WO2012091070A1 - 吸着分離膜モジュール、吸着分離膜モジュールの製造方法、及び仕切部材 - Google Patents
吸着分離膜モジュール、吸着分離膜モジュールの製造方法、及び仕切部材 Download PDFInfo
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- WO2012091070A1 WO2012091070A1 PCT/JP2011/080343 JP2011080343W WO2012091070A1 WO 2012091070 A1 WO2012091070 A1 WO 2012091070A1 JP 2011080343 W JP2011080343 W JP 2011080343W WO 2012091070 A1 WO2012091070 A1 WO 2012091070A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/021—Manufacturing thereof
- B01D63/022—Encapsulating hollow fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/021—Manufacturing thereof
- B01D63/022—Encapsulating hollow fibres
- B01D63/0223—Encapsulating hollow fibres by fixing the hollow fibres prior to encapsulation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/021—Manufacturing thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/021—Manufacturing thereof
- B01D63/022—Encapsulating hollow fibres
- B01D63/0224—Opening the fibre ends after encapsulation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/021—Manufacturing thereof
- B01D63/0233—Manufacturing thereof forming the bundle
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/024—Hollow fibre modules with a single potted end
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/04—Hollow fibre modules comprising multiple hollow fibre assemblies
- B01D63/043—Hollow fibre modules comprising multiple hollow fibre assemblies with separate tube sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/2626—Absorption or adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/62—Cutting the membrane
Definitions
- the present invention relates to an adsorption separation membrane module, a method for producing the same, and a partition member used in the adsorption separation membrane module.
- a hollow fiber membrane bundle composed of a plurality of hollow fiber membranes, a cylindrical body that accommodates the hollow fiber membrane bundle, and a plurality of hollow fiber membrane bundles at the end of the hollow fiber membrane bundle.
- the partition member partitioned off into a film bundle is known (for example, refer to patent documents 1 and 2).
- the partition member is configured by combining plates in a cross shape or the like, and the hollow fiber membrane bundle is divided into, for example, four at the end.
- Such hollow fiber membrane modules perform various water treatments such as concentration of valuables and removal of impurities in various industrial fields such as food and drink, chemical products and pharmaceuticals, ultrapure water production, river water turbidity and wastewater treatment. It has been broken.
- Scalability is the size of the hollow fiber membrane module (specifically, the total length of the hollow fiber membranes determined from the length, inner and outer diameter of the hollow fiber membranes, and the number of hollow fiber membranes in the bundle of hollow fiber membranes) and the processing capacity (for example, unit When the hollow fiber membrane module is made a predetermined size, it is preferable that the processing capacity is accurately increased by a predetermined amount accordingly. If the scalability is high and stable, it is possible to design a desired capacity with sufficient accuracy in an actual process.
- the hollow fiber membrane is divided into a size separation membrane having a “sieving function” and an adsorption membrane having an “adsorption function”.
- the sieving function is a function of separating according to the size of the porous membrane with respect to the pore diameter.
- solute components and solvent components smaller than the pore size of the membrane pass through the membrane, but solute components larger than the pore size of the membrane are separated by being blocked by the membrane.
- the size separation membrane having a sieving function include so-called ultrafiltration membranes, microfiltration membranes, nanofiltration membranes, dialysis membranes, and reverse osmosis membranes.
- Such size separation membranes are mainly used in applications such as water treatment, sewage treatment, food concentration and separation, ultrapure water purification, and general industrial wastewater treatment.
- the actual process size is examined from the beginning instead of the small-scale trial introduction as described above.
- the adsorption function is a function of separating by the difference in interaction force on the pore surface of the membrane.
- the component having affinity with the pore surface due to the interaction force on the pore surface of the membrane is stored and concentrated on the porous surface of the porous membrane.
- Components that do not interact with each other and components that repel are separated by passing through the porous membrane.
- the adsorption film having an adsorption function include an ion adsorption film, a hydrophobic interaction type adsorption film, and an affinity type adsorption film.
- Such an adsorption membrane is mainly used for bio-applications such as protein purification, antibody purification, DNA removal, and virus removal, and metal ion recovery.
- bio-applications such as protein purification, antibody purification, DNA removal, and virus removal, and metal ion recovery.
- the liquid to be purified is expensive, such as for biotechnology, it is common to design an actual process based on experimental data on a small scale.
- Adsorption breakthrough refers to a phenomenon in which an object to be adsorbed that cannot be adsorbed leaks to the permeate side of the membrane.
- the adsorption membrane is required to be much more scalable and stable than the size separation membrane.
- the size of the hollow fiber membrane module to be applied is uniquely determined according to the amount of the stock solution to be purified and the content of the substance, and the desired processing capacity corresponding to the size is ensured. Need to be demonstrated. That is, the hollow fiber membrane module is required to have high scalability.
- the scalability of the hollow fiber membrane module is affected by the volume filling rate, which is the volume occupied by the hollow fiber membrane bundle with respect to the volume of the cylinder, and the volume filling rate of the hollow fiber membrane is within a predetermined range. It came to the knowledge that scalability can be improved and stabilized. Conventionally, there has been no discussion about the hollow fiber membrane module using a hollow fiber membrane in relation to the volume filling rate and the scalability, and the research on the adsorption separation membrane module that requires much higher scalability than the size separation membrane. After that, it was found that the volume filling rate is extremely important.
- an adsorption separation membrane module capable of ensuring high scalability using a hollow fiber membrane having an adsorption function
- an adsorption separation membrane module manufacturing method and a partition member
- the purpose is to provide.
- an object of the adsorption separation membrane module production method and partition member is to be able to produce an adsorption separation membrane module that can obtain a stable volume filling rate.
- the adsorption / separation membrane module comprises a hollow fiber membrane bundle comprising a plurality of hollow fiber membranes having an adsorption function, a cylindrical body for housing the hollow fiber membrane bundle, and at least one end of the hollow fiber membrane bundle.
- An adsorbing / separating membrane module comprising a fixed layer, wherein the fixed layer has a fixing agent dense portion extending over the entire thickness of the fixed layer along the longitudinal direction of the hollow fiber membrane bundle.
- the fixing agent dense portion refers to a region where the fixing agent is a main component in each element region of the fixing layer including the fixing agent, the hollow fiber membrane, and other members.
- a fixed layer is formed by filling the end of a unit comprising a hollow fiber membrane bundle and a cylindrical body with a fixing agent.
- the fixed layer is formed in the longitudinal direction of the hollow fiber membrane bundle. If a space serving as a fixing agent dense portion extending along the entire fixing layer thickness is secured, this space can function as a buffer space and / or a flow path when the fixing agent is filled (details will be described later). To do). Thereby, since it becomes possible to make small the load which acts on the edge part of the hollow fiber membrane bundle at the time of filling with a fixing agent, buckling of a hollow fiber membrane bundle can be suppressed.
- the volume filling rate of the hollow fiber membrane bundle with respect to the cylindrical body is designed to be an optimum value, if the buckling of the hollow fiber membrane bundle increases due to the filling of the fixing agent, the volume filling rate of the hollow fiber membrane bundle with respect to the cylindrical body Becomes larger than the design value.
- the amount of adsorption that is, the amount by which the adsorption separation module can adsorb the object before the adsorption breakthrough
- the relationship between the volume filling rate and the adsorption amount of the adsorption separation membrane module will be described.
- a liquid is allowed to flow from the inner surface side of the hollow membrane and a treatment liquid is obtained as a permeate from the outer surface side.
- the hollow fiber membrane allows the liquid to permeate due to a pressure difference between the inner surface side and the outer surface side (hereinafter referred to as an intermembrane differential pressure).
- the amount of liquid that permeates per unit time depends on the transmembrane pressure difference.
- the processing liquid on the outer surface side of the hollow fiber membrane moves along the longitudinal direction of the hollow fiber membrane to the opening (from here, the processing liquid is discharged) on the end surface of the cylindrical body, Receives a large pressure loss. That is, when the volume filling rate is increased, the pressure distribution on the inner surface side of the hollow fiber membrane does not change, and only the outer surface side of the hollow fiber membrane changes the pressure distribution along the longitudinal direction of the hollow fiber membrane. The variation in the differential pressure increases.
- the volume of the hollow fiber membrane bundle with respect to the cylindrical body is suppressed by causing the fixing agent dense part of the fixing layer to function as a buffer space and / or a flow path when the fixing agent is filled, thereby suppressing buckling of the hollow fiber membrane bundle. Suppressing the packing rate from deviating excessively from the design value and preventing the adsorption amount of the adsorption separation membrane module from decreasing, maintaining high and stable scalability, and reducing the function of the adsorption separation membrane module in the actual process That is, deterioration of the quality of the processing liquid is prevented.
- the cross-sectional area of the fixing agent dense portion may be 3% or more and less than 60% with respect to the occupied cross-sectional area of the hollow fiber membrane bundle.
- buckling can be suppressed by setting the cross-sectional area of the fixing agent dense part to 3% or more and less than 60% with respect to the occupied cross-sectional area of the hollow fiber membrane bundle.
- the occupied cross-sectional area of the hollow fiber membrane bundle is a cross-sectional area occupied by a substantially circumscribed circle of the region where the hollow fiber membrane bundle exists on the end surface of the fixed layer of the hollow fiber membrane module.
- the hollow fiber membrane bundle in the fixed layer, may be divided into a plurality of small bundles, and the small bundles may be arranged at intervals.
- the small bundles may be partly arranged with some space (partly in contact), or may be arranged completely apart.
- the space between the small bundles when the adsorption separation membrane module is manufactured, when filling with the fixing agent, is a space that becomes a fixing agent dense portion, that is, It can function as a buffer space and / or a flow path when the fixing agent is filled.
- the space between the small bundles functions not only as a buffer space but also as a flow path.
- the flow path is a space that guides the fixing agent to a wide space between the hollow fiber membrane bundle and the cylindrical body, and thereby the buffer space can be further expanded.
- the present invention may further include a partition member that partitions the hollow fiber membrane bundle into a plurality of small bundles in the fixed layer and has a penetrating portion that penetrates in the longitudinal direction of the hollow fiber membrane bundle.
- a partition member that partitions the hollow fiber membrane bundle into a plurality of small bundles in the fixed layer and has a penetrating portion that penetrates in the longitudinal direction of the hollow fiber membrane bundle.
- Fixing part extending over the entire thickness of the fixing layer along the longitudinal direction of the bundle of hollow fiber membranes by allowing the part to function as a space to become a fixing agent dense part, that is, a buffer space and / or a flow path when the fixing agent is filled A dense part can be formed.
- the lump of fixing agent is divided for every small bundle by this partition member.
- the fixing agent that forms the fixing layer generates heat during curing, and the larger the fixing agent lump, the greater the amount of heat generated by curing, so that the cooling shrinkage also increases. Therefore, by separating the fixative lump in this way, the amount of curing heat generated per fixative lump is reduced, and cooling shrinkage is suppressed, so that the fixing layer is prevented from peeling or cracking. be able to.
- the present invention allows the penetration portion of the partition member to function as a buffer space and / or a flow path when filling with the fixing agent, so that the fixing layer extends over the entire thickness of the fixing layer along the longitudinal direction of the hollow fiber membrane bundle.
- An extending fixing agent occupying portion (that is, a fixing agent dense portion consisting only of the fixing agent) can be formed. This makes it possible to reliably reduce the load acting on the end of the hollow fiber membrane bundle at the time of filling with the fixing agent, and to suppress buckling of the hollow fiber membrane bundle. And since the fixing agent with which a penetration part is filled is also divided by a partition member, generation
- the partition member may be formed with a penetrating portion by arranging a pair of plate members to face each other.
- the fixing member dense portion extending in the entire thickness of the fixing layer along the longitudinal direction of the hollow fiber membrane bundle is formed in the fixing layer by causing the penetrating portion of the partition member to function as a buffer space and a flow path when filling the fixing agent. Can be formed.
- the partition member by forming the partition member with a pair of plate members, the buffer space and the flow path can be easily constructed with reliable dimensions as designed. Furthermore, separation of the fixing layer and occurrence of cracks due to the partition of the fixing agent mass by the partition member can be prevented.
- the present invention may further comprise a dividing means for dividing the hollow fiber membrane bundle partitioned by the partition member.
- a dividing means for dividing the hollow fiber membrane bundle partitioned by the partition member.
- the present invention may further include a protective member that covers the outer periphery of the hollow fiber membrane bundle partitioned by the partition member.
- a protective member can protect the outer periphery of the hollow fiber membrane bundle.
- the clearance gap between hollow fiber membrane bundles is ensured more and / or it can prevent that the hollow fiber membrane in a hollow fiber membrane bundle is scattered, and can ensure further scalability.
- the partition member may be a combination of a pair of opposingly arranged plate members in a cross shape. In this way, by forming the partition member into a simple cross shape, it is possible to form the penetrating part more easily. Since the partition member has a simple structure, the number of hollow fiber membranes to be filled can be increased accordingly. It becomes. Also, the fixing agent dense portion that extends through the entire thickness of the fixing layer along the longitudinal direction of the hollow fiber membrane bundle by allowing the penetrating portion of the partition member to function as a buffer space and a flow path when filling the fixing agent. Can be formed. Furthermore, separation of the fixing layer and generation of cracks by dividing the fixing agent by the partition member can also be prevented.
- the present invention can be used for separation and purification for bio-use. Thereby, separation and purification for bio use can be performed with sufficient accuracy with a desired ability.
- the method for producing an adsorption / separation membrane module comprises a hollow fiber membrane bundle comprising a plurality of hollow fiber membranes having an adsorption function, a cylindrical body for housing the hollow fiber membrane bundle, and at least one of the hollow fiber membrane bundles.
- An adsorbing / separating membrane module comprising: a fixing layer that fixes an end portion to a cylindrical body, wherein a gap is formed between the hollow fiber membrane bundle, the cylindrical body, and the hollow fiber membrane;
- the end of the hollow fiber membrane is obtained by fixing the hollow fiber membrane bundle to the cylinder by filling the end of the unit with the fixing agent injecting member extending in the direction, and cutting the end of the unit. Open the part.
- the fixing agent injection member may be long enough to be removed together with the end of the cut unit, or may be long enough to remain in the fixed layer of the adsorption separation membrane module.
- the fixing agent injecting member that forms a gap between the hollow fiber membranes extends in the longitudinal direction of the hollow fiber membrane bundle, thereby buffering space when filling the fixing agent.
- a fixing agent dense portion extending in the entire thickness of the fixing layer can be formed in the fixing layer by functioning as a flow path. Therefore, the same operation and effect as the above-mentioned adsorption separation membrane module can be obtained.
- the method for manufacturing an adsorption / separation membrane module according to the present invention it is possible to manufacture an adsorption / separation membrane module having a stable volume filling rate and having high and stable scalability.
- the method for producing an adsorption / separation membrane module comprises a hollow fiber membrane bundle comprising a plurality of hollow fiber membranes having an adsorption function, a cylindrical body for housing the hollow fiber membrane bundle, and at least one of the hollow fiber membrane bundles.
- An adsorption separation membrane module comprising: a fixed layer that fixes an end portion to a cylindrical body; and a partition member that has a through portion that partitions the hollow fiber membrane bundle into a plurality of small bundles and penetrates in the longitudinal direction of the hollow fiber membrane in the fixed layer.
- a manufacturing method wherein a hollow fiber membrane bundle, a cylindrical body, and an end of a unit including a partition member are filled with a fixing agent, thereby fixing the hollow fiber membrane bundle and the partition member to the cylindrical body, and an end of the unit. Is cut to open the end of the hollow fiber membrane.
- the partition member has a penetrating portion that penetrates in the longitudinal direction of the hollow fiber membrane. Therefore, the same operation and effect as the above-mentioned adsorption separation membrane module can be obtained.
- the method for manufacturing an adsorption / separation membrane module according to the present invention it is possible to manufacture an adsorption / separation membrane module having a stable volume filling rate and having high and stable scalability.
- a partition member according to the present invention includes a hollow fiber membrane bundle composed of a plurality of hollow fiber membranes having an adsorption function, a cylindrical body that accommodates the hollow fiber membrane bundle, and at least one end of the hollow fiber membrane bundle as a cylindrical body.
- a partition layer that is provided in an adsorption / separation membrane module that is fixed to a hollow fiber membrane bundle and divides the hollow fiber membrane bundle into a plurality of membrane bundles at an end of the hollow fiber membrane bundle, the penetrating portion penetrating in the axial direction.
- the partition member according to the present invention has a penetrating portion that penetrates in the axial direction, that is, in the direction along the longitudinal direction of the hollow fiber membrane when assembled to the adsorption separation membrane module. Therefore, the adsorption / separation membrane module to which the partition member according to the present invention is applied can exhibit the same operations and effects as the above-described adsorption / separation membrane module, has a stable volume filling rate, and has high and stable scalability.
- An adsorption separation membrane module can be manufactured.
- the adsorption / separation membrane module comprises a hollow fiber membrane bundle comprising a plurality of hollow fiber membranes having an adsorption function, a cylindrical body for housing the hollow fiber membrane bundle, and at least one end of the hollow fiber membrane bundle.
- An adsorption separation membrane module including a fixed layer, wherein the ratio of the dynamic adsorption capacity in the module form to the dynamic adsorption capacity in the single fiber form of the hollow fiber membrane is 90% or more and 100% or less.
- the dynamic adsorption capacity is an index indicating the adsorption performance per unit membrane volume.
- the index substance is supplied to the adsorption separation membrane module or the adsorption membrane itself until adsorption breakthrough, and the amount of the adsorbed index substance is calculated by dividing the total membrane volume of the adsorption membrane used for evaluation. That is, the dynamic adsorption capacity in the module form is the adsorption performance when this evaluation is performed in the module, and the dynamic adsorption capacity in the single yarn form is the hollow fiber filled by dismantling the module. The adsorption performance when the film is taken out and evaluated.
- the dynamic adsorption capacity almost the same as the dynamic adsorption capacity in the single yarn form can be obtained in the module form over all sizes from the small size module to the large size module. It is done. As a result, high and stable scalability can be secured between the adsorption separation membrane modules of different sizes, and a desired capacity can be designed with sufficient accuracy in an actual process.
- the volume filling rate that is the occupied volume of the hollow fiber membrane with respect to the volume of the cylindrical body is 30% or more and less than 70%.
- the adsorption performance per unit membrane volume can be kept constant while securing the processing capacity for the module installation area, so that high and stable scalability can be secured.
- the ratio of the dynamic adsorption capacity in the module form to the dynamic adsorption capacity in the single fiber form of the hollow fiber membrane can be 90% or more and 100% or less.
- the method for producing an adsorption / separation membrane module, and the partition member a high and stable scalability can be ensured by using a hollow fiber membrane having an adsorption function.
- an adsorption separation membrane module that can obtain a stable volume filling rate can be produced.
- FIG. 1 is a schematic configuration diagram showing a cross-sectional configuration along the longitudinal direction of a hollow fiber membrane module 1 according to an embodiment of the present invention.
- FIG. 2 is a schematic configuration diagram showing a cross-sectional configuration of the fixed layer of the hollow fiber membrane module 1 according to the embodiment of the present invention.
- FIG. 3 is an exploded perspective view of a unit assembled in advance to manufacture the hollow fiber membrane module 1 according to the embodiment of the present invention. As shown in FIGS.
- a hollow fiber membrane module 1 includes a hollow fiber membrane bundle 3 including a plurality of hollow fiber membranes 2 having an adsorption function, and a cylindrical housing ( Cylinder) 4, partition members 6 A and 6 B disposed at the end portions 3 a and 3 b of the hollow fiber membrane bundle 3, and fixing layers 7 A and 7 B for fixing the end portions 3 a and 3 b of the hollow fiber membrane bundle 3 to the housing 4.
- the hollow fiber membrane module 1 is also referred to as an adsorption separation membrane module.
- the hollow fiber membrane bundle 3 is divided into a plurality of small bundles 3A, 3B, 3C, 3D by a partition member 6.
- the small bundles 3 ⁇ / b> A, 3 ⁇ / b> B, 3 ⁇ / b> C, and 3 ⁇ / b> D are arranged at a sufficient interval so as not to contact each other.
- each of the small bundles 3 ⁇ / b> A, 3 ⁇ / b> B, 3 ⁇ / b> C, 3 ⁇ / b> D may be covered with a protective member 8 on the outer periphery.
- the protective member 8 is a net-like structure having a mesh.
- the protection member 8 has a fan-shaped cross section so as to cover the small bundles 3A, 3B, 3C, 3D obtained by dividing the hollow fiber membrane bundle 3 into four.
- the material of the protection member 8 is not particularly limited, and a known material can be used.
- polymer materials such as polyester, nylon, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, polysulfone, and polycarbonate, metal materials such as stainless steel and aluminum, glass fiber, and carbon fiber
- inorganic materials such as In particular, from the viewpoint of elution safety and heat sterilization treatment resistance and chemical washing resistance required for each application in pharmaceutical applications and food and beverage applications, from materials such as polyethylene, polypropylene, polysulfone, polycarbonate, and polyfluorinated ethylene It is preferable to choose.
- the mesh shape and mesh size of the net having the mesh of the protective member 8 are not particularly limited as long as the shape and size do not hinder the fluid supply to the hollow fiber membrane.
- it may be a lattice-shaped knitted product, or an injection product having a rectangular or round eye.
- the hollow fiber membrane 2 constituting the hollow fiber membrane bundle 3 is an adsorption membrane having a so-called “adsorption function”, and is open at both end portions 2a and 2b.
- the adsorbing membrane type hollow fiber membrane 2 is not limited in terms of the material and the fine structure of the adsorption action point as long as it has an adsorption function, and a known one can be used. Further, for example, the following publicly known technologies (International Publication No. 2009/054226, US Pat. No. 5,547,575, US Pat. No. 6,780,327, JP-T-2006-519273, JP-A-2009-53191, etc.) are hollow. An adsorption membrane type hollow fiber membrane obtained by application to a yarn membrane may be used.
- the adsorption film is composed of an adsorption action point that develops an adsorption function and a base film for maintaining the shape as a permeable membrane.
- the adsorption action point for developing the adsorption function is formed by introducing a functional group having an adsorption function into the porous substrate surface.
- the functional group having an adsorption function include cation exchange groups such as sulfonic acid group, carboxylic acid group, and phosphoric acid group, primary amino group and primary ammonium group, secondary amino group and secondary ammonium group, and tertiary.
- Anion exchange groups such as amino groups, tertiary ammonium groups, and quaternary ammonium groups, hydrophobic groups such as alkyl groups and aromatic functional groups, chelating functional groups such as iminodiacetic acid groups and ethylenediaminetetraacetic acid groups, protein A And affinity type functional groups composed of biologically related substances. These functional groups may be used in combination of multiple types.
- the fine structure of the adsorption action point is not particularly limited as long as it has an adsorption function.
- it may be chemically bonded directly to the surface of the hollow fiber membrane 2 serving as a base material, or coating May be physically fixed to the porous body of the hollow fiber membrane 2.
- a linear fine structure may be formed and a crosslinked structure may be taken.
- a known ultrafiltration membrane or microfiltration membrane can be used as the base membrane constituting the adsorption membrane.
- the adsorption site is processed later by performing chemical treatment or physical treatment on the hollow fiber membrane 2, it is necessary to select a material that does not change or decompose due to the processing conditions.
- an appropriate material can be selected from known materials according to each usage.
- a more preferable material for the base film polyethylene, polypropylene, polyvinylidene fluoride, and polysulfone can be used.
- the average pore diameter of the hollow fiber membrane 2 can be selected according to the treatment liquid. Preferably they are 0.001 micrometer or more and 10 micrometers or less, More preferably, they are 0.01 micrometer or more and 10 micrometers or less, More preferably, they are 0.1 micrometer or more and 1 micrometer or less.
- the porosity which is the volume ratio of the pores in the hollow fiber membrane 2
- the porosity can be arbitrarily selected as long as there is no practical problem. Preferably they are 5% or more and 99% or less, More preferably, they are 10% or more and 95% or less, More preferably, they are 30 or more and 90% or less.
- the measurement of the average pore diameter and the porosity can be carried out by ordinary methods for those skilled in the art, for example, as described in “Membrane Technology” by Marcel Mulder (IPC Co., Ltd.). Specific examples of the measuring method include observation with an electron microscope, a bubble point method, a mercury intrusion method, and a transmittance method.
- the cross-sectional dimension of the hollow fiber membrane 2 is preferably an inner diameter of 50 ⁇ m to 10 mm, more preferably 100 ⁇ m to 4 mm, and a membrane having an inner / outer diameter ratio of 0.2 to 0.8 can be suitably used.
- a linear one or a crimped one (crimp yarn) can be used as the shape of the hollow fiber membrane 2.
- the housing 4 includes a cylindrical housing body 11, caps 12 ⁇ / b> A and 12 ⁇ / b> B disposed at both ends of the housing body 11, and fixtures 13 ⁇ / b> A and 13 ⁇ / b> B that fix the caps 12 ⁇ / b> A and 12 ⁇ / b> B to the housing body 11. ing.
- materials of the housing body 11, caps 12A and 12B, and fixtures 13A and 13B Polymer materials such as polyvinyl chloride, polysulfone, polycarbonate, and ABS, and metal materials such as stainless steel and aluminum Is applicable. Both ends of the housing body 11 are sealed with fixing layers 7A and 7B, respectively.
- the housing 4 is partitioned into three spaces by the fixed layers 7A and 7B.
- the housing 4 includes a space 4A configured by the fixed layer 7A and the cap 12A, a space 4B configured by the fixed layer 7B and the cap 12B, a housing body 11 and the fixed layers 7A and 7B. 4C.
- the end 2a of the hollow fiber membrane 2 opens to the space 4A, and the end 2b of the hollow fiber membrane 2 opens to the space 4B.
- the space 4A communicates with a tube portion 14A formed on the cap 12A
- the space 4B communicates with a tube portion 14B formed on the cap 12B.
- Pipe portions 16A and 16B formed in the housing body 11 communicate with the space 4C.
- the partition members 6A, 6B partition the hollow fiber membrane bundle 3 into a plurality of small bundles 3A, 3B, 3C, 3D at the end portions 3a, 3b of the hollow fiber membrane bundle 3.
- Partition members 6A and 6B have a predetermined cross-sectional shape and extend along axis L1.
- the axis L ⁇ b> 1 of the partition members 6 ⁇ / b> A and 6 ⁇ / b> B is arranged to coincide with the axis of the housing 4.
- the axial direction of the partition members 6A and 6B (that is, the direction in which the axis L1 extends) is substantially parallel to the longitudinal direction of the hollow fiber membrane 2, and is orthogonal to the direction of partitioning the small bundles 3A, 3B, 3C, and 3D.
- the partition members 6 ⁇ / b> A and 6 ⁇ / b> B have through portions 21, 22, 23, 24, and 26 that penetrate in the longitudinal direction (that is, the axial direction) of the hollow fiber membrane 2.
- the partition members 6 ⁇ / b> A and 6 ⁇ / b> B have a cross shape having four wall portions 31, 32, 33, and 34.
- the wall portion 31 partitions the small bundle 3A and the small bundle 3B.
- the wall 32 partitions the small bundle 3B and the small bundle 3C.
- the wall 33 partitions the small bundle 3C and the small bundle 3D.
- the wall 34 partitions the small bundle 3D and the small bundle 3A.
- the through portion 21 is formed in the wall portion 31.
- the penetrating part 22 is formed in the wall part 32.
- the penetration part 23 is formed in the wall part 33.
- the through portion 24 is formed in the wall portion 34.
- the through portion 26 is formed at the center position of the partition members 6A and 6B (position where the axis L1 is disposed) corresponding to the root portion of each of the wall portions 31 to 34.
- a well-known polymeric material, an inorganic material, and a metal material can be used suitably.
- polymer materials such as epoxy resin, urethane resin, silicone resin, polyvinylidene fluoride, polyethylene, polypropylene, polysulfone, polyethersulfone, polyphenylene oxide, polyvinyl chloride, polycarbonate, ABS resin, inorganic materials such as alumina and zirconia, Metal materials such as stainless steel and aluminum can be applied.
- the same material as the fixing agent from the viewpoint of good adhesiveness with the fixing agent and not causing an abnormality such as peeling to the fixing agent.
- the surface of the partition member may be subjected to surface roughening in order to increase the adhesive force with the fixing agent.
- the wall portion 31 is constituted by a pair of plate members 31a and 31b facing each other.
- the penetration part 21 is formed between the plate member 31a and the plate member 31b.
- the penetrating portion 21 penetrates in the longitudinal direction of the hollow fiber membrane 2 and opens in the outer peripheral direction (the tip side of the plate members 31a and 31b).
- the wall portion 32 is composed of a pair of plate members 32a and 32b facing each other.
- the penetration part 22 is formed between the plate member 32a and the plate member 32b.
- the penetrating portion 22 penetrates in the longitudinal direction of the hollow fiber membrane 2 and opens in the outer peripheral direction (the tip side of the plate members 32a and 32b).
- the wall 33 is constituted by a pair of plate members 33a and 33b facing each other.
- the penetration part 23 is formed between the plate member 33a and the plate member 33b.
- the penetrating portion 23 penetrates in the longitudinal direction of the hollow fiber membrane 2 and opens in the outer peripheral direction (the tip side of the plate members 33a and 33b).
- the wall portion 34 is constituted by a pair of plate members 34a and 34b facing each other.
- the penetration part 24 is formed between the plate member 34a and the plate member 34b.
- the penetrating portion 24 penetrates in the longitudinal direction of the hollow fiber membrane 2 and opens in the outer peripheral direction (the tip side of the plate members 34a and 34b).
- the penetration part 26 is formed in the connection part of each plate member, and penetrates in the longitudinal direction of the hollow fiber membrane 2.
- the wall portions 31, 32, 33, and 34 have a thickness that ensures a sufficient separation distance between the small bundles 3A, 3B, 3C, and 3D. Therefore, in the space 4C of the housing 4, a sufficient gap SP is formed between the small bundles 3A, 3B, 3C, 3D.
- the partition members 6A and 6B shown in FIGS. 2 and 3 include flat plates 41 and 42 arranged in parallel with each other, and flat plates 43 and 44 arranged in parallel with each other perpendicular to the flat plates 41 and 42, respectively. It is comprised by joining in the center position.
- the flat plate 41 constitutes a plate member 31a and a plate member 33a.
- the flat plate 42 constitutes a plate member 31b and a plate member 33b.
- the flat plate 43 constitutes a plate member 32a and a plate member 34a.
- the flat plate 44 constitutes a plate member 32b and a plate member 34b.
- the partition members 6A and 6B can be configured, for example, by forming a slit at the central position of the flat plates 41 and 42, forming a slit at the central position of the flat plates 43 and 44, and abutting and connecting the respective slits. it can.
- partition member 6A, 6B may be comprised by cutting into such a shape, and partition member 6A, 6B may be comprised by shape
- the fixing layer 7A seals one end of the housing body 11 of the housing 4.
- the fixed layer 7A is formed so as to enclose one end portion 3a of the hollow fiber membrane bundle 3 and the partition member 6A.
- the fixed layer 7 ⁇ / b> B seals the other end of the housing body 11 of the housing 4.
- the fixed layer 7B is formed so as to enclose the other end 3b of the hollow fiber membrane bundle 3 and the partition member 6B.
- a two-component mixed type curable resin and a thermoplastic resin are used.
- the two-component mixed curable resin is a resin that is cured by mixing a plurality of reactive compounds.
- the two-component adhesive two-component adhesive
- the two-component cast agent two-
- component resin two components called a main agent and a curing agent are mixed and cured at the time of use.
- a urethane resin composed of a main agent containing isocyanate as a reactive group and a curing agent containing an active hydrogen-containing organic compound, a main agent containing an epoxy group as a reactive group, an active hydrogen-containing organic compound or an organic acid anhydride.
- thermoplastic resin is preferably a resin whose melting point is lower than that of the polymer constituting the hollow fiber membrane and that is physically and chemically stable to the raw water to be filtered.
- specific examples include thermoplastic resins such as polyurethane, polyester, polyethylene, and polypropylene, and waxes.
- the fixed layers 7A and 7B are made of at least one of these materials.
- the fixing agent constituting the fixing layers 7A and 7B is also filled in the through portions 21, 22, 23, 24, and 26 of the partition members 6A and 6B to form a fixing agent dense portion.
- the fixing agent dense portion is a fixing layer including a fixing agent, a hollow fiber membrane, and a partition member, and the density of the hollow fiber membrane is 1/3 or less of the average density of the hollow fiber membrane. It refers to the element region of a fixed layer.
- the fixing agent dense part functions as a buffer space when filling the fixing agent in the module manufacturing process, and is preferably 1/5 or less, more preferably 1 from the viewpoint of suppressing buckling of the hollow fiber membrane bundle. / 10 or less.
- the average density of the hollow fiber membrane bundle and the density of the fixing agent can be confirmed in the cross section of the module fixing layer.
- the average density of the hollow fiber membrane bundle here refers to the sum of the occupied cross-sectional area of each hollow fiber membrane bundle (for example, a small bundle) with respect to the cross-sectional area occupied by the yarn bundle, which will be described in detail later.
- the average length of the partition members 6A and 6B with respect to the average thickness of the fixed layers 7A and 7B is preferably 50% or more from the viewpoint of preventing separation of the fixed layer and occurrence of cracks by dividing the fixing agent lump. 65% or more is more preferable, and 80% or more is more preferable. Moreover, although the partition member may protrude from the interface between the fixed layers 7A and 7B, it is preferable that the partition member completely fits in the fixed layer. Note that the average thickness of the fixed layers 7A and 7B and the average length of the partition members 6A and 6B both indicate the dimensions of the housing 4 in the axial direction.
- the fluid to be processed flows into the housing 4 from the tube portion 14B and passes through the hollow fiber membrane 2 via the hollow portion in the hollow fiber membrane 2.
- the passing component and the non-passing component are separated, and the passing component is taken out from the pipe portions 16A and / or 16B via the space 4C.
- the non-passing component may flow out of the pipe portion 14A and be circulated again to the pipe portion 14B.
- the circulation direction of the fluid to be processed may be reversed.
- the passing component and the non-passing component are separated and passed.
- the component passes through the hollow portion of the hollow fiber membrane 2 and is taken out from the tube portions 14A and / or 14B. Some non-passing components may flow out of the pipe portion 16B and be circulated again to the pipe portion 16A. The circulation direction of the fluid to be processed may be reversed.
- the hollow fiber membrane bundle 3 is configured by bundling a plurality of hollow fiber membranes 2.
- the protective member 8 may be covered on each film bundle.
- step S20 a step of sealing each hollow fiber membrane 2 constituting the hollow fiber membrane bundle 3 is performed (step S20).
- a sealing material is sealed at the end of each hollow fiber membrane 2.
- gypsum is used as the sealing material. Note that the order of the bundling step S10 and the closing step S20 may be reversed.
- step S30 the unit 50 before being sealed with the fixing agent is assembled (step S30).
- the unit 50 in which the hollow fiber membrane bundle 3 and the partition members 6 ⁇ / b> A and 6 ⁇ / b> B are assembled is assembled in the housing main body 11.
- the housing body 11 has cutting margins 11a and 11b that are cut after filling with the fixing agent at both ends.
- the unit 50 includes cups 51 ⁇ / b> A and 51 ⁇ / b> B that are covered on both ends of the housing main body 11.
- the cups 51 ⁇ / b> A and 51 ⁇ / b> B have a pipe part 51 a for allowing the fixing agent to flow into the housing main body part 11.
- the partition members 6A and 6B may be assembled.
- the hollow fiber membrane bundle 3 is divided into small bundles 3A, 3B, 3C, and 3D by assembling the partition members 6A and 6B after assembling a single bundle of hollow fiber membrane bundles 3 into the housing body 11. May be.
- step S40 filling of the fixing agent (fixing agent is finally cured to become a fixing layer) on both ends of the unit 50 is performed (step S40).
- the fixing agent BD is filled into the housing main body 11 of the unit 50 from the pipe portions 51a of the cups 51A and 51B.
- FIG. 5 shows a cross section taken along line CL1 in FIGS. 6 and 7 show only the portions of the wall portions 34 in the small bundles 3A and 3D and the partition member 6A, the flow of the fixing agent BD is different from the other small bundles 3B and 3C and other wall portions.
- the fixing agent BD filled from the pipe portion 51a is between the wall surface of the housing main body 11 and the hollow fiber membrane bundle 3, between the hollow fiber membrane bundle 3 and the partition members 6A and 6B, and between the hollow fiber membrane bundle 3. Flows into the space between the hollow fiber membranes 2. At this time, the fixing agent BD also flows into the through portions 21, 22, 23, 24, and 26 in the partition members 6A and 6B.
- the filled fixing agent BD constitutes a layer that becomes the fixing layers 7A and 7B after curing at the end of the housing body 11.
- the filling of the fixing agent BD can be performed by a so-called centrifugal casting method using centrifugal force.
- the unit 50 is attached to the centrifuge cassette in a state of being laid horizontally, and rotates on a horizontal plane with the vertical axis as a rotation axis.
- the unit 50 is disposed so that the end side to be bonded is on the outside in the centrifugal direction.
- the uncured fixing agent BD in a fluid state is pushed out of the tank by the centrifugal force generated by the rotation of the centrifugal cassette, and flows into the housing main body 11 from the pipe portion 51a.
- the fixing layer 7A is formed on one end side of the housing main body 11
- the fixing layer 7B is formed on the other end side by the same method.
- the center of rotation may be set at the center position of the unit 50, and both ends of the unit 50 may be simultaneously filled with the fixing agent BD.
- you may employ adopt the so-called stationary adhesion method of filling and fixing the fixing agent BD under stationary conditions.
- the fixing layers BD are formed by allowing the layer of the fixing agent BD to stand and cure.
- the fixing agent BD injected from the pipe portion 51a is the end surface between the hollow fiber membranes 2 in the cup 51A, and the end surface of the hollow fiber membrane bundle 3 and the cup 51A. It will be filled from between.
- the space between these is narrow and the inflow resistance of the fixing agent BD is large, it takes a long time to complete the filling.
- the injection speed from the pipe portion 51a and the injection speed into these narrow spaces are not balanced (the injection speed from the pipe portion 51a is faster), and the conventional hollow fiber membrane module is shown in FIG.
- the hollow fiber membrane bundle 3 is pushed by the injection pressure of the fixing agent BD, and the hollow fiber membrane bundle 3 is buckled.
- the partition member 6A penetrates as shown in FIGS.
- the parts 21, 22, 23, 24, 26 can be used as a so-called “buffer space” for temporarily releasing the injection pressure of the injected fixing agent BD (first buffer space).
- the through portions 21, 22, 23, 24 are connected to the inner wall of the housing body 11 and the hollow fiber membrane bundle 3 It is also possible to function as a flow path that communicates with a wide space (second buffer space) between the outer peripheral portions.
- the penetrating portion of the partition member 6A itself becomes a buffer space, and further becomes a communication channel to another buffer space.
- the penetrating portion is surrounded by the plate member, a reliable dimensional design of the flow path is possible. This makes it possible to effectively relieve the injection pressure of the fixative BD.
- the first and second buffer spaces acquired by the partition member 6A absorb the fast injection of the fixing agent BD from the pipe portion 51a by temporarily storing the fixing agent DB. Then, the temporarily stored fixing agent BD is injected between the hollow fiber membrane bundle 3 and the partition member and between the hollow fiber membranes 2 in the hollow fiber membrane bundle 3 without using a long time. Therefore, buckling can be effectively suppressed.
- the hollow fiber membrane bundle 3 is maintained linearly along the axial direction of the housing, as shown in FIG.
- the partition member formed by arranging a pair of plate members to face each other serves as a buffer space, and further serves as a communication channel to another buffer space. It is preferable from the viewpoint that it can be ensured and buckling is effectively suppressed. Furthermore, by arranging the pair of plate members in a cross shape, it is possible to secure a large space for storing the hollow fiber membrane bundle 3 in the housing, which is more preferable.
- the excessively filled fixative BD overflows from the tube portions 16A and 16B formed on the side surface of the housing main body 11, and the interface of the fixative BD and the inner walls of the tube portions 16A and 16B. Almost equal.
- the through portions 21, 22, 23, 24, and 26 of the partition members 6A and 6B are arranged along the longitudinal direction of the hollow fiber membrane bundle 3.
- a fixing agent dense portion is formed over the entire thickness of the fixing layers 7A and 7B.
- both ends of the unit 50 are cut (step S50).
- the open end portions 2a and 2b of the hollow fiber membrane 2 are formed.
- cutting is performed at a portion indicated by CL1 from the viewpoint of improving workability after cutting.
- the cups 51A and 51B, the cutting margins 11a and 11b of the housing body 11, the end of the hollow fiber membrane 2 in which the sealing material is sealed (the portion sealed by the sealing material), the partition member 6A. , 6B are removed.
- cutting may be performed at a portion indicated by CL2. In that case, the cups 51A and 51B, the ends of the hollow fiber membrane 2 (portions that are sealed by the sealing material), and the ends of the partition members 6A and 6B are removed.
- step S60 the caps 12A and 12B and the fixtures 13A and 13B are attached (step S60).
- the process shown in FIG. 4 ends, and the hollow fiber membrane module 1 is completed.
- the hollow fiber membrane module 1 manufactured in this manner is such that the ratio of the dynamic adsorption capacity in the module form to the dynamic adsorption capacity in the single fiber form of the hollow fiber membrane is 90% or more and 100% or less. Manufactured.
- the volume filling rate that is the occupied volume of the hollow fiber membrane bundle 3 with respect to the volume of the housing main body 11 is set to 30% or more and less than 70%.
- the lower limit of the volume filling rate is preferably 40% or more, more preferably 50% or more, and even more preferably 55% or more.
- the upper limit of the volume filling rate is preferably less than 70%, more preferably less than 68%. That is, it is most preferably 55% or more and less than 68%.
- the volume Vf of the hollow fiber membrane bundle 3 is represented by the formula (2).
- Vf (Do / 2) 2 ⁇ ⁇ ⁇ L ′ ⁇ n (2)
- Do is the average outer diameter of the hollow fiber membrane 2
- L ′ is the average effective length of the hollow fiber membrane 2
- n is the number of hollow fiber membranes 2 filled in the housing 4.
- Vh (Dh / 2) 2 ⁇ ⁇ ⁇ L (3)
- Dh is the average inner diameter of the housing body 11
- L is the distance between the interfaces of the fixed layers 7 A and 7 B in the hollow fiber membrane module 1.
- the volume filling rate Rv is obtained by disassembling the hollow fiber membrane module 1 and filling the number n of the hollow fiber membranes 2, the average effective length L ′ of the hollow fiber membranes 2, the average outer diameter Do of the hollow fiber membranes 2, It is calculated by actually measuring the average inner diameter Dh and the inter-interface distance L between the fixed layers 7A and 7B.
- the hollow fiber membrane module 1 is disassembled, the hollow fiber membrane bundle 3 is cut out from the interface between the fixed layers 7A and 7B, and the number of filling n is counted.
- the number corresponding to 10% of the number of fillings n is uniformly sampled from the entire area of the hollow fiber membrane bundle 3, the length and outer diameter thereof are measured, the average value is calculated, the average effective length L ′ and the average outer diameter Do And the volume Vf of the hollow fiber membrane bundle 3 is obtained by the above equation (2).
- the average inner diameter Dh of the housing and the inter-interface distance L between the fixed layers 7A and 7B are measured, and the internal volume Vh of the housing main body 11 is obtained by Equation (3).
- the volume filling rate will be described in more detail with reference to FIGS.
- the horizontal axis represents the volume filling rate [%] indicating the occupied volume of the hollow fiber membrane bundle 3 with respect to the volume of the housing body 11, and the vertical axis represents the unit membrane of the hollow fiber membrane 2 in the module form.
- It is adsorption capacity [mg / mL] which shows the adsorption amount [mg] of the adsorption object per volume [mL].
- the hollow fiber membrane module 1 using the adsorption membrane type hollow fiber membrane 2 has a dynamic adsorption capacity in the module form regardless of the increase or decrease of the volume filling rate while the volume filling rate is small. It becomes almost constant and high scalability is secured. However, when the volume filling rate exceeds a predetermined value, the dynamic adsorption capacity in the module form decreases as the volume filling rate increases, so that high scalability cannot be secured.
- the present inventors studied the relationship between the volume filling rate and the dynamic adsorption capacity in the module form it was found that the dynamic adsorption capacity in the module form can be kept substantially constant when the volume filling rate is less than 70%.
- the volume filling rate is less than 30%, the total volume of the hollow fiber membrane filled with respect to the housing size is reduced, so that the adsorption processing capacity of the module with respect to the installation area is lowered and the processing efficiency is lowered.
- the dynamic adsorption capacity in the module form is almost constant (that is, the single yarn) while ensuring the adsorption processing capacity.
- the dynamic adsorption capacity in the form Regardless of the size of the module from small size to large size, the same dynamic adsorption capacity as the single yarn dynamic adsorption capacity is always exhibited in the module form, ensuring high scalability between modules of different sizes be able to.
- the hollow fiber membrane bundle 3 when the hollow fiber membrane bundle 3 is pushed in by the injection pressure of the fixing agent BD, it buckles. Even if the volume filling rate is designed to be 30% or more and less than 70%, if the buckling of the hollow fiber membrane bundle 3 increases, the volume filling rate becomes larger than the design value.
- the deviation between the design value of the volume filling rate and the value after manufacture is evaluated by the degree of buckling (buckling rate).
- buckling rate degree of buckling
- W Rv / Rv0
- the theoretical volume filling rate Rv0 is a volume filling rate in a state where there is no buckling (that is, all the hollow fiber membranes 2 filled in the hollow fiber membrane module are arranged linearly between the fixed layers).
- the buckling rate is a numerical range of 100% or more. Further, it is preferably 120% or less, more preferably 110% or less, and further preferably 105% or less.
- the amount of adsorption object that is stored and concentrated in the porous membrane gradually increases as the adsorption process proceeds. If the adsorption process is continued as it is, leakage of the adsorption object to the permeate side of the film will eventually occur. That is, adsorption breakthrough begins. Therefore, in the adsorption film, it is necessary to finish the adsorption process before adsorption breakthrough occurs.
- the partition members 6A and 6B having the penetrating portions 21, 22, 23, 24, and 26 penetrating in the longitudinal direction of the hollow fiber membrane 2 include the hollow fiber membrane bundle.
- the three small bundles 3A, 3B, 3C, 3D are arranged so as to partition.
- the penetrating parts 21, 22, 23, 24, and 26 formed by the partition members 6A and 6B function as buffer spaces and flow paths when filling the fixing agent BD, so that the ends of the hollow fiber membrane bundle 3 are
- the buckling of the hollow fiber membrane bundle 3 can be suppressed as shown in FIG. 10 (a). For this reason, since it is suppressed that a volume filling rate becomes larger than expected, the difference in the timing which the adsorption breakthrough which arises in the hollow fiber membrane 2 starts is also eliminated, and high scalability is securable.
- the hollow fiber membrane module 1 manufactured in this way has a cross-sectional area (fixing agent dense part cross-sectional area) of the fixing agent dense part with respect to the occupied cross-sectional area of the hollow fiber membrane bundle 3 (yarn bundle occupied cross-sectional area Sf).
- a certain fixing agent dense part ratio Rb is set to 3% or more and less than 60%.
- the fixing agent dense part ratio Rb is represented by the formula (5).
- Rb Sb / Sf (5)
- the lower limit value of the fixing agent dense part ratio Rb is more preferably 4% or more, still more preferably 7% or more, and the upper limit value of the fixing agent dense part ratio Rb is more preferably less than 50%, and still more preferably. Is less than 30%. That is, it is most preferably 7% or more and less than 30%.
- the yarn bundle occupying cross-sectional area is an occupying cross-sectional area of the hollow fiber membrane bundle 3, and is a cross-sectional area occupied by substantially circumscribed circles of all the small bundles 3A, 3B, 3C, 3D constituting the hollow fiber membrane bundle 3. .
- the fixing agent dense part cross-sectional area Sb is a cross-sectional area of a part (fixing agent dense part) in which the fixing agent is densely filled among the parts included in the occupied cross-sectional area of the hollow fiber membrane bundle 3.
- the yarn bundle occupation cross-sectional area Sf includes the small bundles 3A, 3B, 3C, 3D, the wall portions 31, 32, 33, 34 of the partition members 6A, 6B, and the partition members 6A,
- the cross-sectional area of the 6B penetrating parts 21, 22, 23, 24, 26 is combined, and the fixing agent dense part cross-sectional area Sb is the cross-sectional area of the penetrating parts 21, 22, 23, 24, 26 of the partition members 6A, 6B. It becomes.
- the fixing agent dense portion cross-sectional area Sb is Among the cross-sectional areas included in the occupied cross-sectional area, the cross-sectional areas of all the portions in which the fixing agent is filled in the gaps between the small bundles.
- the fixing agent dense part ratio Rb to 3% or more and less than 60%, it becomes possible to control the buckling suppression, and the volume filling rate can be easily set to 30% or more and less than 70%.
- the boundary between the partition member and the fixing agent in the fixing layer it is possible to measure the dimensions and calculate the fixing agent dense part ratio.
- the boundary between the partition member and the fixing agent is determined according to the scheme shown in FIG.
- the scheme for determining the boundary between the partition member and the fixing agent first determines whether or not the hollow fiber membrane bundle is partitioned (step S1). If it is determined that the hollow fiber membrane bundle is not partitioned (step S1: NO), it is determined that there is no partition member (step S5). On the other hand, if it is determined that the hollow fiber membrane bundle is partitioned (step S1: YES), it is then determined whether or not the partition member is visible on the module end face (step S2). If it is determined that the partition member is visible on the module end face (step S2: YES), it is determined that there is a partition member (step S6).
- Step S3 can be determined by, for example, the difference in color of slice pieces obtained by thinly slicing the fixed layer. And if it determines with a partition member being visible in a fixed layer embedding part (step S3: YES), it will determine with there being a partition member (step S6). On the other hand, if it is determined that the partition member is not visible at the fixed layer embedded portion (step S3: NO), it is then determined whether the fixed layer slice piece is broken at the interface between the fixative and the partition member (step S4). .
- step S4 determines with a fixed layer slice piece breaking at the interface of a fixing agent and a partition member (step S4: YES)
- step S6 determines with there being a partition member
- step S5 determines that there is no partition member. In this way, the boundary between the partition member and the fixing agent is determined.
- the hollow fiber membrane inside the small bundle is preferably disposed at a position within 12 times, more preferably within 10 times the outer diameter of the hollow fiber membrane from any outer peripheral portion. It is the state that was done. For example, when the outer diameter of the hollow fiber membrane is 3 mm, the hollow fiber membrane is preferably disposed at a position within 36 mm, more preferably within 30 mm from any outer peripheral portion. If it is in this state, there is no restriction
- the distance between the closest hollow fiber membranes is preferably 1 mm or more and 30 mm or less, more preferably 3 mm or more and 20 mm or less.
- the processing capacity is ensured by setting the volume filling rate of the hollow fiber membrane 2 to the housing body 11 to be 30% or more and less than 70%.
- the dynamic adsorption capacity in the module form can be kept almost constant, high and stable scalability can be ensured.
- the hollow fiber membrane module 1 even when used for separation and purification for bio purposes, it can be performed with a desired ability and sufficient accuracy.
- the fixing layers 7A and 7B are formed by filling the end portion of the unit 50 including the hollow fiber membrane 2 and the housing body 11 with the fixing agent BD.
- the partition members 6A, 6B By partitioning the small bundles 3A, 3B, 3C, 3D of the hollow fiber membrane bundle 3 with the partition members 6A, 6B forming the portions 21, 22, 23, 24, 26, the penetrating portions 21, 22, 23, 24, 26 Can function as a flow path for the fixative BD.
- the load which acts on the edge part of the hollow fiber membrane bundle 3 becomes small and the buckling of the hollow fiber membrane bundle 3 is suppressed, the volume filling rate of the hollow fiber membrane with respect to the cylinder is increased from the design value. It is possible to suppress detachment and maintain high scalability, and it is possible to suppress deterioration in the function of the hollow fiber membrane module due to uneven volume filling rate and deterioration in the quality of the treatment liquid.
- the fixing members 6A and 6B are divided into small bundles 3A, 3B, 3C and 3D into which the fixing agent mass is divided.
- the fixing agent that forms the fixing layers 7A and 7B generates heat during curing, and the larger the fixing agent lump, the greater the amount of heat generated by curing. Therefore, by separating the fixing agent lump in this way, the amount of curing heat generated per one fixing agent lump is reduced, and cooling shrinkage is suppressed. Therefore, peeling and cracking of the fixing layers 7A and 7B occur. Can be prevented.
- the present invention is not limited to the embodiment described above.
- segmented into small bundle 3A, 3B, 3C, 3D, partition member 6A, 6B, and fixed layer 7A, 7B is taken as an example.
- the hollow fiber membrane module may have any configuration as long as the volume filling ratio that is the volume occupied by the hollow fiber membrane with respect to the volume of the cylindrical body is 30% or more and less than 70%.
- a hollow fiber membrane bundle 3 composed of a plurality of hollow fiber membranes 2 is assembled into a housing main body without being divided into small bundles.
- the fixed layer 7 may be formed around the bundle 3.
- the fixing layer only needs to be formed with a fixing agent dense portion that extends over the entire thickness of the fixing layer along the longitudinal direction of the hollow fiber membrane, and the partition member need not necessarily be provided.
- a pipe member extending over the entire thickness of the fixed layer along the longitudinal direction of the hollow fiber membrane is arranged near the central axis of the hollow fiber membrane bundle, and the pipe interior of the pipe member is used as a “buffer space” to fix the fixing agent. May be used to form a fixed layer.
- the hollow fiber membrane bundle 3 composed of a plurality of hollow fiber membranes 2 is divided into a plurality of small bundles, and each small bundle is separated at intervals.
- the small bundles may be arranged by bringing the small bundles into contact with each other, and the fixed layer 7 may be formed between the small bundles by setting the interval between the small bundles as a “buffer space”.
- the hollow fiber membrane module shown in FIG. 11B can be manufactured, for example, by the method shown in FIG.
- FIG. 12 (a) a plurality of small bundles of hollow fiber membranes 3 in which a plurality of hollow fiber membranes 2 whose ends are plugged are prepared. Then, an elongated straw-shaped fixing agent injection member 81 is arranged between the hollow fiber membrane bundles 3 so that the hollow fiber membrane bundles 3 are arranged at intervals in the housing main body, and the unit is assembled. Then, the end of the hollow fiber membrane 2 on which the fixing layer 7 is formed penetrates in the longitudinal direction of the hollow fiber membrane bundle 3 by the fixing agent injection member 81.
- the fixing agent is filled from both ends of the unit. Then, since the penetration part of the fixing agent injection member 81 functions as a flow path for the fixing agent, the filled fixing agent flows into the housing body from the penetration part of the fixing agent injection member 81. And the fixing layer 7 which fixes the hollow fiber membrane bundle 3 to a housing main-body part is formed by hardening a fixing agent. Thereby, each small bundle is arrange
- the both ends of the unit are cut to remove the seals of the hollow fiber membrane 2, and the ends of the hollow fiber membrane 2 are opened.
- the fixing agent injection member 81 is removed together with the cut pieces when the both ends of the unit are cut, so that the fixing agent injection member 81 does not remain on the cut surface, but the long fixing agent injection member 81 is provided. When used, the fixing agent injection member 81 may remain on the cut surface.
- the manufacture of the hollow fiber membrane module shown in FIG.11 (b) is complete
- any configuration may be adopted as long as it has a through portion penetrating in the longitudinal direction of the hollow fiber membrane 2 as well as the partition member.
- a partition member 71 of the hollow fiber membrane module shown in FIG. 13A a plurality of cylindrical members formed with penetrating portions penetrating in the longitudinal direction of the hollow fiber membrane bundle 3 are connected to form a cross shape as a whole. It may be what you did.
- a plurality of nets are arranged opposite to each other at regular intervals, and the plurality of nets are crossed into a cross shape. May be.
- a corrugated flat plate disposed in an inner region surrounded by a net (or a plate member) like a cross-sectional configuration of cardboard. It may be crossed into a cross shape.
- the partition member is not limited to the cross shape, and various shapes can be adopted.
- a pair of oppositely arranged plate members are arranged in three sets horizontally and one set in length, so that the hollow fiber membrane bundle 3 A small bundle of may be divided into eight.
- the means for partitioning the hollow fiber membrane bundle 3 is not limited to the partition member, and for example, the hollow fiber membrane bundle 3 may be divided by a divided net 76 as shown in FIG. Thus, by dividing the hollow fiber membrane bundle 3 by the division net 76, the hollow fiber membrane bundle 3 can be further reduced.
- the partition member 78 may be one in which one flat plate is crossed in a cross shape and no through portion is provided. Further, as shown in FIG. 15 (b), the hollow fiber membrane bundle 3 is completely formed by disposing a block-shaped spacer 77 between the hollow fiber membrane bundles 3 that are made into small bundles instead of the partition members. Even without partitioning, the fixing layer 7 can be formed by allowing a fixing agent to flow between the hollow fiber membrane bundles 3.
- the partition member may have any structure as long as it has a buffer space that can release the injection pressure of the fixing agent when the fixing agent is filled.
- the partition member may further include a flow path that guides the fixing agent to the space between the outer peripheral portion of the hollow fiber membrane bundle 3 and the inner wall side of the housing body 11 (second buffer space). More preferable.
- one end portion of the penetrating portion in the axial direction of the partition member and a side surface portion of the penetrating portion are If at least one hole is large enough to allow air to escape, it may be closed.
- one end of the penetrating portion of the partition members 6A and 6B is blocked by a lid with a small hole, and the side portion of the penetrating portion of the partition members 6A and 6B is completely blocked by a lid without a hole.
- one end portion covered with the lid is disposed on the interface side of the fixed layer.
- the other end portion that is open without being covered with the lid becomes an opening into which the fixing agent flows, and functions as a space forming a fixing agent dense portion, that is, a buffer space. Thereby, buckling can be suppressed.
- air can escape from the small hole provided in the lid, so that the fixing agent can be filled into the penetrating portion.
- one end portion of the penetrating portion of the partition members 6A and 6B is completely closed by a lid without a hole, and a side surface portion of the penetrating portion of the partition members 6A and 6B is blocked by a lid having a small hole.
- a small hole is formed in the vicinity of one end portion covered with the lid, and the one end portion covered with the lid is disposed on the interface side of the fixed layer.
- buckling can be suppressed.
- the paired plate members may not be arranged in parallel to the axial direction and / or the direction perpendicular to the axis. In this case, since the number of filled yarns can be increased, it is preferable to arrange the pair of plate members in parallel.
- the number n of filled hollow fiber membranes was confirmed.
- the hollow fiber membrane module was carefully disassembled, then the hollow fiber membrane bundle was cut out from the interface of the fixed layer, and the hollow fiber membrane bundle was collected. Finally, by counting the number of hollow fiber membranes constituting this hollow fiber membrane bundle, “the number n of filled hollow fiber membranes” was obtained.
- the “average housing inner diameter Dh” and the “interfacial distance L of the fixed layer” were confirmed. Several dimensions were measured from the module after the hollow fiber membrane bundle was cut out, and “average housing inner diameter Dh” and “interfacial distance L between fixed layers” were obtained from the average values.
- the “volume Vf of the hollow fiber membrane bundle” was obtained by substituting n, Do, and L ′ obtained by the evaluation method 1 into the equation (6).
- the “inner housing volume Vh” was obtained by substituting Dh and L obtained by the evaluation method 1 into the equation (7).
- Vf (Do / 2) 2 ⁇ ⁇ ⁇ L ′ ⁇ n (6)
- Vh (Dh / 2) 2 ⁇ ⁇ ⁇ L (7)
- the hollow fiber membrane volume filling rate Rv is obtained by substituting the “hollow fiber membrane bundle volume Vf” and “housing inner volume Vh” obtained from the equations (6) and (7) into the equation (8). I asked more.
- Rv Vf / Vh (8)
- the “yarn bundle occupation cross-sectional area Smb” refers to the cross-sectional area of the region surrounded by the entire hollow fiber membrane bundle. For example, when the hollow fiber membrane is divided into a plurality of small bundles, the cross-sectional area occupied by the smallest substantially circumscribed circle including all the small bundles is indicated.
- the “fixing agent dense portion cross-sectional area Sb” is a cross-sectional area of a portion filled with the fixing agent among the portions included in the occupied cross-sectional area of the hollow fiber membrane bundle.
- the “yarn bundle occupation cross-sectional area Smb” includes the small bundles 3A, 3B, 3C, 3D, the wall portions 31, 32, 33, 34 of the partition members 6A, 6B, and the through portions 21, 22, of the partition members 6A, 6B. 23, 24, and 26 are cross-sectional areas.
- the “fixing agent dense portion cross-sectional area Sb” is a cross-sectional area of the through portions 21, 22, 23, 24, and 26 of the partition members 6A and 6B.
- the partition member is not provided and the hollow fiber membrane bundle 3 is made into a small bundle, and a gap is formed between the small bundles to fill the fixing agent.
- the cross-sectional area of the fixing agent dense part is the cross-sectional area of all the portions of the cross-sectional area included in the cross-sectional area occupied by the yarn bundle that is filled with the fixing agent in the gaps between the small bundles.
- the boundary between the partition member and the fixing agent in the fixing layer is determined according to the scheme shown in FIG.
- Tris (hydroxymethyl) aminomethane (Nacalai Tesque) was dissolved in ultrapure water and adjusted to pH 8 by adding hydrochloric acid to a concentration of 20 mmol / L (pH 8). Thereafter, a filter having a pore diameter of 0.45 ⁇ m was used.
- BSA was dissolved in 20 mmol / L (pH 8) Tris-HCl buffer to obtain 1 [g (BSA) / L (buffer)].
- a filter having a pore diameter of 0.45 ⁇ m was used.
- Preparation before measurement of adsorption performance was performed according to the following procedure.
- the hollow fiber membrane module was fixed in an upright state, and a supply pipe from HPLC was connected to a cap below the hollow fiber membrane module.
- the air in the module was discharged while supplying the liquid to the module.
- the nozzle below the side of the hollow fiber membrane module was connected to the HPLC inlet pipe, and the upper cap and the nozzle on the side were closed. That is, the hollow fiber membrane module was set in a state where total filtration by an internal pressure filtration method was possible.
- the measurement of the adsorption performance was performed by performing the filtration operation of each solution in the following order. That is, first, the adsorption membrane module is equilibrated using a buffer solution, the protein is adsorbed using an indicator protein solution, and the buffer solution is used again to adsorb the membrane. The fourth step is to elute the adsorbed protein adsorbed on the adsorption membrane using a salt buffer, and the fifth is to use the buffer again to adjust the salt concentration of the adsorption membrane module. Reducing playback operation was performed. Each solution was subjected to an internal pressure type total filtration operation at a constant flow rate with respect to the hollow fiber membrane module.
- the adsorption behavior and elution behavior of the protein were traced using a visible ultraviolet absorptiometer, and the leakage trend of the protein to the filtrate side was confirmed by the change in absorbance at a wavelength of 280 nm.
- the measurement of adsorption performance was performed in the same procedure as described in Evaluation Method 7. However, the adsorption behavior and elution behavior of the protein were confirmed by tracking the change in absorbance at 280 nm using a visible ultraviolet absorptiometer for each fraction of the filtrate after the filtrate was fractionated and collected at a fixed time interval with a fracolator.
- dynamic adsorption capacity The amount of protein adsorbed per unit membrane volume when the filtrate reaches an absorbance of 10% is referred to as “dynamic adsorption capacity”.
- the dynamic adsorption capacity calculated by this method is referred to as a dynamic adsorption capacity in a module form or simply “module adsorption capacity”.
- module adsorption capacity In the field of biotechnology purification, etc., “dynamic adsorption capacity” is a commonly used term.
- the dynamic adsorption capacity in the form of the adsorption hollow fiber membrane calculated by this method is referred to as the dynamic adsorption capacity in the form of a single thread or simply “adsorption capacity of a single thread”, and is shown in [Evaluation Method 9]. Used for comparison with “module adsorption capacity”.
- the hollow fiber membrane module was repeatedly used up to 10 times, and the number of times until a defect occurred in the fixed layer was counted. That is, in the durability evaluation of the fixed layer, the number of repetitions that can be used without causing a defect of the fixed layer is evaluated as the number of durability. For example, the first adsorption and elution is counted as 1, and when the defect of the fixed layer occurs during the second use, the durability is set to one time.
- the hollow fiber membrane of the adsorption membrane can elute the protein to be adsorbed by changing the conditions of the liquid to be supplied (pH, conductivity, etc.) such as a series of operation procedures described in Evaluation Method 7. .
- Module A first evaluated the adsorption amount of the module according to Evaluation Methods 6 and 7. Next, the module was disassembled according to the evaluation methods 1, 2, 3, and 4, and the volume filling rate Rv, the buckling rate W, and the membrane volume Vmm were calculated. Then, the adsorption capacity per unit membrane volume in the module form was calculated from the evaluation method 9. Furthermore, the fixing agent dense part ratio Rb was determined according to Evaluation Method 5.
- Module B first disassembled the module according to the evaluation methods 1, 2, 3, and 4, and calculated the volume filling rate Rv and the buckling rate W. Next, the adsorption capacity per unit membrane volume in a single yarn form was calculated from the adsorbed membrane sampled after disassembly and according to Evaluation Method 10. Furthermore, the fixing agent dense part ratio Rb was determined according to Evaluation Method 5.
- the scalability of the adsorption membrane module was calculated from the adsorption capacity of the module A of the module A and the adsorption capacity of the single yarn of the module B according to the evaluation method 11.
- the difference between the buckling rates was compared with the absolute value of the difference as the buckling rate difference.
- Module C evaluated the durability of the fixed layer according to Evaluation Method 12.
- Example 1 Three hollow fiber membrane modules (1A, 1B, 1C) shown in FIG. In Example 1, no partition member was used.
- module adsorption capacity was evaluated for module 1A, 27.4 g of BSA was adsorbed per module. Thereafter, when the disassembly investigation was performed, the number n of the hollow fiber membranes filled in the module 1A was 460, the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm, and the hollow fiber membranes The average effective length L ′ was 206 mm. Further, the inter-interface distance L between the fixed layers was 190.0 mm, and the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 61.9%
- the buckling rate W was 108.4%
- the membrane volume (annular portion) Vmm was 633 mL. From this, the adsorption capacity of the module was calculated to be 43.3 mg / mL.
- the fixing agent dense part ratio Rb was 0%.
- the number n of the hollow fiber membranes filled in the module 1B was 460, and the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm.
- the average effective length L ′ of the yarn membrane was 212 mm.
- the inter-interface distance L between the fixed layers was 190.0 mm, and the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 63.8%
- the buckling rate W was 111.6%
- the membrane volume (annular portion) Vmm was 652 mL.
- the dynamic adsorption capacity of the single yarn of the extracted hollow fiber membrane was 44.3 mg / mL, and the scalability was 97.7%.
- Example 1 a hollow fiber membrane module with scalability can be manufactured.
- Example 2 Three hollow fiber membrane modules (2A, 2B, 2C) shown in FIG. In Example 2, no partition member was used.
- module adsorption capacity of module 2A 29.8 g of BSA was adsorbed per module. Thereafter, a disassembly investigation was performed.
- the number n of hollow fiber membranes filled in the module 2A was 510, and the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm.
- the average effective length L ′ was 206 mm.
- the inter-interface distance L between the fixed layers was 190.0 mm
- the housing inner diameter Dh 104.7 mm.
- the volume filling rate Rv was 68.7%
- the buckling rate W was 108.4%
- the membrane volume (annular portion) Vmm was 702 mL. From this, the adsorption capacity of the module was calculated to be 42.5 mg / mL.
- the fixing agent dense part ratio Rb was 0%.
- the number n of hollow fiber membranes filled in the module 2B was 510, and the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm.
- the average effective length L ′ of the yarn membrane was 213 mm.
- the inter-interface distance L between the fixed layers was 190.0 mm, and the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 71.0%
- the buckling rate W was 112.1%
- the film volume (annular portion) Vmm was 726 mL.
- the extracted hollow fiber membrane had a dynamic adsorption capacity of 44.7 mg / mL and a scalability of 95.1%.
- Example 2 a hollow fiber membrane module with scalability can be manufactured.
- Example 3 In the bundling process shown in FIG. 4, three hollow fiber membrane modules are arranged between six bundles of hollow fiber membrane bundles by arranging six straw-shaped fixing agent injection members having an outer diameter of 10 mm and an inner diameter of 8 mm ( 3A, 3B, 3C). In Example 3, no partition member was used.
- module adsorption capacity of module 3A 28.6 g of BSA was adsorbed per module. Thereafter, when the disassembly investigation was performed, the number n of hollow fiber membranes filled in the module 3A was 480, the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm, and the hollow fiber membranes The average effective length L ′ was 197 mm. Further, the inter-interface distance L between the fixed layers was 190.0 mm, and the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 61.8%
- the buckling rate W was 103.7%
- the film volume (annular portion) Vmm was 632 mL. From this, the adsorption capacity of the module was calculated to be 45.3 mg / mL.
- the fixing agent dense part ratio Rb was 4.2%.
- the number n of hollow fiber membranes filled in the module 3B was 480, and the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm.
- the average effective length L ′ of the yarn membrane was 198 mm.
- the inter-interface distance L between the fixed layers was 190.0 mm, and the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 62.1%
- the buckling rate W was 104.2%
- the membrane volume (annular portion) Vmm was 635 mL.
- the dynamic adsorption capacity of the extracted hollow fiber membrane was 46.4 mg / mL, and the scalability was 97.6%.
- Example 3 a hollow fiber membrane module with scalability can be manufactured.
- the fixing agent injection member is used to form a fixing agent dense portion extending over the entire thickness of the fixing layer along the longitudinal direction of the hollow fiber membrane, and further, buckling is suppressed and buckling variation also occurs. It was shown that by making it small, there is an effect of preventing deviating from the assumed volume filling rate.
- Example 4 In the bundling process shown in FIG. 4, by arranging a straw-shaped fixing agent injection member having an outer diameter of 10 mm and an inner diameter of 8 mm between the hollow fiber membrane bundles divided into seven small bundles, FIG. 3) (4A, 4B, 4C) were produced. In Example 4, no partition member was used.
- module adsorption capacity of module 4A 26.3 g of BSA was adsorbed per module. Thereafter, a disassembly investigation was performed.
- the number n of hollow fiber membranes filled in the module 4A was 480
- the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm
- the hollow fiber membranes The average effective length L ′ was 190 mm.
- the inter-interface distance L between the fixed layers was 190.0 mm
- the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 59.6%
- the buckling rate W was 100%
- the membrane volume (annular portion) Vmm was 609 mL. From this, the adsorption capacity of the module was calculated to be 43.1 mg / mL.
- the fixing agent dense part ratio Rb was 32.7%.
- the number n of hollow fiber membranes filled in the module 4B was 480, and the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm.
- the average effective length L ′ of the yarn membrane was 190 mm.
- the inter-interface distance L between the fixed layers was 190.0 mm, and the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 59.6%
- the buckling rate W was 100%
- the membrane volume (annular portion) Vmm was 609 mL.
- the dynamic adsorption capacity of the extracted hollow fiber membrane was 43.7 mg / mL, and the scalability was 98.7%.
- Example 4 it was shown in Example 4 that it is possible to manufacture a hollow fiber membrane module that achieves scalability.
- a fixing agent dense portion extending across the entire thickness of the fixing layer along the longitudinal direction of the hollow fiber membrane is formed at an interval between the small bundles, and further, buckling is suppressed and buckling is uneven. It was shown that by making it small, there is an effect of preventing deviating from the assumed volume filling rate.
- Example 5 In the bundling process shown in FIG. 4, a block-shaped spacer 77 having a cross section of 6 mm ⁇ 6 mm is disposed between the hollow fiber membrane bundles 3 that are made into small bundles in place of the partition member, whereby FIG. 3) (5A, 5B, 5C) were produced. In Example 5, no partition member was used.
- module adsorption capacity of module 5A 29.1 g of BSA was adsorbed per module. Thereafter, a disassembly investigation was conducted.
- the number n of hollow fiber membranes filled in the module 5A was 540
- the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm
- the hollow fiber membranes The average effective length L ′ was 190 mm.
- the inter-interface distance L between the fixed layers was 190.0 mm
- the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 67.1%
- the buckling rate W was 100%
- the film volume (annular portion) Vmm was 686 mL. From this, the adsorption capacity of the module was calculated to be 42.5 mg / mL.
- the fixing agent dense part ratio Rb was 12.6%.
- the number n of the hollow fiber membranes filled in the module 5B was 540, the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm, hollow The average effective length L ′ of the yarn membrane was 190 mm. Further, the inter-interface distance L between the fixed layers was 190.0 mm, and the housing inner diameter Dh was 104.7 mm. As a result, the volume filling rate Rv was 67.1%, the buckling rate W was 100%, and the film volume (annular portion) Vmm was 686 mL.
- the extracted hollow fiber membrane had a dynamic adsorption capacity of 45.0 mg / mL and a scalability of 94.4%.
- Example 5 it was shown in Example 5 that it is possible to manufacture a hollow fiber membrane module that achieves scalability.
- a fixing agent dense portion that extends over the entire thickness of the fixed layer along the longitudinal direction of the hollow fiber membrane, and further suppressing buckling and reducing variation in buckling, the assumed volume filling It was shown that it has the effect of preventing the deviation from the rate.
- Example 6 In the bundling process shown in FIG. 4, the hollow fiber membrane bundle is divided into four small bundles, and each small bundle is divided by a partition member, so that three hollow fiber membrane modules (6A) shown in FIG. 6B, 6C). A partition member having a plate thickness of 4 mm and a width of 102 mm was used.
- the module 6A was evaluated for the adsorption capacity of the module, and 31.5 g of BSA was adsorbed per module. Thereafter, a disassembly investigation was conducted. As a result, the number n of hollow fiber membranes filled in the module 6A was 512, the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm, and the hollow fiber membranes. The average effective length L ′ was 205 mm. Further, the inter-interface distance L between the fixed layers was 190.0 mm, and the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 68.6%
- the buckling rate W was 107.9%
- the film volume (annular portion) Vmm was 701 mL. From this, the adsorption capacity of the module was calculated to be 44.8 mg / mL.
- the fixing agent dense part ratio Rb was 0.0%.
- the number n of hollow fiber membranes filled in the module 6B was 512, and the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm.
- the average effective length L ′ of the yarn membrane was 211 mm.
- the inter-interface distance L between the fixed layers was 190.0 mm, and the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 70.6%
- the buckling rate W was 111.1%
- the film volume (annular portion) Vmm was 722 mL.
- the dynamic adsorption capacity of the extracted hollow fiber membrane was 47.3 mg / mL, and the scalability was 94.8%.
- the difference in buckling rate between modules 6A and 6B was 3.2%.
- the durability of module 6C was 10 times or more.
- Example 6 it was shown in Example 6 that it is possible to manufacture a hollow fiber membrane module that achieves scalability. In addition, it was shown that cracks did not occur in the fixed layer, and that repeated durability was improved.
- Example 7 In the bundling step shown in FIG. 4, the hollow fiber membrane bundle is divided into four small bundles, and each small bundle is partitioned by a plurality of cylindrical members connected in a cross shape, whereby the hollow shown in FIG. Three yarn membrane modules (7A, 7B, 7C) were produced.
- the cylindrical members constituting the cross shape ten cylindrical members having an outer diameter of 14.5 mm and an inner diameter of 12 mm were used.
- module adsorption capacity of module 7A 26.8 g of BSA was adsorbed per module. Thereafter, when the disassembly investigation was performed, the number n of the hollow fiber membranes filled in the module 7A was 460, the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm, and the hollow fiber membranes The average effective length L ′ was 193 mm. Further, the inter-interface distance L between the fixed layers was 190.0 mm, and the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 58.0%
- the buckling rate W was 101.6%
- the film volume (annular portion) Vmm was 593 mL. From this, the adsorption capacity of the module was calculated to be 45.1 mg / mL.
- the fixing agent dense part ratio Rb was 14.1%.
- the number n of the hollow fiber membranes filled in the module 7B was 460, and the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm.
- the average effective length L ′ of the yarn membrane was 193.5 mm.
- the inter-interface distance L between the fixed layers was 190.0 mm, and the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 58.2%
- the buckling rate W was 101.8%
- the film volume (annular portion) Vmm was 595 mL.
- the extracted hollow fiber membrane had a dynamic adsorption capacity of 45.5 mg / mL and a scalability of 99.1%.
- module 7A and 7B The difference in buckling rate between modules 7A and 7B was 0.3%.
- the durability of module 7C was 10 times or more.
- Example 7 a hollow fiber membrane module with scalability can be manufactured.
- a fixing agent dense portion that extends over the entire thickness of the fixed layer along the longitudinal direction of the hollow fiber membrane, and further suppressing buckling and reducing variation in buckling, the assumed volume filling It was shown that it has the effect of preventing the deviation from the rate.
- Example 8 the hollow fiber membrane bundle is divided into eight small bundles, and each pair of small bundles is divided into a pair of opposingly arranged plate members arranged in three sets and one set in the vertical direction.
- three hollow fiber membrane modules (8A, 8B, 8C) shown in FIG. As the partition member, a plate member having a plate thickness of 4 mm and a pair of plate members having a separation distance of 4 mm was used.
- module adsorption capacity of module 8A 18.8 g of BSA was adsorbed per module. Thereafter, a disassembly investigation was performed.
- the number n of hollow fiber membranes filled in the module 8A was 340
- the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm
- the hollow fiber membranes The average effective length L ′ was 190 mm.
- the inter-interface distance L between the fixed layers was 190.0 mm
- the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 42.2%
- the buckling rate W was 100.0%
- the film volume (annular portion) Vmm was 432 mL. From this, the adsorption capacity of the module was calculated to be 43.6 mg / mL.
- the fixing agent dense part ratio Rb was 14.3%.
- the number n of hollow fiber membranes filled in the module 8B was 340, and the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm.
- the average effective length L ′ of the yarn membrane was 190 mm.
- the inter-interface distance L between the fixed layers was 190.0 mm, and the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 42.2%
- the buckling rate W was 100.0%
- the film volume (annular portion) Vmm was 432 mL.
- the dynamic adsorption capacity of the extracted hollow fiber membrane was 43.9 mg / mL, and the scalability was 99.4%.
- the difference in buckling rate between modules 8A and 8B was 0.0%.
- the durability of module 8C was 10 times or more.
- Example 8 it was shown in Example 8 that it is possible to manufacture a hollow fiber membrane module that achieves scalability. In addition, it was shown that cracks did not occur in the fixed layer, and that repeated durability was improved. In addition, by forming a fixing agent dense portion that extends over the entire thickness of the fixed layer along the longitudinal direction of the hollow fiber membrane, and further suppressing buckling and reducing variation in buckling, the assumed volume filling It was shown that it has the effect of preventing the deviation from the rate.
- Example 9 In the bundling process shown in FIG. 4, the hollow fiber membrane bundle is divided into four small bundles, and a pair of opposingly arranged plate members are partitioned by a partition member arranged in a cross shape. Three hollow fiber membrane modules shown in 2 (9A, 9B, 9C) were produced. As the partition member, a plate member having a plate thickness of 4 mm and a pair of plate members having a separation distance of 4 mm was used.
- the module adsorption capacity of module 9A 25.9 g of BSA was adsorbed per module. Thereafter, when the disassembly investigation was performed, the number n of hollow fiber membranes filled in the module 9A was 460, the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm, and the hollow fiber membranes The average effective length L ′ was 190 mm. Further, the inter-interface distance L between the fixed layers was 190.0 mm, and the housing inner diameter Dh was 104.7 mm. As a result, the volume filling rate Rv was 57.1%, the buckling rate W was 100.0%, and the film volume (annular portion) Vmm was 584 mL. From this, the adsorption capacity of the module was calculated to be 44.3 mg / mL. The fixing agent dense part ratio Rb was 8.9%.
- the number n of the hollow fiber membranes filled in the module 9B was 460, and the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm.
- the average effective length L ′ of the yarn membrane was 190 mm.
- the inter-interface distance L between the fixed layers was 190.0 mm, and the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 57.1%
- the buckling rate W was 100.0%
- the film volume (annular portion) Vmm was 584 mL.
- the dynamic adsorption capacity of the extracted hollow fiber membrane was 44.4 mg / mL, and the scalability was 99.8%.
- the difference in buckling rate between modules 9A and 9B was 0.0%.
- the durability of module 9C was 10 times or more.
- Example 9 a hollow fiber membrane module with scalability can be manufactured. In addition, it was shown that cracks did not occur in the fixed layer, and that repeated durability was improved. In addition, by forming a fixing agent dense portion that extends over the entire thickness of the fixed layer along the longitudinal direction of the hollow fiber membrane, and further suppressing buckling and reducing variation in buckling, the assumed volume filling It was shown that it has the effect of preventing the deviation from the rate.
- Example 10 In the bundling step shown in FIG. 4, the hollow fiber membrane bundle is divided into eight small bundles, and a pair of opposingly arranged plate members are divided into two bundles by a partition member arranged in a cross shape, Two hollow fiber membrane modules (10A, 10B, 10C) shown in FIG. 14B were created by dividing the two small bundles partitioned by the partition member with a divided net.
- a partition member a plate member having a plate thickness of 4 mm and a pair of plate members having a separation distance of 4 mm was used. A thin net having a mesh was used as the divided net.
- module adsorption capacity of module 10A 26.8 g of BSA was adsorbed per module. Thereafter, a disassembly investigation was performed.
- the number n of the hollow fiber membranes filled in the module 10A was 460
- the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm
- the hollow fiber membranes The average effective length L ′ was 190 mm.
- the inter-interface distance L between the fixed layers was 190.0 mm
- the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 57.1%
- the buckling rate W was 100.0%
- the film volume (annular portion) Vmm was 587 mL. From this, the adsorption capacity of the module was calculated to be 45.9 mg / mL.
- the fixing agent dense part ratio Rb was 21.5%.
- the number n of the hollow fiber membranes filled in the module 10B was 460, and the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm.
- the average effective length L ′ of the yarn membrane was 190 mm.
- the inter-interface distance L between the fixed layers was 190.0 mm, and the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 57.1%
- the buckling rate W was 100.0%
- the film volume (annular portion) Vmm was 584 mL.
- the dynamic adsorption capacity of the extracted hollow fiber membrane was 46.0 mg / mL, and the scalability was 99.8%.
- the difference in buckling rate between modules 10A and 10B was 0.0%.
- the durability of module 10C was 10 times or more.
- Example 10 a hollow fiber membrane module with scalability can be manufactured. In addition, it was shown that cracks did not occur in the fixed layer, and that repeated durability was improved. In addition, by forming a fixing agent dense portion that extends over the entire thickness of the fixed layer along the longitudinal direction of the hollow fiber membrane, and further suppressing buckling and reducing variation in buckling, the assumed volume filling It was shown that it has the effect of preventing the deviation from the rate.
- Example 11 the hollow fiber membrane bundle is divided into four small bundles, the outer circumferences of the divided small bundles are each covered with a protective member, and a pair of opposed plate members are arranged in a cross shape.
- a protective member By partitioning each small bundle covered with the protective member with the partition member, three hollow fiber membrane modules (11A, 11B, 11C) shown in FIGS. 2 and 3 were produced.
- the partition member a plate member having a plate thickness of 4 mm and a pair of plate members having a separation distance of 4 mm was used. A thin net having a mesh was used as the divided net.
- module adsorption capacity of module 11A was evaluated, 18.9 g of BSA was adsorbed per module. Thereafter, a disassembly investigation was conducted.
- the number n of hollow fiber membranes filled in the module 11A was 332
- the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm, and the hollow fiber membranes.
- the average effective length L ′ was 190 mm.
- the inter-interface distance L between the fixed layers was 190.0 mm
- the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 41.2%
- the buckling rate W was 100.0%
- the film volume (annular portion) Vmm was 422 mL. From this, the adsorption capacity of the module was calculated to be 44.9 mg / mL.
- the fixing agent dense part ratio Rb was 39.2%.
- the number n of the hollow fiber membranes filled in the module 11B was 332, the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm, hollow The average effective length L ′ of the yarn membrane was 190 mm. Further, the inter-interface distance L between the fixed layers was 190.0 mm, and the housing inner diameter Dh was 104.7 mm. As a result, the volume filling rate Rv was 41.2%, the buckling rate W was 100.0%, and the film volume (annular portion) Vmm was 422 mL. The dynamic adsorption capacity of the extracted hollow fiber membrane was 45.1 mg / mL, and the scalability was 99.5%.
- the difference in buckling rate between modules 11A and 11B was 0.0%.
- the durability of module 11C was 10 times or more.
- Example 11 it was shown in Example 11 that it is possible to manufacture a hollow fiber membrane module that achieves scalability. In addition, it was shown that cracks did not occur in the fixed layer, and that repeated durability was improved. In addition, by forming a fixing agent dense portion that extends over the entire thickness of the fixed layer along the longitudinal direction of the hollow fiber membrane, and further suppressing buckling and reducing variation in buckling, the assumed volume filling It was shown that it has the effect of preventing the deviation from the rate.
- module 1'A When module 1'A was evaluated for module adsorption capacity, 28.9 g of BSA was adsorbed per module. Thereafter, a disassembly investigation was performed. As a result, the number n of hollow fiber membranes filled in the module 1′A was 560, and the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm. The average effective length L ′ of the yarn membrane was 204 mm. Further, the inter-interface distance L between the fixed layers was 190.0 mm, and the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 74.7%
- the buckling rate W was 107.4%
- the membrane volume (annular portion) Vmm was 763 mL. From this, the module adsorption capacity was calculated to be 37.8 mg / mL.
- the fixing agent dense part ratio Rb was 0.0%.
- the number n of hollow fiber membranes filled in the module 1′B was 560, and the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.
- the average effective length L ′ of the hollow fiber membrane was 209 mm.
- the inter-interface distance L between the fixed layers was 190.0 mm, and the housing inner diameter Dh was 104.7 mm.
- the volume filling rate Rv was 76.5%
- the buckling rate W was 110.0%
- the film volume (annular portion) Vmm was 782 mL.
- the dynamic adsorption capacity of the extracted hollow fiber membrane was 43.2 mg / mL, and the scalability was 87.6%.
- the module 2'A When the module 2'A was evaluated for the adsorption capacity of the module, 239.4 g of BSA was adsorbed per module. Thereafter, a disassembly investigation was conducted. As a result, the number n of the hollow fiber membranes filled in the module 2′A was 880, and the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.69 mm. The average effective length L ′ of the yarn membrane was 1016 mm. Further, the inter-interface distance L between the fixed layers was 936.0 mm, and the housing inner diameter Dh was 130.0 mm.
- the volume filling rate Rv was 77.0%
- the buckling rate W was 108.5%
- the film volume (ring portion) Vmm was 5975 mL. From this, the adsorption capacity of the module was calculated to be 40.1 mg / mL.
- the fixing agent dense part ratio Rb was 0.0%.
- the number n of hollow fiber membranes filled in the module 2′B was 880, and the average inner diameter Di / average outer diameter Do of the hollow fiber membranes was 2.26 mm / 3.
- the average effective length L ′ of the hollow fiber membrane was 996 mm.
- the inter-interface distance L between the fixed layers was 936.0 mm, and the housing inner diameter Dh was 130.0 mm.
- the volume filling rate Rv was 75.4%
- the buckling rate W was 106.4%
- the membrane volume (annular portion) Vmm was 5857 mL.
- the dynamic adsorption capacity of the extracted hollow fiber membrane was 45.8 mg / mL, and the scalability was 87.6%.
- FIG. 17 shows the relationship between the volume filling rate and the adsorption capacity performance ratio in Examples 1 to 11 and Comparative Examples 1 and 2.
- Comparative Examples 1 and 2 in which the volume filling rate is 70% or more, the module adsorption capacity with respect to the single yarn adsorption capacity shows a low value of less than 90%, and it is difficult to ensure scalability.
- the volume filling rate in the range of 30% or more and less than 70%, the module adsorption capacity with respect to the single yarn adsorption capacity is as high as 90% or more, and high scalability is ensured. It turns out that it is possible.
- Comparative Example 2 is a model of the hollow fiber membrane module described in Japanese Patent Application Laid-Open No. 2011-016116 and Japanese Patent Application Laid-Open No. 2011-016119.
- the hollow fiber membrane was greatly buckled by filling with the fixing agent, and the volume filling rate was increased to 77.0%.
- the adsorption capacity per unit membrane volume was low, and the adsorption capacity of the module relative to the adsorption capacity of the single yarn was as low as 87.5%.
- the fixing agent dense part ratio is 0.0%, 4.2%, 8 .9%, 12.6%, 32.7%
- buckling rate difference is 3.2%, 0.5%, 0.0%, 0.0%, 0.0%, fixing agent It was confirmed that the variation in the volume filling rate due to buckling can be suppressed when the dense portion ratio is 3% or more.
- Examples 1 to 5 are examples in which no partition member is provided in the fixed layer
- Examples 6 to 11 are examples in which the partition member is provided in the fixed layer. It was confirmed that the repetition durability of the fixed layer was improved by providing the partition member.
- SYMBOLS 1 Hollow fiber membrane module (adsorption separation membrane module), 2 ... Hollow fiber membrane, 2a, 2b ... End part, 3 ... Hollow fiber membrane bundle, 3A, 3B, 3C, 3D ... Small bundle, 3a, 3b ... Hollow fiber End of membrane bundle, 4 ... Housing (cylinder), 4A ... Space, 4B ... Space, 4C ... Space, 6, 6A, 6B ... Partition member, 7, 7A, 7B ... Fixed layer, 8 ... Protection member, 11 ... Housing body (cylinder), 11a, 11b ... Cutting allowance, 12A, 12B ... Cap, 13A, 13B ... Fixing tool, 14A, 14B ... Pipe part, 16A, 16B ...
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Abstract
Description
Rv=Vf/Vh (1)
Vf=(Do/2)2×π×L’×n (2)
Doは中空糸膜2の平均外径、L’は中空糸膜2の平均有効長、nはハウジング4に充填された中空糸膜2の充填本数である。
Vh=(Dh/2)2×π×L (3)
Dhはハウジング本体部11の平均内径、Lは中空糸膜モジュール1における固定層7A,7Bの界面間距離である。
W=Rv/Rv0 (4)
理論体積充填率Rv0とは、座屈が全くない(すなわち、中空糸膜モジュールに充填されたすべての中空糸膜2が固定層間で直線状に配置された)状態の体積充填率で、上述した中空糸膜束3の体積を求める式(2)において、中空糸膜2の平均有効長L’に、中空糸膜モジュール1における固定層7A,7Bの界面間距離Lを代入したときの体積充填率である。座屈率は100%以上の数値範囲となる。また、120%以下であることが好ましく、110%以下であることがより好ましく、105%以下であることがさらに好ましい。
Rb=Sb/Sf (5)
固定剤密部率Rbの下限値は、より好ましくは4%以上とし、さらにより好ましくは7%以上とし、固定剤密部率Rbの上限値は、より好ましくは50%未満とし、さらにより好ましくは30%未満とする。すなわち、7%以上30%未満とするのが最も好ましい。
次の手順で中空糸膜モジュール1を解体し、本数と寸法とを実測することで、「中空糸膜の充填本数n」と、「中空糸膜の平均有効長L’」と、「中空糸膜の平均内径Di」および「中空糸膜の平均外径Do」と、「ハウジングの平均内径Dh」と、「固定層の界面間距離L」とを得た。
「中空糸膜束の体積充填率Rv」は、「中空糸膜束の体積Vf」および「ハウジング内容積Vh」から求めた。
Vf=(Do/2)2×π×L’×n (6)
Vh=(Dh/2)2×π×L (7)
「中空糸膜の体積充填率Rv」は、式(6)および式(7)より求められる「中空糸膜束の体積Vf」および「ハウジング内容積Vh」を、式(8)に代入することより求めた。
Rv=Vf/Vh (8)
中空糸膜の座屈の程度を示す「座屈率W」は、体積充填率Rvと理論体積充填率Rv0とを用いて、式(9)から求めた。
W=Rv/Rv0 (9)
Vf0=(Do/2)2×π×L×n (10)
「座屈率W」は、式(8)および式(10)を、式(9)に代入することより求めた。また、式(9)を展開すると、座屈率Wは式(11)のように簡素化できる。
W= L’/L (11)
「中空糸膜モジュールに充填された中空糸膜体積Vmm」は、評価方法1より得たn、Di、Do、L’を、式(12)に代入することから求めた。なお、中空糸膜の場合には、吸着に寄与する部分の膜体積として、中空糸膜の円環体積を用いるのが適当である。中空糸膜体積Vmmは、円環断面積×平均有効長×充填本数となり、式(12)で表される。
Vmm={(Do/2)2-(Di/2)2}×π×L’×n (12)
固定層の固定剤密部率Rbとは、中空糸膜束の占有断面積(糸束占有断面積Smb)に対する固定剤密部の断面積(固定剤密部断面積Sb)として、式(13)で定義する。
Rb=Sb/Smb (13)
「糸束占有断面積Smb」とは、中空糸膜束全体で囲われた領域の断面積を指す。例えば中空糸膜が複数の小束に分割されている場合には、全ての小束を含む最小の略外接円の占める断面積を指す。「固定剤密部断面積Sb」とは、中空糸膜束の占有断面積に含まれる部分のうち、固定剤が充填される部分の断面積である。
被吸着物質としては、指標タンパク質を用いた。精製装置の性能を示すために最も適したタンパク質を用いることが好ましく、一般に用いられるタンパク質としては、BSA(牛血清アルブミン)やリゾチームがある。アニオン交換膜の評価ではBSAを、カチオン交換膜の評価ではリゾチームを使用することが多いが、評価条件(pH、緩衝液など)によって適当なものを選ぶことが可能である。本実施例では、指標タンパク質としてSIGMA社製のBSAを用いた。被吸着物質として精製されたタンパク質の市販品を用いて吸着性能を計測することは、バイオテクノロジーの精製装置の性能表示を行う際に一般に用いられている。
トリス(ヒドロキシメチル)アミノメタン(ナカライテスク)を超純水に溶解し、塩酸を加えpH8に調整後、濃度20mmol/L(pH8)とした。その後、孔径0.45μmのフィルターを通したものを用いた。
20mmol/L(pH8)トリス塩酸緩衝液に対しBSAを溶解させ、1[g(BSA)/L(緩衝液)]とした。孔径0.45μmのフィルターを通したものを用いた。
上記トリス塩酸緩衝液にNaCl(和光試薬特級)を溶解し、濃度1mol/Lの塩化ナトリウムを含む緩衝液を調製した。その後、孔径0.45μmのフィルターを通したものを用いた。
吸着膜モジュールの指標タンパク質吸着性能の評価には、高速液体クロマトグラフィー(HPLC)システムを用いた。HPLCとしては、送液ポンプ、流量計、圧力計、可視紫外吸光度計から構成される、株式会社ワイエムシィの中圧クロマト装置「BP-5000S-L」を使用した。
吸着中空糸膜の指標タンパク質吸着性能の評価には、チューブポンプを用いた。予め送液量調整したチューブポンプに、圧力計と、有効膜長7cmの吸着中空糸膜を接続し、中空部の空気を排除することで、内圧ろ過方式の全ろ過ができる状態に設定した。
評価方法7において、指標タンパク質吸着操作時のろ過液側へのタンパク質の漏洩動向から、ろ液後の吸光度が、ろ過前の指標タンパク質溶液(原液)の吸光度の10%になる時点のろ液量[mL]を確認した。そして、このろ液量を1g/Lの関係からタンパク質の重量に換算することで、吸光度の10%になる時点のタンパク質吸着量[mg]を算出した。さらに、このタンパク質吸着量[mg]を、評価方法4で求めた吸着膜モジュールに充填された中空糸膜体積Vmm[mL]で割ることによって、モジュール形態での単位膜体積当たりのタンパク質吸着量[mg/mL]を算出した。
評価方法8において得られた値を基に、評価方法9と同様の手順により、吸着中空糸膜形態での単位膜体積当たりのタンパク質吸着量[mg/mL]を算出した。ただし、評価方法8での中空糸膜の体積Vmm[mL]は、円環断面積×有効膜長で表されるため、式(14)に、評価方法1で求めたDi,Doと、評価に用いた中空糸膜の有効膜長Lsを代入することで求めた。
Vms=={(Do/2)2-(Di/2)2}×π×Ls (14)
「吸着膜モジュールのスケーラビリティ」を、評価方法10で得た「中空糸膜単糸形態の動的吸着容量」と、評価方法9で得た「吸着膜モジュールの動的吸着容量」を用いて、式(15)で定義する。
吸着膜モジュールのスケーラビリティ=(モジュールの動的吸着容量)/(単糸の動的吸着容量)×100 (15)
固定層の耐久性評価として、中空糸膜モジュールの繰り返し使用を最大10回行ない、固定層に不良が発生するまでの回数をカウントした。すなわち、固定層の耐久性評価は、固定層の不良が発生せずに使用できた繰り返し回数を耐久性の回数として評価する。例えば、初回の吸着及び溶出を1としてカウントを始め、2回目の使用中に固定層の不良が発生した場合は、耐久性1回分とする。吸着膜の中空糸膜は、例えば評価方法7に記載の一連の操作手順をなど、供給する液の条件(pH、伝導度など)を変えることで、被吸着タンパク質を溶出させることが可能である。
図11(a)に示す中空糸膜モジュールを3本(1A、1B、1C)作成した。なお、実施例1では、仕切部材を用いなかった。
図11(a)に示す中空糸膜モジュールを3本(2A、2B、2C)作成した。なお、実施例2では、仕切部材を用いなかった。
図4に示す整束工程において、一束の中空糸膜束の間に、外径が10mm、内径が8mmのストロー状の固定剤注入部材を6本配置することにより、中空糸膜モジュールを3本(3A、3B、3C)作成した。なお、実施例3では、仕切部材を用いなかった。
図4に示す整束工程において、7本の小束に分割された中空糸膜束の間に、外径が10mm、内径が8mmのストロー状の固定剤注入部材を配置することにより、図11(b)に示す中空糸膜モジュールを3本(4A、4B、4C)作成した。なお、実施例4では、仕切部材を用いなかった。
図4に示す整束工程において、仕切部材に代えて小束化された中空糸膜束3同士の間に、断面が6mm×6mmのブロック状のスペーサー77を配置することで、図15(b)に示す中空糸膜モジュールを3本(5A、5B、5C)作成した。なお、実施例5では、仕切部材を用いなかった。
図4に示す整束工程において、中空糸膜束を4本の小束に分割し、各小束を仕切部材で区切ることで、図15(a)に示す中空糸膜モジュールを3本(6A、6B、6C)作成した。仕切部材は、板厚が4mm、幅が102mmのものを用いた。
図4に示す整束工程において、中空糸膜束を4本の小束に分割し、各小束を十字型に連結された複数の円筒部材で仕切ることにより、図13(a)に示す中空糸膜モジュールを3本(7A、7B、7C)作成した。十字型を構成する各円筒部材は、外径が14.5mm、内径が12mmのものを10本用いた。
図4に示す整束工程において、中空糸膜束を8本の小束に分割し、一対の対向配置された板部材が横に三組かつ縦に一組配置された仕切部材で各小束を仕切ることで、図14(a)に示す中空糸膜モジュールを3本(8A、8B、8C)作成した。仕切部材は、各板部材の板厚が4mm、一対の板部材の離間距離が4mmのものを用いた。
図4に示す整束工程において、中空糸膜束を4本の小束に分割し、一対の対向配置された板部材が十字型に配置された仕切部材で各小束を仕切ることで、図2に示す中空糸膜モジュールを3本(9A、9B、9C)作成した。仕切部材は、各板部材の板厚が4mm、一対の板部材の離間距離が4mmのものを用いた。
図4に示す整束工程において、中空糸膜束を8本の小束に分割し、一対の対向配置された板部材が十字型に配置された仕切部材で小束を二束ずつに仕切り、仕切部材で仕切られた二束の小束を分割ネットで仕切ることで、図14(b)に示す中空糸膜モジュールを3本(10A、10B、10C)作成した。仕切部材は、各板部材の板厚が4mm、一対の板部材の離間距離が4mmのものを用いた。分割ネットは、網目を有する薄いネットを用いた。
図4に示す整束工程において、中空糸膜束を4本の小束に分割し、分割した小束の外周をそれぞれ保護部材で覆い、一対の対向配置された板部材が十字型に配置された仕切部材で、保護部材で覆われた各小束を仕切ることで、図2及び図3に示す中空糸膜モジュールを3本(11A、11B、11C)作成した。仕切部材は、各板部材の板厚が4mm、一対の板部材の離間距離が4mmのものを用いた。分割ネットは、網目を有する薄いネットを用いた。
図4に示す整束工程において、中空糸膜のみを一束に整束することで、図11(a)に示す中空糸膜モジュールを3本(1’A、1’B、1’C)作成した。なお、比較例1では、仕切部材を用いなかった。
図4に示す整束工程において、中空糸膜のみを一束に整束することで、図11(a)に示す中空糸膜モジュールを3本(2’A、2’B、2’C)作成した。なお、比較例2では、仕切部材を用いなかった。
Claims (15)
- 複数本の吸着機能を有する中空糸膜からなる中空糸膜束と、
前記中空糸膜束を収容する筒体と、
前記中空糸膜束の少なくとも一方の端部を前記筒体に固定する固定層と、
を備える吸着分離膜モジュールであって、
前記固定層は、前記中空糸膜の長手方向に沿って、前記固定層厚み全域に亘って延びる固定剤密部を有する、
吸着分離膜モジュール。 - 前記固定剤密部の断面積が、前記中空糸膜束の占有断面積に対して3%以上60%未満である、
請求項1に記載の吸着分離膜モジュール。 - 前記固定層において、前記中空糸膜束が複数の小束に分割されるとともに、各小束が間隔をあけて配置されている、
請求項1又は2に記載の吸着分離膜モジュール。 - 前記固定層において前記中空糸膜束を複数の小束に仕切り、前記中空糸膜束の長手方向に貫通する貫通部を有する仕切部材を更に備える、
請求項1~3の何れか一項に記載の吸着分離膜モジュール。 - 前記貫通部に前記固定層を構成する固定剤が充填されている、
請求項4に記載の吸着分離膜モジュール。 - 前記仕切部材は、一対の板部材が対向配置されることによって前記貫通部が形成されている、
請求項4又は5に記載の吸着分離膜モジュール。 - 前記仕切部材で仕切られた前記中空糸膜束を分割する分割手段を更に備える、
請求項4~6の何れか一項に記載の吸着分離膜モジュール。 - 前記仕切部材で仕切られた前記中空糸膜束の外周を覆う保護部材を更に備える、
請求項4~7の何れか一項に記載の吸着分離膜モジュール。 - 前記仕切部材は、一対の対向配置された板部材が十字型に組み合わされている、
請求項4~8の何れか一項に記載の吸着分離膜モジュール。 - バイオ用途の分離精製に使用される、
請求項1~9の何れか一項に記載の吸着分離膜モジュール。 - 複数本の吸着機能を有する中空糸膜からなる中空糸膜束と、前記中空糸膜束を収容する筒体と、前記中空糸膜束の少なくとも一方の端部を前記筒体に固定する固定層と、を備える吸着分離膜モジュールの製造方法であって、
前記中空糸膜束、前記筒体、及び前記中空糸膜間に隙間を形成して前記中空糸膜束の長手方向に向けて延びる固定剤注入部材を備えるユニットの端部に固定剤を充填することによって、前記中空糸膜束を前記筒体に固定し、
前記ユニットの前記端部を切断することによって、前記中空糸膜の端部を開口させる、
吸着分離膜モジュールの製造方法。 - 複数本の吸着機能を有する中空糸膜からなる中空糸膜束と、前記中空糸膜束を収容する筒体と、前記中空糸膜束の少なくとも一方の端部を前記筒体に固定する固定層と、前記固定層において前記中空糸膜束を複数の小束に仕切り前記中空糸膜の長手方向に貫通する貫通部を有する仕切部材と、を備える吸着分離膜モジュールの製造方法であって、
前記中空糸膜束、前記筒体、及び前記仕切部材を備えるユニットの端部に固定剤を充填することによって、前記中空糸膜束及び前記仕切部材を前記筒体に固定し、
前記ユニットの前記端部を切断することによって、前記中空糸膜の端部を開口させる、
吸着分離膜モジュールの製造方法。 - 複数本の吸着機能を有する中空糸膜からなる中空糸膜束と、前記中空糸膜束を収容する筒体と、前記中空糸膜束の少なくとも一方の端部を前記筒体に固定する固定層と、を備える吸着分離膜モジュールに設けられ、前記中空糸膜束の端部で前記中空糸膜束を複数の膜束に仕切る仕切部材であって、
軸線方向に貫通する貫通部を有する、
仕切部材。 - 複数本の吸着機能を有する中空糸膜からなる中空糸膜束と、
前記中空糸膜束を収容する筒体と、
前記中空糸膜束の少なくとも一方の端部を前記筒体に固定する固定層と、
を備える吸着分離膜モジュールであって、
前記中空糸膜の動的吸着容量に対する前記吸着分離膜モジュールの動的吸着容量の比が90%以上100%以下である、
吸着分離膜モジュール。 - 前記筒体の容積に対する前記中空糸膜の占有体積である体積充填率が30%以上70%未満である、
請求項14に記載の吸着分離膜モジュール。
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| EP11852651.6A EP2659951A4 (en) | 2010-12-27 | 2011-12-27 | Adsorption/separation membrane module, method for producing adsorption/separation membrane module, and partition member |
| JP2012551028A JP5596178B2 (ja) | 2010-12-27 | 2011-12-27 | 吸着分離膜モジュール、吸着分離膜モジュールの製造方法、及び仕切部材 |
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| CN201180063139.5A CN103298544B (zh) | 2010-12-27 | 2011-12-27 | 吸附分离膜组件、吸附分离膜组件的制造方法及分隔构件 |
| KR1020137016514A KR101527301B1 (ko) | 2010-12-27 | 2011-12-27 | 흡착분리막 모듈, 흡착분리막 모듈의 제조 방법, 및 구획 부재 |
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| KR20140125098A (ko) * | 2013-04-18 | 2014-10-28 | 코오롱인더스트리 주식회사 | 중공사막 모듈 |
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| JP2020146676A (ja) * | 2019-03-05 | 2020-09-17 | 東レ株式会社 | 吸着材の切断方法および装置 |
| JP7395881B2 (ja) | 2019-03-05 | 2023-12-12 | 東レ株式会社 | 吸着材の切断方法および装置 |
| JP2024044648A (ja) * | 2022-09-21 | 2024-04-02 | 芯動能設備股▲分▼有限公司 | 電子級ガスの精製方法 |
| WO2025182701A1 (ja) * | 2024-02-27 | 2025-09-04 | 東レ株式会社 | 中空糸膜エレメント及び外圧式中空糸膜モジュールとその運転方法、及び精製設備、及び精製方法 |
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| JP5596178B2 (ja) | 2014-09-24 |
| AU2011350543A1 (en) | 2013-08-01 |
| AU2011350543B2 (en) | 2016-02-04 |
| TW201233433A (en) | 2012-08-16 |
| KR101527301B1 (ko) | 2015-06-09 |
| CA2823157A1 (en) | 2012-07-05 |
| KR20130093666A (ko) | 2013-08-22 |
| CN103298544A (zh) | 2013-09-11 |
| EP2659951A1 (en) | 2013-11-06 |
| CA2823157C (en) | 2017-09-19 |
| JPWO2012091070A1 (ja) | 2014-06-05 |
| EP2659951A4 (en) | 2017-04-26 |
| CN103298544B (zh) | 2016-05-18 |
| TWI476040B (zh) | 2015-03-11 |
| US20130306545A1 (en) | 2013-11-21 |
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