inner diameter of the hollow fiber membrane 211 is preferably 100 μm or more, more preferably 120 to 250 μm, and still more preferably 130 to 200 μm. 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 housing 214, and it is easy to maintain the degassing performance and durability.

[0224] The membrane thickness of the hollow fiber membrane 211 is preferably 20 to 70 μm, more preferably 25 to 55 μm.

[0225] If the membrane thickness of the hollow fiber membrane 211 is below the above upper limit value, the durability during repeated decompression inside the hollow fiber membrane 211 in the housing 214 is excellent. If the membrane thickness of the hollow fiber membrane 211 is above the lower limit value of the above range, it is easy to maintain good degassing performance.

[0226] In addition, the calculation method of the membrane thickness of the hollow fiber membrane and the measurement methods of the inner diameter and outer diameter of the hollow fiber membrane are as described in the first embodiment.

[0227] The Gurley stiffness of the hollow fiber membrane 211 is preferably 15 mN or more, and still more preferably 18 to 25 mN. If the Gurley stiffness of the hollow fiber membrane 211 is above the lower limit value of the above range, it is easy to ensure the shape retention of the hollow fiber membrane bundle, and the shape distortion of the hollow fiber membrane bundle and the decrease in degassing efficiency can be suppressed. If the Gurley stiffness of the hollow fiber membrane is below the upper limit value of the above range, the operability during manufacturing the component is also good.

[0228] In addition, the measurement method of the Gurley stiffness of the hollow fiber membrane is as described in the first embodiment.

[0229] In the hollow fiber membrane 211, from the perspective of the operability during manufacturing the component, the breaking strength is preferably 0.5 N / fil or more and the breaking elongation is preferably 50% or more, more preferably the breaking strength is 0.8 to 5 N / fil and the breaking elongation is 70 to 400%, and still more preferably the breaking strength is 1 to 4 N / fil and the breaking elongation is 140 to 300%.

[0230] The measurement methods of the breaking strength and the breaking elongation are as described in the first embodiment.

[0231] As the hollow fiber membrane 211, a gas-permeable hollow fiber membrane that can permeate gas between the hollow part inside the membrane and the outside of the membrane is preferably used. In addition, from the perspective of excellent strength and being able to perform degassing more efficiently while suppressing the leakage of the liquid to be treated, as the hollow fiber membrane 211, a composite hollow fiber membrane having a gas-permeable homogeneous layer and a porous support layer supporting the homogeneous layer is more preferably used.

[0232] As the structure of the composite hollow fiber membrane, a double-layer structure with a porous support layer provided on the inner or outer side of the homogeneous layer, or a three-layer structure with porous support layers provided on both the inner and outer sides of the homogeneous layer is preferred. From the viewpoints of strength and degassing performance, a three-layer structure is more preferred.

[0233] The material for forming the homogeneous layer is as described in the first embodiment. As the material for forming the homogeneous layer in the second embodiment, from the viewpoints of excellent degassing performance during high-flow perfusion of the liquid to be treated and easy ensuring of the shape retention of the hollow fiber membrane bundle, a polyolefin resin is preferred, and polyethylene is more preferred.

[0234] As the polyolefin resin for forming the homogeneous layer in the second embodiment, one having higher gas permeability and drug resistance is preferred, and metallocene polyethylene is more preferred.

[0235] The material for forming the porous support layer is as described in the first embodiment. From the viewpoint of easy ensuring of the shape retention of the hollow fiber membrane bundle, as the material for forming the porous support layer in the second embodiment, for the stability of membrane formation, a polyethylene having the same melt flow rate (MFR) as the homogeneous layer and capable of obtaining high strength is preferred.

[0236] The pore diameter of the porous support layer is preferably 0.01 to 1 μm. If the pore diameter is below the upper limit value of the above range, the micropores (gas-permeating pores) of the homogeneous layer are not easily wetted, and the homogeneous layer is not easily deteriorated. If the pore diameter is below the lower limit value of the above range, the degassing performance is excellent.

[0237] The porosity of the porous support layer is preferably 30 to 80% by volume. If the porosity is above the lower limit value of the above range, the degassing performance is excellent. If the porosity is below the upper limit value of the above range, the mechanical strength such as the pressure resistance of the hollow fiber membrane is improved.

[0238] As long as the film thickness is within the above range, the thicknesses of the homogeneous layer and the porous support layer can be appropriately set.

[0239] The method for measuring the thicknesses of the homogeneous layer and the porous support layer is as described in the first embodiment.

[0240] On the cross-section obtained by cutting the outer shell 214 in a direction perpendicular to the length direction of the hollow fiber membrane bundle 210, the filling rate of the hollow fiber membrane bundle 210 in the outer shell 214 is preferably 20 to 50%, and more preferably 30 to 45%. If the filling rate of the hollow fiber membrane is above the lower limit value, it is easy to suppress the uneven flow of the liquid to be treated in the outer shell. If the filling rate of the hollow fiber membrane is below the upper limit value, the filling of the hollow fiber membrane becomes easy and the degassing performance is improved.

[0241] In addition, the filling rate is the ratio (%) of the total cross-sectional area of the individual hollow fiber membranes 211 that form the hollow fiber membrane bundle 210 to the cross-sectional area inside the outer shell 214, measured on a cross-section obtained by cutting the outer shell 214 in a direction perpendicular to the length direction of the hollow fiber membrane bundle 210.

[0242] When using the component 21, the liquid to be treated is made to flow into the outer shell body 218 of the outer shell 214 from the first port 224 and flow out of the liquid to be treated from the third port 222c. Thus, the liquid to be treated is perfusion outside the membranes of the individual hollow fiber membranes 211 in the region from the pouring portion 216 inside the outer shell 214 to the second end portion 210b side of the hollow fiber membrane bundle 210. There is no particular limitation on the structure for making the liquid to be treated flow in from the first port 224 and flow out from the third port 222c. For example, it may be a structure in which a pump is connected to the first port 224 to pump the liquid to be treated, or a structure in which a pump is connected to the third port 222c to suck the liquid to be treated.

[0243] The liquid to be treated flowing in from the first port 224 flows through the space 226 between the hollow fiber membrane bundle 210 inside the outer shell 214 and the inner wall surface of the outer shell body 218, goes around to the opposite side of the first port 224 of the hollow fiber membrane bundle 210, and at the same time flows into the spaces between the individual hollow fiber membranes 211 toward the central portion of the hollow fiber membrane bundle 210 and moves toward the third port 222c side. By connecting a vacuum pump to the second port 220c of the first lid portion 220 to evacuate, the dissolved gas in the liquid to be treated between the individual hollow fiber membranes 211 is sucked into the membranes of the hollow fiber membranes 211 and flows out from the second port 220c. Therefore, the liquid to be treated can be degassed.

[0244] In the component 21, the hollow fiber membranes 211 having an outer diameter of 350 μm or less and a Gurley stiffness of 15 mN or more are bundled to form the hollow fiber membrane bundle 210. Thus, by bundling the hollow fiber membranes 211 having an outer diameter below a specific value and excellent rigidity, the shape retention of the hollow fiber membrane bundle 210 is excellent. Therefore, even if the component becomes larger, the hollow fiber membranes 211 become longer, and the flow rate of the liquid to be treated becomes faster, the shape of the hollow fiber membrane bundle 210 is difficult to distort. Since the shape is not easily distorted, a decrease in degassing performance can be suppressed.

[0245] There is no particular limitation on the manufacturing method of the component 21. For example, the following methods can be cited.

[0246] For example, as Figure 9As shown, a long strip of hollow fiber membrane 211A is repeatedly folded in the opposite directions in an alternating manner multiple times to form a U-shape, and a strip-shaped hollow fiber membrane sheet 213 is formed. At both end sides in the width direction of the hollow fiber membrane sheet 213, the hollow fiber membrane 211A is woven in the length direction of the membrane sheet by the warp 228, and the portions extending in the width direction of the hollow fiber membrane 211A are connected to each other. Next, as Figure 10 shown, with the width direction of the hollow fiber membrane sheet 213 as the axis, the hollow fiber membrane sheet 213 is wound into a cylindrical shape. Next, as Figure 11 shown, the cylindrical hollow fiber membrane sheet 213 is inserted into the housing body 218, and by using a known method such as the centrifugal method, the resin 252 is poured to fix one end of the hollow fiber membrane sheet 213 to the side of the first opening end 218a of the housing body 218. At this time, the U-shaped folded-back portion of the hollow fiber membrane 211A on the side fixed by the poured resin 252 on the hollow fiber membrane sheet 213, and a part of the poured resin 252 protrude from the housing body 218. Then, along the plane X2 of the first opening end 218a of the housing body 218, the protruding portions of the hollow fiber membrane sheet 213 and the poured resin 252 are cut off. Thus, a cylindrical hollow fiber membrane bundle 210 is formed in which the end faces 211a of the respective hollow fiber membranes 211 folded in a U-shape are fixed to the housing body 218 by the pouring portion 216 in an open state. Next, the first cover portion 220 and the second cover portion 222 are installed at both end portions of the housing body 218, and thus the assembly 21 is obtained.

[0247] As described above, in the external perfusion type hollow fiber membrane assembly according to the second embodiment of the present invention, hollow fiber membranes having a Gurley stiffness of 15 mN or more are bundled to form a hollow fiber membrane bundle. By using hollow fiber membranes having excellent rigidity in this way, even if the assembly becomes larger and the hollow fiber membranes become longer, the shape retention of the hollow fiber membrane bundle can be ensured, and the decrease in the degassing efficiency can be suppressed regardless of the direction of flow of the liquid to be treated, such as the vertical direction or the horizontal direction.

[0248] In addition, the external perfusion type hollow fiber membrane assembly according to the second embodiment of the present invention is not limited to the assembly 21 described above. For example, the external perfusion type hollow fiber membrane assembly according to the second embodiment of the present invention may also be such that each hollow fiber membrane forming the hollow fiber membrane bundle is not folded into a U-shape, and the second end opposite to the first end fixed to the pouring portion is a free end whose opening end is blocked by resin or the like.

[0249] In the external perfusion type hollow fiber membrane assembly according to the second embodiment of the present invention, the two end portions in the length direction of the hollow fiber membrane bundle may be fixed to the housing by the pouring portion.

[0250] The external perfusion type hollow fiber membrane assembly according to the second embodiment of the present invention may also be Figure 12The exemplary external perfusion type hollow fiber membrane module 22 (hereinafter also referred to as "module 22"). Figure 12 In Figure 8 the same parts have the same symbols, and their descriptions are omitted.

[0251] Module 22 includes: a hollow fiber membrane bundle 210A and a housing 214A. The hollow fiber membrane bundle 210A is housed in the housing 214A, and the first end 210a and the second end 210b in the longitudinal direction of the hollow fiber membrane bundle 210A are fixed in the housing 214A by casting parts 216A and 216B, respectively.

[0252] The housing 214A includes: a cylindrical housing body 218A, a first cover portion 220 provided on the side of the first open end 218a in the longitudinal direction of the housing body 218A, and a second cover portion 222 provided on the side of the second open end 218b of the housing body 218A. The housing 214A is formed into a cylindrical appearance by the housing body 218A, the first cover portion 220, and the second cover portion 222.

[0253] On the portion of the housing body 218A of the housing 214A near the first open end 218a, similar to the housing 214, a first port 224 that protrudes outward from the outer peripheral surface of the housing body 218A and communicates with the inside of the housing body 218A is provided. In addition, on the portion of the housing body 218A of the housing 214A near the second open end 218b, a fourth port 230 that protrudes from the outer peripheral surface of the housing body 218A to the opposite side of the first port 224 and communicates with the inside of the housing body 218A is provided.

[0254] The shape of the fourth port 230 is not particularly limited, and examples thereof include a cylindrical shape, a polygonal cylindrical shape, etc.

[0255] The hollow fiber membrane bundle 210A is formed by bundling a plurality of hollow fiber membranes 211 into a cylindrical shape while being aligned in one direction.

[0256] The first open end 218a of the housing body 218A is blocked by the casting part 216A, and the first end 210a in the longitudinal direction of the hollow fiber membrane bundle 210A is buried in the casting part 216A and fixed to the portion on the side of the first open end 218a inside the housing body 218A. The end face 216a on the side of the first cover portion 220 of the casting part 216A is flush with the first open end 218a of the housing body 218A. At the end face 216a of the casting part 216A, the end faces 211a on the side of the first open end 218a of the respective hollow fiber membranes 211 are in an open state. Due to the end faces 211a on the side of the first open end 218a of the respective hollow fiber membranes 211 being in an open state, the space inside the membranes of the respective hollow fiber membranes 211 and the space on the side of the first cover portion 220 of the casting part 216A inside the housing 214A are in a communicating state.

[0257] In addition, the second open end 218b of the housing body 218A is blocked by the casting portion 216B, and the second end portion 210b of the hollow fiber membrane bundle 210A is buried in the casting portion 216B and fixed to the portion on the second open end 218b side within the housing body 218A. The end face 216b on the side of the second cover portion 222 of the casting portion 216B is flush with the second open end 218b of the housing body 218A. At the end face 216b of the casting portion 216B, the end faces 211c on the second open end 218b side of the respective hollow fiber membranes 211 are in an open state. Due to the end faces 211c on the second open end 218b side of the respective hollow fiber membranes 211 being in an open state, the space inside the membranes of the respective hollow fiber membranes 211 and the space on the side of the second cover portion 222 of the casting portion 216B within the housing 214A are in a communicating state.

[0258] The inner wall surface of the housing body 218A is separated from the hollow fiber membrane bundle 210A, and a space 226 is formed outside the hollow fiber membrane bundle 210A within the housing 214A.

[0259] When using the assembly 22, for example, the liquid to be treated is made to flow into the housing body 218A of the housing 214A from the first port 224, and the liquid to be treated flows out from the fourth port 230. Thus, within the region between the casting portion 216A and the casting portion 216B within the housing 214A, the liquid to be treated is poured outside the membranes of the respective hollow fiber membranes 211. Then, a vacuum pump is connected to the second port 220c of the first cover portion 220 and the third port 222c of the second cover portion 222 to evacuate the air. Thereby, the dissolved gas in the liquid to be treated between the respective hollow fiber membranes 211 is sucked into the membranes of the hollow fiber membranes 211 and flows out from the second port 220c and the third port 222c. Therefore, the liquid to be treated can be degassed.

[0260] In the assembly 22 as well, the hollow fiber membranes 211 with a Gurley stiffness of 15 mN or more are bundled to form the hollow fiber membrane bundle 210A. Thus, by bundling the hollow fiber membranes 211 with an outer diameter below a specific value and excellent rigidity, the shape retention of the hollow fiber membrane bundle 210A is excellent. Therefore, during manufacturing or use, the shape of the hollow fiber membrane bundle 210A is difficult to distort. Since the shape is not easily distorted, a decrease in degassing performance can be suppressed.

[0261] [Third Embodiment]

[0262] The external perfusion type hollow fiber membrane module according to the third embodiment of the present invention includes: a cylindrical hollow fiber membrane bundle with a cavity formed inside, which is formed by bundling a plurality of hollow fiber membranes, and a housing that houses the hollow fiber membrane bundle. The first end portion in the length direction of the hollow fiber membrane bundle is fixed in the housing by a casting portion in a state where the end faces of the respective hollow fiber membranes are open, and the second end portion of the hollow fiber membrane bundle, which is opposite to the first end portion, is a free end. In the external perfusion type hollow fiber membrane module according to the third embodiment of the present invention, only the hollow fiber membrane bundle is provided in the region between the casting portion in the housing and the second end portion of the hollow fiber membrane bundle.

[0263] The external perfusion type hollow fiber membrane module according to the third embodiment of the present invention can be used as a component for degassing to remove the gas dissolved in the external perfusion liquid or for supplying gas to the external perfusion liquid. As the use of the external perfusion type hollow fiber membrane module according to the third embodiment of the present invention, there is no particular limitation, and examples include inkjet ejection devices such as inkjet printers and color filter manufacturing devices.

[0264] An example of the external perfusion type hollow fiber membrane module according to the third embodiment of the present invention will be described below. In addition, the dimensions of the illustrated figures in the following description are merely examples, and the third embodiment of the present invention is not limited thereto, and appropriate changes can be made within the scope of not changing its gist.

[0265] The external perfusion type hollow fiber membrane module 31 (hereinafter also referred to as "module 31") according to the third embodiment of the present embodiment, as Figure 14 shown, includes a hollow fiber membrane bundle 310 and a housing 314. The hollow fiber membrane bundle 310 is housed in the housing 314, and the first end portion 310a in the length direction of the hollow fiber membrane bundle 310 is fixed in the housing 314 by a casting portion 316. The second end portion 310b of the hollow fiber membrane bundle 310, which is opposite to the first end portion 310a, is a free end.

[0266] The housing 314 includes: a cylindrical housing body 318, a first lid portion 320 provided on the side of the first open end 318a in the length direction of the housing body 318, and a second lid portion 322 provided on the side of the second open end 318b of the housing body 318. The housing 314 is formed into a cylindrical appearance by the housing body 318, the first lid portion 320, and the second lid portion 322.

[0267] As the housing in the external perfusion type hollow fiber membrane module according to the third embodiment of the present invention, preferably, as in this example, it is a housing having a cylindrical appearance with a cylindrical housing body. In addition, in the third embodiment of the present invention, it is not limited to a housing having a cylindrical appearance, and it may be, for example, a housing having a polygonal columnar appearance with a polygonal tubular housing body.

[0268] In a portion near the first open end 318a of the housing body 318 of the housing 314, a first port 324 is provided which protrudes outward from the outer peripheral surface of the housing body 318 and communicates with the inside of the housing body 318. The first port 324 is cylindrical and serves as a liquid inlet / outlet port for allowing liquid to flow in and out of the housing body 318. The shape of the first port 324 is not limited to cylindrical, and for example, it can also be a polygonal cylindrical shape or the like.

[0269] The first lid portion 320 includes: a circular flat plate portion 320a, a cylindrical portion 320b that protrudes toward the housing body 318 around the entire outer peripheral edge of the flat plate portion 320a, and a second port 320c that protrudes outward from the central portion of the flat plate portion 320a. The first end portion 319a of the housing body 318 is inserted into the cylindrical portion 320b, and the first lid portion 320 is mounted on the housing body 318. The second port 320c is located on the central axis L31 of the housing 314.

[0270] The second port 320c is cylindrical and serves as a gas outlet port for allowing gas to flow out of the housing 314 or a gas inlet port for allowing gas to flow in. The shape of the second port 320c is not limited to cylindrical, and for example, it can also be a polygonal cylindrical shape or the like.

[0271] The second lid portion 322 includes: a circular flat plate portion 322a, a cylindrical portion 322b that protrudes toward the housing body 318 around the entire outer peripheral edge of the flat plate portion 322a, and a third port 322c that protrudes outward from the central portion of the flat plate portion 322a. The second end portion 319b of the housing body 318 is inserted into the cylindrical portion 322b, and the second lid portion 322 is mounted on the housing body 318. The third port 322c is located on the central axis L31 of the housing 314.

[0272] The third port 322c is cylindrical and serves as a liquid inlet / outlet port for allowing liquid to flow in and out of the housing 314. The shape of the third port 322c is not limited to cylindrical, and for example, it can also be a polygonal cylindrical shape or the like. In order to better remove air bubbles in the housing 314, the flat plate portion 322a can also be conical.

[0273] The size of the housing 314 can be set appropriately. For example, in the case of having a cylindrical housing body 318, the outer diameter of the housing body 318 can be 3 to 15 cm, and the length can be 5 to 50 cm. The outer diameter and length of the housing body 318 can also be changed appropriately.

[0274] As the material for forming the housing 314, a material that can preferably ensure sufficient mechanical strength and durability can be cited, for example, the same as those cited for the housing 112 in the first embodiment. As the material for forming the housing 314, one type can be used alone, or two or more types can be used in combination.

[0275] The hollow fiber membrane bundle 310, asFigure 14 and Figure 15 As shown in Figure 15 , it is formed by bundling a plurality of hollow fiber membranes 311 into a cylindrical shape with a hollow portion 312 inside. The shape of the hollow fiber membrane bundle 310 is preferably cylindrical as in this example. In addition, the shape of the hollow fiber membrane bundle 310 is not limited to a cylindrical shape, and may also be an elliptical cylinder shape, a square shape, etc.

[0276] The hollow fiber membrane bundle 310 is housed in the housing body 318 of the housing 314, and the first end portion 310a in the length direction of the hollow fiber membrane bundle 310 is fixed to the end portion on the side of the first opening end 318a of the housing body 318 by the casting portion 316. The plurality of hollow fiber membranes 311 forming the hollow fiber membrane bundle 310 are bundled in a state where the central portion in the length direction is folded into a U shape, and both end faces 311a on both sides of each hollow fiber membrane 311 are buried in the casting portion 316 and fixed in an open state.

[0277] In the third embodiment of the present invention, preferably as in this example, a plurality of hollow fiber membranes are bundled in a state where the central portion in the length direction is folded into a U shape, and both end faces on both sides of each hollow fiber membrane are fixed in the housing by the casting portion in an open state. By bundling each hollow fiber membrane in this state, even if the number of hollow fiber membranes is small, the filling rate of the hollow fiber membrane bundle can be sufficiently increased, and the manufacturing efficiency is improved. In addition, since it is easy to maintain the self-supporting state of the hollow fiber membrane bundle, it is easy for the liquid to enter between the hollow fiber membranes of the entire hollow fiber membrane bundle, and the efficiency of degassing or supplying gas is improved.

[0278] The second end portion 310b, which is located on the side opposite to the first end portion 310a of the hollow fiber membrane bundle 310 and is formed by the U-shaped turning-back portion of each hollow fiber membrane 311, is not fixed to the housing 314 and is a free end. Thus, it is easy for the liquid to enter between the hollow fiber membranes 311 of the entire hollow fiber membrane bundle 310, so that the degassing or supplying of the liquid can be efficiently performed.

[0279] The first opening end 318a of the housing body 318 is blocked by the casting portion 316. The end face 316a on the side of the first cover portion 320 of the casting portion 316 is flush with the first opening end 318a of the housing body 318, and on the end face 316a of the casting portion 316, both end faces 311a of each hollow fiber membrane 311 are in an open state. A space is formed on the side of the first cover portion 320 of the end face 316a of the casting portion 316 in the housing 314, and the space from the casting portion 316 in the housing body 318 to the second end portion 310b side of the hollow fiber membrane bundle 310 is separated by the casting portion 316. By both end faces 311a of each hollow fiber membrane 311 being in an open state, the inside of each hollow fiber membrane 311 is in communication with the space on the side of the first cover portion 320 of the casting portion 316 in the housing 314.

[0280] In the hollow fiber membrane bundle 310 housed in the housing 314, each hollow fiber membrane 311 is bundled in a cylindrical shape around the central axis L31 of the housing 314, and a cylindrical cavity 312 is formed inside the hollow fiber membrane bundle 310. The cavity 312, the second port 320c, and the third port 322c are all located on the central axis L31 of the housing 314. In addition, the inner wall surface of the housing body 318 is separated from the hollow fiber membrane bundle 310, and a space 326 is formed outside the hollow fiber membrane bundle 310 in the housing 314.

[0281] In the assembly 31, in the region between the end face 316b of the casting part 316 in the housing 314 on the second end 310b side of the hollow fiber membrane bundle 310 and the second end 310b of the hollow fiber membrane bundle 310, only the hollow fiber membrane bundle 310 is provided. That is, nothing is disposed in the cavity 312 inside the cylindrical hollow fiber membrane bundle 310. Thus, in the entire hollow fiber membrane bundle 310, the liquid flowing between the respective hollow fiber membranes 311 moves unobstructed between the outer space 326 of the cylindrical hollow fiber membrane bundle 310 and the inner cavity 312 of the hollow fiber membrane bundle 310.

[0282] In the hollow fiber membrane bundle 310, the respective hollow fiber membranes 311 may also be bundled in a state of being connected to each other by the warp yarns 328. Specifically, in a portion near the U-shaped folded-back portion of each hollow fiber membrane 311, in a direction perpendicular to the central axis L31, that is, in a direction perpendicular to the length direction of each hollow fiber membrane 311, a plurality of hollow fiber membranes 311 are woven by the warp yarns 328, whereby the respective hollow fiber membranes 311 are connected to each other. In the third embodiment of the present invention, it is preferable to bundle the respective hollow fiber membranes in a state of being connected to each other by the warp yarns in this way. Thereby, it is possible to suppress the dispersion of the respective hollow fiber membranes 311 forming the hollow fiber membrane bundle 310, and the hollow fiber membrane bundle 310 is easily maintained in a self-supporting state. When the viscosity of the perfusion liquid is high, the hollow fiber membranes 311 are particularly likely to disperse, and it is difficult to ensure the self-supporting property of the hollow fiber membrane bundle 310. Therefore, the method of connecting the hollow fiber membranes by the warp yarns is particularly effective when the viscosity of the perfusion liquid is high, for example, when the liquid is ink or the like.

[0283] As a method of connecting a plurality of hollow fiber membranes by the warp yarns, there is no particular limitation, and for example, a method of chain stitch type weaving can be cited.

[0284] In the second end portion 310b of the hollow fiber membrane bundle 310, in the direction of the central axis L31 of the outer shell 314, the positions of the end portions 311b formed by the U-shaped folded-back portions of the respective hollow fiber membranes 311 are aligned with each other. That is, the lengths of the portions of the respective hollow fiber membranes 311 exposed to the casting portion 316 are aligned with each other. The alignment of the positions of the end portions 311b of the respective hollow fiber membranes 311 means that, with respect to the average value of the lengths of the portions of all the hollow fiber membranes 311 forming the hollow fiber membrane bundle 310 exposed to the casting portion 316, the error of this length of each hollow fiber membrane 311 is ±5%.

[0285] In the third embodiment of the present invention, preferably, in the second end portion of the hollow fiber membrane bundle, the end portions of the respective hollow fiber membrane bundles are aligned with each other. Thereby, it is easy to suppress local uneven flow of the liquid in the outer shell. In addition, it is easy to suppress the deformation of the shape of the hollow fiber membrane bundle, the liquid easily enters the entire hollow fiber membrane bundle, and the efficiency of degassing or gas supply is improved.

[0286] As the hollow fiber membrane 311, a gas-permeable hollow fiber membrane that can permeate gas between the hollow portion inside the membrane and the outside of the membrane is preferably used. In addition, from the viewpoints of excellent strength and more efficient degassing or gas supply, as the hollow fiber membrane 311, a composite hollow fiber membrane having a gas-permeable homogeneous layer and a porous support layer supporting the homogeneous layer is more preferably used.

[0287] As the structure of the composite hollow fiber membrane, a double-layer structure in which a porous support layer is provided inside or outside the homogeneous layer or a three-layer structure in which porous support layers are provided on both the inside and outside of the homogeneous layer is preferably used. From the viewpoints of strength and degassing or gas supply performance, a three-layer structure is more preferably used.

[0288] The material forming the homogeneous layer is as described in the first embodiment. As the material forming the homogeneous layer in the third embodiment, from the viewpoints of excellent degassing or gas supply performance during high-flow perfusion of the liquid and excellent drug resistance, a polyolefin resin is preferably used, and a low-density polyethylene resin is more preferably used from the viewpoint of excellent film-forming properties.

[0289] The material forming the porous support layer is as described in the first embodiment. From the viewpoint of easily ensuring the self-supporting property of the hollow fiber membrane bundle, as the material forming the homogeneous layer in the third embodiment, high-density polyethylene showing the same MFR value as the homogeneous layer is preferably used.

[0290] The pore diameter of the porous support layer is preferably 0.01 to 1 μm.

[0291] The porosity of the porous support layer is preferably 30 to 80% by volume. If the porosity is above the lower limit value of the above range, the degassing or gas supply performance is excellent. If the porosity is below the upper limit value of the above range, the mechanical strength such as the pressure resistance of the hollow fiber membrane is improved.

[0292] The outer diameter of the hollow fiber membrane 311 is preferably 350 μm or less, more preferably 150 - 330 μm, and still more preferably 200 - 300 μm. If the outer diameter of the hollow fiber membrane 311 is within the above range, a more efficient flow path can be formed between the hollow fiber membranes 311 in the housing 314.

[0293] The inner diameter of the hollow fiber membrane 311 is preferably 100 μm or more, more preferably 120 - 250 μm, and still more preferably 130 - 200 μm. If 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 housing 314, and it is easy to maintain the performance and durability of degassing or air supply.

[0294] The film thickness of the hollow fiber membrane 311 is preferably 20 - 70 μm, more preferably 25 - 55 μm. If the film thickness of the hollow fiber membrane 311 is below the above upper limit value, the durability is excellent when the inside of the hollow fiber membrane 311 in the housing 314 is repeatedly decompressed or pressurized. If the film thickness of the hollow fiber membrane 311 is above the above lower limit value, it is easy to maintain good degassing or air supply performance.

[0295] In addition, the calculation method of the film thickness of the hollow fiber membrane and the measurement methods of the inner diameter and outer diameter of the hollow fiber membrane are as described in the first embodiment.

[0296] As long as the film thickness is within the above range, the thicknesses of the homogeneous layer and the porous support layer can be appropriately set. The thickness of the homogeneous layer is preferably 0.3 - 2 μm, more preferably 0.5 - 1.2 μm.

[0297] The measurement methods of the thicknesses of the homogeneous layer and the porous support layer are as described in the first embodiment.

[0298] In the hollow fiber membrane 311, from the perspective of the operability during the manufacture of the component, the breaking strength is preferably 0.5 N / fil or more and the elongation at break is preferably 50% or more, more preferably the breaking strength is 0.8 - 5 N / fil and the elongation at break is 70 - 400%, and still more preferably the breaking strength is 1 - 4 N / fil and the elongation at break is 140 - 300%.

[0299] The measurement methods of the breaking strength and the elongation at break are as described in the first embodiment.

[0300] On the cross - section obtained by cutting the housing 314 in a direction perpendicular to the length direction of the hollow fiber membrane bundle 310, the filling rate of the hollow fiber membrane bundle 310 in the housing 314 is preferably 20 - 50%, more preferably 30 - 45%. If the filling rate of the hollow fiber membrane is above the lower limit value, it is easy to suppress the liquid uneven flow in the housing. If the filling rate of the hollow fiber membrane is below the upper limit value, the filling of the hollow fiber membrane becomes easy and the performance of degassing or air supply is improved.

[0301] In addition, the packing ratio is the ratio (%) of the total cross-sectional area of the hollow fiber membranes 311 that form the hollow fiber membrane bundle 310 to the cross-sectional area inside the outer shell 314 on a cross-section obtained by cutting the outer shell 314 in a direction perpendicular to the length direction of the hollow fiber membrane bundle 310.

[0302] The Gurley stiffness of the hollow fiber membrane is preferably 10 mN or more, more preferably 15 - 30 mN, and still more preferably 18 - 25 mN. If the Gurley stiffness of the hollow fiber membrane is at or above the lower limit value 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 the decrease in the efficiency of degassing or gas supply. If the Gurley stiffness of the hollow fiber membrane is at or below the upper limit value of the above range, there is less membrane distortion that occurs as the membrane length increases when forming the membrane bundle, and the module can be formed in an aligned state.

[0303] In addition, the method for measuring the Gurley stiffness of the hollow fiber membrane is as described in the first embodiment.

[0304] The method for manufacturing the module 31 is not particularly limited, and examples thereof include the following methods.

[0305] For example, as Figure 16 shown, a long strip of hollow fiber membrane 311A is repeatedly folded in a U-shape in opposite directions multiple times to form a belt-like hollow fiber membrane sheet 313. On both end sides in the width direction of the hollow fiber membrane sheet 313, the hollow fiber membranes 311A are woven in the length direction of the sheet by the warp yarns 328 to connect the portions extending in the width direction of the hollow fiber membranes 311A to each other. Then, as Figure 17 shown, the hollow fiber membrane sheet 313 is wound around a cylindrical mandrel 350. As Figure 18 shown, the hollow fiber membrane sheet 313 in the state of being wound around the mandrel 350 is inserted into the outer shell body 318. After the mandrel 350 is withdrawn, by a known method such as the centrifugation method, one end of the hollow fiber membrane sheet 313 is fixed to the first opening end 318a side of the outer shell body 318 with a casting resin 352. At this time, the U-shaped folded-back portion of the hollow fiber membrane 311A on the side fixed by the casting resin 352 on the hollow fiber membrane sheet 313 and a part of the casting resin 352 protrude from the outer shell body 318. Then, along the plane X3 of the first opening end 318a of the outer shell body 318, the protruding portions of the hollow fiber membrane sheet 313 and the casting resin 352 are cut off. Thus, the end faces 311a of the hollow fiber membranes 311 folded in a U-shape are fixed to the outer shell body 318 in an open state by the cast portion 316, forming a cylindrical hollow fiber membrane bundle 310 with a hollow portion 312 inside. Then, the first cover portion 320 and the second cover portion 322 are installed at both ends of the outer shell body 318, thereby obtaining the module 31.

[0306] The mechanism of component 31 is described below. Component 31 can be used, for example, as follows.

[0307] In component 31, liquid is made to flow into the housing body 318 of the housing 314 from the first port 324 and flow out of the liquid from the third port 322c. Thus, in the region from the casting portion 316 in the housing 314 to the second end portion 310b side of the hollow fiber membrane bundle 310, the liquid is poured outside the membranes of the respective hollow fiber membranes 311.

[0308] As the structure for making the liquid flow in from the first port 324 and flow out from the third port 322c, there is no particular limitation. For example, a pump can be connected to the first port 324 to pump the liquid, or a pump can be connected to the third port 322c to suck the liquid.

[0309] The liquid flowing in from the first port 324 flows through the space 326 between the hollow fiber membrane bundle 310 in the housing 314 and the inner wall surface of the housing body 318, and while going around to the opposite side of the first port 324 of the hollow fiber membrane bundle 310, it flows through between the respective hollow fiber membranes 311 from the outside to the inner cavity portion 312 of the hollow fiber membrane bundle 310. For example, by connecting a vacuum pump to the second port 320c of the first cover portion 320 to evacuate, the dissolved gas in the liquid flowing through between the respective hollow fiber membranes 311 is sucked into the membranes of the hollow fiber membranes 311 and flows out from the second port 320c, so that the liquid can be degassed. In addition, by connecting a gas supply pump to the second port 320c of the first cover portion 320 and supplying gas, gas can be supplied to the liquid flowing through between the respective hollow fiber membranes 311 through the respective hollow fiber membranes 311.

[0310] In component 31, in the region between the casting portion 316 in the housing 314 and the second end portion 310b of the hollow fiber membrane bundle 310, only the hollow fiber membrane bundle 310 is provided, and nothing is disposed in the cavity portion 312 inside the cylindrical hollow fiber membrane bundle 310. Thus, in the entire hollow fiber membrane bundle 310 in the housing 314, the liquid flowing through between the respective hollow fiber membranes 311 can smoothly move from the outer space 326 of the hollow fiber membrane bundle 310 to the inner cavity portion 312 without obstruction. Therefore, even if the component becomes larger and the flow rate of the poured liquid becomes faster, in the entire hollow fiber membrane bundle 310, the liquid easily flows from the outer space 326 of the hollow fiber membrane bundle 310 to the inner cavity portion 312. Therefore, partial flow of the liquid in the space 326 in the housing 314 can be suppressed, and thus a decrease in the efficiency of degassing or gas supply can be suppressed.

[0311] As described above, in the external perfusion type hollow fiber membrane module according to the third embodiment of the present invention, in the region between the casting portion in the outer shell and the second end of the hollow fiber membrane bundle, only the hollow fiber membrane bundle is provided. Thus, within the entire hollow fiber membrane bundle, between the outside of the cylindrical hollow fiber membrane bundle and the hollow portion inside the hollow fiber membrane bundle, the liquid can move through the spaces between the respective hollow fiber membranes without obstruction. Therefore, even if the module is enlarged and the flow rate of the perfusion liquid is increased, the liquid flow deviation within the outer shell can be suppressed, and the reduction in the efficiency of degassing or gas supply can be suppressed.

[0312] In addition, the external perfusion type hollow fiber membrane module according to the third embodiment of the present invention is not limited to the module 31 described above. For example, the external perfusion type hollow fiber membrane module according to the third embodiment of the present invention may also be such that each hollow fiber membrane forming the hollow fiber membrane bundle is not folded into a U shape, and the second end opposite to the first end fixed to the casting portion has an open end buried in resin or the like and is a free end in a blocked state.

[0313] The external perfusion type hollow fiber membrane module of the present invention may also be a combination of the first embodiment and the second embodiment, may also be a combination of the first embodiment and the third embodiment, may be a combination of the second embodiment and the third embodiment, or may be a combination of the first embodiment, the second embodiment, and the third embodiment.

[0314] The present invention will be specifically described below by way of examples, but the present invention is not limited to the following description.

[0315] [Melt Flow Rate (MFR)]

[0316] The MFR of the resin is measured according to Condition E of ASTM D1238 at a test temperature of 190 °C and a test load of 21.18 N.

[0317] [Gurley Stiffness of Fabric]

[0318] The Gurley stiffness of the hollow fiber membrane is measured using a Gurley stiffness tester according to JIS L 1096A method. A measurement sample is a bundle of 7 hollow fiber membrane bundles folded in units of 32 (32 fil) hollow fiber membranes, and the size of the measurement sample is 25 - 26 mm in width and 51 mm in length.

[0319] [Example A1]

[0320] Fabricate an external perfusion type hollow fiber membrane module with the same embodiment as the Figure 1 illustrated module 11.

[0321] As the hollow fiber membrane 111, a composite hollow fiber membrane having a three-layer structure is used, in which a porous support layer formed of high-density polyethylene resin (MFR: 1.35 g / 10 min) is provided on the inner and outer sides of a homogeneous layer formed of metallocene low-density polyethylene resin (MFR: 1.0 g / 10 min). The outer diameter of the composite hollow fiber membrane is 197 μm, the inner diameter is 133 μm, and the membrane thickness is 32 μm. The Gurley stiffness of the composite hollow fiber membrane is 5 mN.

[0322] The inner diameter of the housing body 116 of the housing 112 is 52 mm. The hollow fiber membrane bundle 110 is fixed in the housing 112 by the casting portion 124, and the effective membrane area is 1.42 m 2 . On a cross section obtained by cutting the housing 112 in a direction perpendicular to the length direction of the hollow fiber membrane bundle 110, the filling rate of the hollow fiber membrane bundle 110 in the housing 112 is 30%.

[0323] As the anti-channeling body 114, a ring having a rectangular cross-sectional shape with a width D1 of 5 mm, an inner diameter of 46 mm, and a protruding height H1 of 3 mm along the direction of the central axis L11 is used. The distance d12 from the position of the central axis L12 of the first port 122 to the anti-channeling body 114 is 9 mm, and d12 / d11 is 0.075.

[0324] [Example A2]

[0325] The outer diameter of the composite hollow fiber membrane is changed to 283 μm, the inner diameter is 199 μm, the Gurley stiffness is 20 mN, and the effective membrane area of the hollow fiber membrane bundle 110 fixed in the housing 112 by the casting portion 124 is 1.15 m 2 . The filling rate of the hollow fiber membrane bundle 110 in the housing 112 is 30%. Except for this, an external perfusion type hollow fiber membrane module is produced in the same manner as in Example A1.

[0326] [Example A3]

[0327] An external perfusion type hollow fiber membrane module is produced in the same manner as in Example A1, except that no anti-channeling body is provided in the housing.

[0328] [Example A4]

[0329] An external perfusion type hollow fiber membrane module is produced in the same manner as in Example A2, except that no anti-channeling body is provided in the housing.

[0330] [Evaluation of degassing performance]

[0331] Water was passed through the external perfusion type hollow fiber membrane module for each example. Water flowed in from the first port (liquid inlet port) and flowed out from the third port (liquid outlet port). A vacuum pump was connected to the second port (vent port), and degassing was performed under a vacuum of -88 kPa. The temperature of the water was 25 °C. The flow rate of the externally perfused water was changed to 250, 500, 750, 1000, 1250, and 1500 mL / min, and the dissolved oxygen removal rate in the treated water after degassing was measured at each flow rate.

[0332] The dissolved oxygen content M1 (mg / L) of the raw water before degassing treatment and the dissolved oxygen content M2 (mg / L) of the treated water after degassing treatment were measured respectively using an optical DO Meter FD 0925 (Central Kagaku Corporation), and the dissolved oxygen removal rate was obtained according to the following formula (2).

[0333] Dissolved oxygen removal rate (%) = [(M1 - M2) / M1] × 100 ··· (2)

[0334] The results are as Figure 7 shown.

[0335] As Figure 7 shown, in the modules of Examples A1, A2, and A4 that satisfy any one or both of having a short-circuit prevention body provided and the Gurley stiffness of the hollow fiber membrane being 15 mN or more, compared with the module of Example A3 that does not have a short-circuit prevention body provided and the Gurley stiffness of the hollow fiber membrane being less than 15 mN, the dissolved oxygen removal rate of the treated water is high and the degassing performance is high.

[0336] [Example A5]

[0337] The inner diameter of the housing body 116 was 48 mm, the inner diameter of the short-circuit prevention body 114 was 46 mm, the protruding height H1 was 3 mm, and the effective membrane area of the hollow fiber membrane bundle 110 was 1.63 m 2 , and d12 / d11 was 0.060. Except for this, an external perfusion type hollow fiber membrane module was fabricated in the same manner as in Example A1.

[0338] [Example A6]

[0339] The outer diameter of the composite hollow fiber membrane was changed to 283 μm, the inner diameter was changed to 199 μm, the Gurley stiffness was 20 mN, and the effective membrane area of the hollow fiber membrane bundle 110 was 1.21 m 2 . Except for this, an external perfusion type hollow fiber membrane module was fabricated in the same manner as in Example A5.

[0340] [Example A7]

[0341] An external perfusion type hollow fiber membrane module was fabricated in the same manner as in Example A5 except that no short-circuit prevention body was provided inside the housing.

[0342] [Example A8]

[0343] An externally perfused hollow fiber membrane module was produced in the same manner as in Example A6, except that no short-range prevention body was provided inside the housing.

[0344] [Evaluation of degassing performance]

[0345] Water was passed through the externally perfused hollow fiber membrane module of each example. The water flowed in from the liquid inlet port and out from the liquid outlet port. A vacuum pump was connected to the second port (vent port), and vacuum degassing was performed at a vacuum degree of -88 kPa. The temperature of the water was 25 °C. The flow rate of the externally perfused water was 1500 mL / min. The dissolved oxygen removal rate in the treated water after degassing at each flow rate was measured in Tests (i) to (iv) with the following water passing methods. The dissolved oxygen removal rate was obtained according to the above formula (2).

[0346] Test (i): The module was set longitudinally with the first port 122 on the lower side and the third port 120c on the upper side. The first port 122 was the liquid inlet port, and the third port 120c was the liquid outlet port. Water was passed through (upflow, side-in).

[0347] Test (ii): The module was set longitudinally with the third port 120c on the lower side and the first port 122 on the upper side. The third port 120c was the liquid inlet port, and the first port 122 was the liquid outlet port. Water was passed through (upflow, cap-in).

[0348] Test (iii): The module was set horizontally with both the first port 122 and the third port 120c in the horizontal direction. The first port 122 was the liquid inlet port, and the third port 120c was the liquid outlet port. Water was passed through (side flow, side-in).

[0349] Test (iv): The module was set horizontally with both the first port 122 and the third port 120c in the horizontal direction. The third port 120c was the liquid inlet port, and the first port 122 was the liquid outlet port. Water was passed through (side flow, cap-in).

[0350] The results are as Figure 21 shown.

[0351] As Figure 21As shown, in the components of Example A5, A6, and A8 where either one or both of the Gurley fabric stiffness of the anti-short-range body and the hollow fiber membrane are 15 mN or more, compared with the component of Example A7 where the Gurley fabric stiffness of the anti-short-range body and the hollow fiber membrane is less than 15 mN, in any one of Tests (i) to (iv), the dissolved oxygen removal rate of the treated water is higher, the degassing performance is high, and the difference in the dissolved oxygen removal rate of each test method is less. Thus, in the components of Example A5, A6, and A8, regardless of whether the liquid to be treated flows in the vertical direction or the horizontal direction, the degassing performance is high.

[0352] [Production Example B1]

[0353] As the material for forming the homogeneous layer, metallocene low-density polyethylene (MFR: 1.0 g / 10 min) was used, and as the material for forming the porous support layer, high-density polyethylene (MFR: 1.35 g / 10 min) was used to produce a three-layer composite hollow fiber membrane A having porous support layers on both the inner and outer sides of the homogeneous layer. The outer diameter of the composite hollow fiber membrane is 197 μm, the inner diameter is 133 μm, and the membrane thickness is 32 μm. The Gurley fabric stiffness of the obtained composite hollow fiber membrane A is 5 mN.

[0354] [Production Examples B2 and B3]

[0355] Except for changing the materials for forming the homogeneous layer and the porous support layer, and the outer diameter, inner diameter, and membrane thickness of the hollow fiber membrane as shown in Table 1, composite hollow fiber membranes B to C were manufactured in the same manner as in Production Example B1. The Gurley fabric stiffness of the obtained composite hollow fiber membranes B and C is shown in Table 1.

[0356] [Production Example B4]

[0357] As the material for forming the homogeneous layer, linear low-density polyethylene (MFR: 18.5 g / 10 min) was used, and as the material for forming the porous support layer, high-density polyethylene (MFR: 5.2 g / 10 min) was used to produce a three-layer composite hollow fiber membrane D having porous support layers on both the inner and outer sides of the homogeneous layer. The outer diameter of the composite hollow fiber membrane D is 284 μm, the inner diameter is 206 μm, and the membrane thickness is 39 μm. The Gurley fabric stiffness of the obtained composite hollow fiber membrane D is 12 mN.

[0358] [Table 1]

[0359]

[0360] [Example B1]

[0361] Produce Figure 8Exemplary component 21. As the hollow fiber membrane 211, a composite hollow fiber membrane B is used. The inner diameter of the housing body 218 is 30 mm, the filling height is 135 mm, and the effective membrane area is 0.46 m 2 The filling rate of the cylindrical hollow fiber membrane bundle 210 is 30% and it is fixed in the housing 214.

[0362] [Example B2]

[0363] The hollow fiber membrane 211 is changed to a composite hollow fiber membrane C. The filling height is 135 mm, the effective membrane area is 0.43 m 2 The filling rate of the cylindrical hollow fiber membrane bundle 210 is 30% and it is fixed in the housing 214. Other than this, an external perfusion type hollow fiber membrane module is produced in the same manner as in Example B1.

[0364] [Examples B3 - B5]

[0365] The hollow fiber membrane 211 is changed to a composite hollow fiber membrane A. The diameter, height, effective membrane area, and filling rate of the hollow fiber membrane bundle 210 are changed as shown in Table 2. Other than this, an external perfusion type hollow fiber membrane module is produced in the same manner as in Example B1.

[0366] [Examples B6 - B7]

[0367] The hollow fiber membrane 211 is changed to a composite hollow fiber membrane D. The diameter, height, effective membrane area, and filling rate of the hollow fiber membrane bundle 210 are changed as shown in Table 2. Other than this, an external perfusion type hollow fiber membrane module is produced in the same manner as in Example B1.

[0368] [Table 2]

[0369]

[0370]

[0371] [Evaluation of degassing performance]

[0372] For each external perfusion type hollow fiber membrane module of each example, water is passed through such that it flows in from the first port and out from the third port. A vacuum pump is connected to the second port and degassing is performed under a reduced pressure of 100 Torr. The temperature of the water is 25°C. The flow rate of the externally perfused water is changed to 100, 200, 300, 400 mL / min, and the dissolved oxygen removal rate in the treated water after degassing is measured at each flow rate.

[0373] The dissolved oxygen removal rate is obtained according to the formula (2).

[0374] The results are as Figure 13 shown.

[0375] As Figure 13As shown, in the external perfusion type hollow fiber membrane modules of Examples B1 and B2 in which a hollow fiber membrane bundle is formed using a Hollie fabric stiffness of 15 mN or more, compared with the external perfusion type hollow fiber membrane modules of Examples B3 to B7 in which a hollow fiber membrane with a Hollie fabric stiffness of less than 15 mN is used, even when the flow rate of the water to be treated is high, the dissolved oxygen removal rate is high and the degassing performance is excellent.

[0376] [Example C1]

[0377] Fabricate Figure 14 the illustrated module 31. As the hollow fiber membrane 311, a composite hollow fiber membrane manufactured by Mitsubishi Chemical Corporation (product name “MHF130EPE”) is used. The inner diameter of the housing body 318 is 52 mm. Using a mandrel 350 with a diameter of 10 mm, a cylindrical hollow fiber membrane bundle 310 having a cylindrical cavity 312 with a diameter of 10 mm formed therein is fabricated, and is fixed in the housing 314 by a casting portion 316, and the effective membrane area is 1.45 m 2 . On a cross section obtained by cutting the housing 314 in a direction perpendicular to the length direction of the hollow fiber membrane bundle 310, the filling rate of the hollow fiber membrane bundle 310 in the housing 314 is 28%.

[0378] [Example C2]

[0379] Fabricate an external perfusion type hollow fiber membrane module 3101 which is the same embodiment as the module 31 of Example C1 except that the hollow fiber membrane bundle changes from a cylindrical shape to a columnar shape and no cavity is formed inside. Figure 20 On a cross section obtained by cutting the housing 3114 in a direction perpendicular to the length direction of the hollow fiber membrane bundle 3110, the filling rate of the hollow fiber membrane bundle 3110 in the housing 3114 is the same as the filling rate of Example C1.

[0380] [Example C3]

[0381] The inner diameter of the housing body 318 is 48 mm. As the hollow fiber membrane, the same composite hollow fiber membrane as in Example A2 with an outer diameter of 283 μm, an inner diameter of 199 μm, and a Hollie fabric stiffness of 20 mN is used to fabricate a columnar hollow fiber membrane bundle with no cavity formed inside and an effective membrane area of 1.21 m 2 . The filling rate of the hollow fiber membrane bundle is 30%. Except for this, an external perfusion type hollow fiber membrane module is fabricated in the same manner as in Example C1.

[0382] [Example C4]

[0383] The inner diameter of the housing body 318 is 48 mm. As the hollow fiber membrane, a composite hollow fiber membrane identical to that of Example A2 with an outer diameter of 283 μm, an inner diameter of 199 μm, and a Gurley stiffness of 20 mN is used. The filling rate of the cylindrical hollow fiber membrane bundle with a cylindrical cavity portion 312 having a diameter of 10 mm formed on the inner side is 30%. Other than this, an external perfusion type hollow fiber membrane module is produced in the same manner as in Example C1.

[0384] [Example C5]

[0385] The inner diameter of the housing body 318 is 48 mm. As the hollow fiber membrane, a composite hollow fiber membrane identical to that of Example A1 with an outer diameter of 197 μm, an inner diameter of 133 μm, and a Gurley stiffness of 5 mN is used. It is made into a cylindrical hollow fiber membrane bundle without a cavity portion formed on the inner side, and the effective membrane area is 1.63 m 2 The filling rate of the hollow fiber membrane bundle is 30%. Other than this, an external perfusion type hollow fiber membrane module is produced in the same manner as in Example C1.

[0386] [Evaluation of degassing performance]

[0387] For the external perfusion type hollow fiber membrane modules of each example, water is passed through from the first port and flows out from the third port, and a vacuum pump is connected to the second port to perform vacuum degassing at a vacuum degree of -88 kPa. The temperature of the water is 25 °C. The flow rate change of the externally perfused water is 250, 500, 750, 1000, 1250, 1500 mL / min, and the dissolved oxygen removal rate in the treated water after degassing is measured at each flow rate.

[0388] The dissolved oxygen removal rate is obtained according to the formula (2).

[0389] The results of Example C1 and Example C2 are as Figure 19 shown, and the results of Examples C3 - C5 are as Figure 22 shown.

[0390] As Figure 19 shown, in the external perfusion type hollow fiber membrane module of Example C1 having a hollow fiber membrane bundle with a cavity portion formed on the inner side and the region between the casting portion in the housing and the second end of the hollow fiber membrane bundle being provided with only the hollow fiber membrane bundle, compared with the external perfusion type hollow fiber membrane module of Example C2 having a cylindrical hollow fiber membrane bundle without a cavity portion formed on the inner side, the dissolved oxygen removal rate of the treated water is high and the degassing performance is high.

[0391] As Figure 22As shown, in Example C3 where the Gurley stiffness of the hollow fiber membrane is 15 mN or more and there is no void in the hollow fiber membrane bundle, and in the component of Example C4 where the Gurley stiffness of the hollow fiber membrane is 15 mN or more and there is a void in the hollow fiber membrane bundle, the dissolved oxygen removal rate of the treated water is high and the degassing performance is high compared to the component of Example C5 where the Gurley stiffness of the hollow fiber membrane is less than 15 mN and there is no void in the hollow fiber membrane bundle.

Claims

1. An externally perfused hollow fiber membrane module, comprising: a cylindrical hollow fiber membrane bundle formed by bundling a plurality of hollow fiber membranes and having a cavity portion formed therein, and a housing that houses the hollow fiber membrane bundle. The outer diameter of the housing body is 3 to 15 cm, and the length is 5 to 50 cm. The first end portion in the longitudinal direction of the hollow fiber membrane bundle is fixed in the housing by a casting portion in a state where the end surfaces of the respective hollow fiber membranes are open. The second end portion of the hollow fiber membrane bundle, which is opposite to the first end portion, is a free end. The Gurley stiffness of the hollow fiber membrane is 18 to 25 mN, and the outer diameter of the hollow fiber membrane is 350 μm or less. Liquid is perfused outside the membranes of the respective hollow fiber membranes from the casting portion in the housing to the second end portion side, and only the hollow fiber membrane bundle is provided in the region between the casting portion in the housing and the second end portion.

2. The externally perfused hollow fiber membrane module according to claim 1, wherein the plurality of hollow fiber membranes are bundled in a state of being interconnected by warp yarns.

Images