WO2021230112A1 - Procédé de fabrication d'un module de membrane à fibres creuses de type cartouche - Google Patents

Procédé de fabrication d'un module de membrane à fibres creuses de type cartouche Download PDF

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Publication number
WO2021230112A1
WO2021230112A1 PCT/JP2021/017219 JP2021017219W WO2021230112A1 WO 2021230112 A1 WO2021230112 A1 WO 2021230112A1 JP 2021017219 W JP2021017219 W JP 2021017219W WO 2021230112 A1 WO2021230112 A1 WO 2021230112A1
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WO
WIPO (PCT)
Prior art keywords
hollow fiber
epoxy resin
fiber membrane
potting portion
potting
Prior art date
Application number
PCT/JP2021/017219
Other languages
English (en)
Japanese (ja)
Inventor
康作 竹内
智子 金森
真人 柳橋
亜弓 森
Original Assignee
東レ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to CN202180035096.3A priority Critical patent/CN115605284B/zh
Priority to JP2021525845A priority patent/JP7081723B2/ja
Priority to KR1020227039910A priority patent/KR102574621B1/ko
Publication of WO2021230112A1 publication Critical patent/WO2021230112A1/fr

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Definitions

  • the present invention relates to a method for manufacturing a cartridge type hollow fiber membrane module used in a water treatment field, a fermentation industry field, a pharmaceutical manufacturing field, a food industry field, and the like.
  • Filtration using a separation membrane is used in various fields such as drinking water production, water purification treatment, water treatment such as wastewater treatment, fermentation field involving cultivation of microorganisms and cultured cells, and food industry field.
  • hollow fiber membrane modules used for food and pharmaceutical applications are biologically active by performing sterilization using hot water, sterilization using saturated water vapor, and chemical cleaning using acid or alkali. It can be used in a membrane treatment system that handles various liquids to be treated. For that purpose, not only the hollow fiber membrane but also all the members constituting the module are required to have heat resistance and chemical resistance.
  • a hollow fiber membrane module in which a hollow fiber membrane bundle is fixed by an adhesive resin containing a heat-resistant epoxy resin as a main component is preferably used while using a module case made of stainless steel.
  • a heat cycle generated by the temperature difference between the membrane filtration operation and saturated steam sterilization acts on the module peeling occurs due to the difference in thermal expansion of the epoxy resin that adheres to the stainless steel case. Occasionally, the filtrate to be treated was mixed with the undiluted solution.
  • Patent Document 2 describes a hollow fiber membrane module in which the potting portion has a plurality of layers of two or more layers in order to secure the sealing property of the potting portion, and the dimensional change of the sealing portion due to the curing shrinkage of the potting agent is suppressed. It has been disclosed.
  • these hollow fiber membrane modules have a configuration in which a bundle of hundreds to tens of thousands of hollow fiber membranes is bundled, stored in a cylindrical case, and the ends are bonded and fixed with resin.
  • a centrifugal method is used in which a liquid uncured resin is permeated between the hollow fiber membranes using centrifugal force, and a liquid uncured resin is sent by a metering pump or a head and naturally.
  • a static potting method in which the hollow fiber membrane is permeated between the hollow fiber membranes.
  • the centrifugal method If you try to manufacture a hollow fiber membrane module by the centrifugal method, a large investment such as introduction of a centrifugal molding device is required. Further, it is necessary to maintain the centrifugal motion while the uncured resin is cured, which requires a large amount of power consumption and inevitably increases the cost. On the other hand, the latter static potting method has an advantage that the hollow fiber membrane module can be manufactured at low cost because it does not require a special and large-sized device such as the centrifugal method.
  • the present invention provides a cartridge-type hollow fiber membrane module that can prevent leakage and contamination by germs due to peeling of the potting agent even when steam sterilization used for food and pharmaceutical applications is applied, and is a static potting method with a large cost merit. It is an object to provide a method of manufacturing by.
  • the present invention provides the following method for manufacturing a cartridge type hollow fiber membrane module.
  • the hollow fiber membrane is opened at at least one end of the housing, the hollow fiber membrane bundle having a plurality of hollow fiber membranes arranged in the housing, and the plurality of hollow fiber membranes.
  • a method for manufacturing a cartridge-type hollow fiber membrane module comprising: a first potting portion for adhering the hollow fiber membrane, and a sealing material for liquid-tightly fixing between the first potting portion and the housing.
  • a step of forming the inner layer potting portion included in the first potting portion (A) A step of forming the inner layer potting portion included in the first potting portion, and (B) A step of forming an outer layer potting portion included in the first potting portion and covering the inner layer potting portion, and a step of forming the outer layer potting portion.
  • step (a) is (A-1) An inner layer potting agent placement step of filling the inner layer potting agent forming the inner layer potting portion between the hollow fiber membranes, and (A-2) A curing step of curing the inner layer potting agent, Equipped with The step (b) is (B-1) After the curing step of (a-2), the outer layer potting portion is such that the outer layer potting portion covers the inner layer potting portion at least in the portion where the first potting portion is in contact with the sealing material.
  • Condition (p) The viscosity of the epoxy resin composition forming the inner layer potting portion at 25 ° C. is 400 mPa ⁇ s or more, and the glass transition temperature Tg1 of the cured product of the epoxy resin composition is 95 ° C. or more and 160 ° C. or less.
  • the epoxy resin composition forming the outer layer potting portion contains an alicyclic polyamine composed of one cyclohexyl ring, the viscosity at 25 ° C. is 1200 mPa ⁇ s or less, and the glass of the cured product of the epoxy resin composition.
  • the transition temperature Tg2 is 110 ° C. or higher and 160 ° C. or lower.
  • Condition (r) The relationship between the glass transition temperature Tg1 and the glass transition temperature Tg2 is 5 ⁇ Tg2-Tg1 ⁇ 20.
  • the alicyclic polyamine composed of one cyclohexyl ring contained in the epoxy resin composition forming the outer layer potting portion is selected from the group consisting of isophoronediamine, cyclohexanediamine and 1,3-bisaminomethylcyclohexane.
  • a cartridge type hollow fiber membrane module capable of preventing leakage of the potting portion even when steam treatment used for food and pharmaceutical applications is applied.
  • FIG. 1 is a schematic vertical sectional view of the hollow fiber membrane cartridge of the present invention.
  • FIG. 2 is a flowchart showing an example of the manufacturing method of the present invention.
  • FIG. 3 is a schematic diagram illustrating an example of the manufacturing method of the present invention.
  • FIG. 4 is a schematic diagram illustrating an example of the manufacturing method of the present invention.
  • FIG. 5 is a schematic diagram illustrating an example of the manufacturing method of the present invention.
  • FIG. 6 is a schematic diagram illustrating an example of the manufacturing method of the present invention.
  • FIG. 7 is a schematic vertical sectional view of the cartridge type hollow fiber membrane module according to the embodiment of the present invention.
  • FIG. 8 is a cross-sectional view taken along the line AA of the cartridge type hollow fiber membrane module shown in FIG. 7.
  • FIG. 9 is a cross-sectional view taken along the line BB of the cartridge type hollow fiber membrane module shown in FIG. 7.
  • the manufacturing method of the cartridge type hollow fiber membrane module of the present invention (hereinafter, also referred to as “the manufacturing method of the present invention”) will be described with reference to the drawings.
  • the directions such as “up” and “down” are based on the states shown in the drawings and are for convenience.
  • the outflow side is the "upward” direction.
  • the vertical direction thereof coincides with the vertical direction in the drawing.
  • “mass” is synonymous with "weight”.
  • the hollow fiber membrane cartridge 100 has a hollow fiber membrane bundle 2 having a plurality of hollow fiber membranes 1, and the hollow fiber membranes 1 are adhered to each other by potting portions at both ends of the hollow fiber membrane bundle 2.
  • the manufacturing method of the present invention includes the following steps (a) and (b) in forming the potting portion (first potting portion 9) located on the side where the filtered liquid is discharged in the hollow fiber membrane cartridge. (A) Step of forming the inner layer potting portion included in the first potting portion (b) Step of forming the outer layer potting portion included in the first potting portion and covering the inner layer potting portion.
  • the potting method is a centrifugal potting method in which a liquid potting agent is permeated between hollow fiber membranes using centrifugal force to cure it, and a hollow fiber is sent by sending a liquid potting agent with a metering pump or a head and allowing it to flow naturally.
  • a static potting method in which the material is infiltrated between the filament membranes and then cured, and the production method of the present invention uses the static potting method.
  • Step S1 the hollow fiber membrane bundle 2 including the plurality of hollow fiber membranes 1 is inserted into the first potting cap 15A, the inner layer potting agent is supplied, and the inner layer potting portion 9A is supplied.
  • the first potting portion 9 is shown at the upper end, but in FIG. 3, it is shown downward as in the case of static potting.
  • the end portion of the hollow fiber membrane on the side to be inserted into the first potting cap 15A (hereinafter, also referred to as "first end portion") is preliminarily sealed with a silicone adhesive.
  • a pump for charging the potting agent is connected to the first potting cap 15A, and the potting agent for forming the inner layer (inner layer potting agent) can be supplied to the first potting cap 15A by the pump.
  • the inner layer potting portion 9A is formed by allowing the potting agent to harden and stand still until it loses fluidity.
  • the first potting cap 15A is removed to complete the curing of the inner layer potting portion 9A (step S2).
  • heat treatment may be performed to promote the reaction.
  • the dimensions of the first potting portion 9 can be stabilized.
  • the steps of forming the inner layer potting portion include an inner layer potting agent placement step (step (a-1)) in which the inner layer potting agent is filled between the hollow fiber membranes and a curing step (step (a)) in which the potting agent is cured. -2)) and is included.
  • the inner layer potting agent placement step is performed by the static potting in step S1. Then, a part of the curing step also proceeds in step S1. Further, the curing step is also performed in step S2, and the curing of the inner layer potting portion is completed.
  • the heat treatment conditions for promoting curing differ depending on the type of potting agent used, it may be appropriately set according to the type of potting agent.
  • an outer layer potting portion that covers the inner layer potting portion is formed.
  • the outer layer potting portion is formed so that the outer layer potting portion covers the inner layer potting portion at least in the portion where the first potting portion contacts the sealing material described later. It includes an outer layer potting agent placement step (step (b-1)) in which the outer layer potting agent to be formed is placed by a static potting method, and a curing step (step (b-2)) in which the potting agent is cured.
  • the first end portion of the hollow fiber membrane bundle 2 in which the inner layer potting portion 9A is formed is attached to the first potting caps 15B and 15C, and the outer layer potting portion 9B is formed by static potting. Step S3).
  • the first potting portion 9 is shown at the upper end, but in FIG. 4, it is shown downward as in the case of static potting.
  • the first potting cap 15B and the first potting cap 15C are shown in FIG.
  • the inner diameter of the cap is gradually increased or decreased.
  • the clearance between the first potting caps 15B and 15C and the inner layer potting portion 9A is preferably 2 mm or more, and more preferably 4 mm or more.
  • the clearance is preferably 8 mm or less, more preferably 6 mm or less.
  • the air in the potting cap is discharged upward (in the direction in which the hollow fiber membrane extends). Therefore, in order to improve the discharge property of bubbles and prevent the bubbles from staying in the potting agent, it is preferable to add the potting agent from below (the end side of the hollow fiber membrane).
  • step S3 the outer layer potting portion 9B is arranged so that the outer layer potting portion 9B covers the inner layer potting portion 9A at the portion in contact with the sealing material when the cartridge is incorporated in the module.
  • the first potting caps 15B and 15C are removed to complete the curing of the outer layer potting portion 9B (step S4).
  • heat treatment may be performed to promote the reaction.
  • step S3 the step of arranging the potting agent for forming the outer layer potting portion 9B on the outer side of the inner layer potting portion 9A is performed in step S3, and a part of the step of curing the potting agent also proceeds in step S3.
  • step S4 the curing is further advanced to complete the curing.
  • the end portion of the hollow fiber membrane 1 (hereinafter, also referred to as “second end portion”) on the side opposite to the side on which the first potting portion 9 is formed is the second potting portion case. It is inserted in 11.
  • the pin 17 is inserted into the through hole at the bottom of the second potting portion case 11, and the second potting portion case 11 and the pin 17 are housed inside the second potting cap 16.
  • static potting is performed to form the second potting portion 10 (step S5).
  • the hollow portion of the second end portion of the hollow fiber membrane 1 is sealed with a potting agent.
  • the curing of the second potting portion 10 is completed (step S6). When curing, heat treatment may be performed to promote the reaction.
  • the CC line portion at a desired position from the tip of the first potting portion 9 is cut with a tip saw type rotary blade or the like to open the first end portion of the hollow fiber membrane 1 ( By step S7), the hollow fiber membrane cartridge 100 can be manufactured.
  • the hollow fiber membrane cartridge 100 manufactured by the above method is inserted into the housing body 3, fixed with a sealing material (for example, O-ring 13), and the upper cap 4 and the lower cap 5 are attached. Therefore, the cartridge type hollow fiber membrane module 101A shown in FIG. 7 can be manufactured.
  • a sealing material for example, O-ring 13
  • the surface of the inner layer potting portion 9A and the inner surface of the second potting portion case 11 may be filed, plasma-treated, primer-treated, or the like in order to improve the adhesiveness.
  • the cartridge-type hollow fiber membrane module has a housing, a hollow fiber membrane bundle having a plurality of hollow fiber membranes arranged in the housing, and at least one end of the plurality of hollow fiber membranes.
  • a first potting portion for adhering the hollow fiber membrane and a sealing material for liquidally fixing the space between the hollow fiber membrane and the housing are provided so that the hollow fiber membrane is opened.
  • the cartridge type hollow fiber membrane module 101A includes a housing and the hollow fiber membrane cartridge 100 shown in FIG. 1 housed in the housing.
  • the housing is composed of a hollow housing body 3, an upper cap 4 and a lower cap 5 provided at both ends of the housing body 3.
  • the upper part of the housing body 3 has an upper cap 4 having a filtrate outlet 7 and the lower part of the housing body 3 has a lower cap 5 having an undiluted solution inlet 6. It is tightly and airtightly connected.
  • the upper cap 4 and the lower cap 5 use a gasket 14 as shown in FIG. 7, for example, and are fixed to the housing body 3 with a clamp or the like.
  • the housing body 3 has flanges 3A and 3B at the upper and lower ends thereof over the entire circumference of the housing body 3. Further, on the side portion of the housing body 3, an undiluted liquid outlet 8 is provided near the filter liquid outlet 7.
  • the upper cap 4 has an inner diameter substantially equal to the inner diameter of the housing body 3, and the upper end side thereof is reduced in diameter to form the filtrate outlet 7.
  • a step portion 4A for forming a groove when connected to the housing body 3 is formed over the entire circumference of the upper cap 4.
  • the lower cap 5 has an inner diameter substantially equal to the inner diameter of the housing body 3, and the lower end side thereof is reduced in diameter to form the stock solution inlet 6.
  • FIG. 8 is a cross-sectional view taken along the line AA at the first potting position of the cartridge type hollow fiber membrane module 101A shown in FIG. 7.
  • the hollow fiber membrane cartridge 100 is provided at both ends of a hollow fiber membrane bundle 2 including a plurality of hollow fiber membrane bundles 1 and both ends of the hollow fiber membrane bundle 2, and potting between the hollow fiber membranes 1 is adhered to each other. It has a part.
  • the hollow fiber membrane cartridge 100 has a first potting portion 9 arranged on the filter liquid outlet 7 side of the housing and a second potting portion 10 arranged on the stock solution inlet 6 side of the housing. ..
  • the first potting portion 9 arranged on the filter liquid outlet 7 side of the housing, that is, on the upper end side of the hollow fiber membrane cartridge 100, is a potting that adheres between the hollow fiber membranes 1 at the first end portion of the hollow fiber membrane bundle 2. It is formed of an agent.
  • the hollow fiber membrane bundle 2 is bundled with the upper end face of the hollow fiber membrane 1 opened.
  • the first potting portion 9 has a columnar shape, and a flange portion 9C is provided at the upper end portion thereof over the entire circumference of the first potting portion 9. Further, on the side surface of the first potting portion 9, a step portion 9D is provided over the entire circumference. By providing the step portion 9D, the outer diameter of the upper portion of the first potting portion 9 is larger than the outer diameter of the lower portion.
  • the flange portion 9C of the first potting portion 9 is inserted into a groove (fixed portion) formed between the housing body 3 and the upper cap 4 by attaching the upper cap 4 to the housing body 3. In this way, the first potting portion 9 is fixed to the upper end portion of the housing body 3.
  • An O-ring 13 as a sealing material is installed between the stepped portion 9D of the first potting portion 9 and the housing body 3, and the first potting portion 9 is fixed liquidtightly and airtightly.
  • the first potting portion 9 is liquid-tightly and airtightly fixed by crushing the O-ring 13 in the radial direction (horizontal direction in FIG. 1) of the hollow fiber membrane module.
  • the crushing allowance of the O-ring 13 is preferably 8% or more and 30% or less.
  • the first potting portion 9 is not directly adhered to the housing body 3, but is liquid-tightly and airtightly fixed by the O-ring 13.
  • fixing the first potting portion with a sealing material such as an O-ring in a liquid-tight and airtight manner is referred to as a seal
  • a portion fixed with the sealing material is referred to as a sealing portion.
  • Epoxy resin is used as the potting agent, and these potting agents mix and cure the two liquids, but the volume shrinks at the time of curing. If the size of the step 9D changes due to shrinkage or strain occurs, it cannot be sealed by a sealing material such as an O-ring, and the undiluted solution may leak to the filtered solution side.
  • the first potting portion 9 includes an inner layer potting portion 9A and an outer layer potting portion 9B.
  • the outer layer potting portion 9B is formed on the outside of the inner layer potting portion 9A after the inner layer potting portion 9A is sufficiently cured and shrunk.
  • the inner layer potting portion 9A has already been cured and shrunk. Therefore, the dimensional deviation that occurs in the final outer shape of the first potting portion 9 is derived only from the curing shrinkage of the outer layer potting portion 9B. do. In this way, the dimensional deviation can be suppressed to be smaller than when the potting portion is composed of a single layer.
  • both the inner layer potting portion and the outer layer potting portion are formed in the portion where the first potting portion is in contact with the sealing material. Must be.
  • the inner layer potting portion may have a simple shape such as a cylinder.
  • the structures such as the flange portion 9C and the step portion 9D provided on the surface of the first potting portion 9 are formed by the outer layer potting portion 9B.
  • the present invention is not limited to this, and for example, the inner layer potting portion 9A may also have a structure such as a step portion or a flange portion.
  • the outer layer potting portion 9B is in contact with the sealing material. That is, the outer layer potting portion 9B is arranged so as to cover the inner layer potting portion 9A, and the outer surface of the first potting portion 9 is formed by the outer layer potting portion 9B.
  • An epoxy resin composition is used as the potting agent for forming the inner layer potting portion and the outer layer potting portion.
  • the glass transition temperature of the cured product of the epoxy resin composition forming the inner layer potting portion of the present embodiment (hereinafter referred to as Tg1) and the glass transition temperature of the cured product of the epoxy resin composition forming the outer layer potting portion (hereinafter referred to as Tg2). Satisfies the following equation (i) (condition (r)). 5 ⁇ Tg2-Tg1 ⁇ 20 ⁇ ⁇ ⁇ (i)
  • the difference in glass transition temperature of the cured product of the epoxy resin composition forming the inner layer potting part and the outer layer potting part in the range of 5 ° C to 20 ° C, high temperature conditions such as filtration of high temperature liquid, hot water sterilization, steam sterilization, etc. It is possible to suppress the generation of cracks due to the difference in expansion and contraction due to the heat of the inner layer and the outer layer when used in.
  • the curing calorific value Q1 of the epoxy resin composition forming the inner layer potting portion of the present embodiment is preferably 350 mJ / mg or less.
  • the curing heat generation amount of the epoxy resin composition is more preferably 280 mJ / mg or less.
  • the method for measuring the calorific value of curing is differential scanning calorimetry (DSC).
  • the curing calorific value Q1 [mJ / mg] ⁇ mass W1 [g] (hereinafter, Q1 ⁇ W1 value) of the epoxy resin composition forming the inner layer potting portion of the present embodiment is preferably 500 kJ or less.
  • the mass W1 of the epoxy resin composition forming the inner layer potting portion (hereinafter, also referred to as epoxy mass W1) is the mass W2 of the epoxy resin composition forming the outer layer potting portion (hereinafter, epoxy mass W2).
  • the same amount or more is preferable, and more is more preferable. Further, as the amount of epoxy resin increases, heat generation during curing tends to increase, which deteriorates the hollow fiber membrane. Therefore, deterioration of the hollow fiber membrane can be suppressed by setting the Q1 ⁇ W1 value to 500 kJ or less.
  • the Q1 ⁇ W1 value is more preferably 400 kJ or less.
  • the viscosity of the epoxy resin composition forming the inner layer potting portion of the present embodiment at 25 ° C. is 400 mPa ⁇ s or more, and the glass transition temperature Tg1 of the cured product of the epoxy resin composition is 95 ° C. or more and 160 ° C. or less (conditions). (P)).
  • the viscosity in the present invention is "cone-plate type" in JISZ8803 (1991) using an E-type viscometer (TVE-30H manufactured by Toki Sangyo Co., Ltd.) equipped with a standard cone rotor (1 ° 34'x R24). Measure at a measurement temperature of 25 ° C. according to "Viscosity measurement method using a rotational viscometer”. The viscosity of the present invention is one minute after the start of measurement.
  • the glass transition temperature Tg1 When the glass transition temperature Tg1 is 95 ° C or higher, it can be used under high temperature conditions such as high temperature liquid filtration, hot water sterilization, and steam sterilization. Further, when the glass transition temperature Tg1 is 160 ° C. or lower, the residual stress of the cured product of the epoxy resin composition forming the inner layer potting portion is reduced, and the mechanical properties of the potting portion tend to be improved.
  • the glass transition temperature Tg1 is more preferably 100 ° C. or higher, and even more preferably 105 ° C. or higher. Further, 150 ° C. or lower is more preferable, and 140 ° C. or lower is further preferable.
  • the method for measuring the glass transition temperature is differential scanning calorimetry (DSC).
  • composition of the epoxy resin composition of the inner layer potting portion is not limited, and various known epoxy resins can be used.
  • the epoxy resin composition of the inner layer potting portion preferably contains an alicyclic polyamine containing two or more cyclohexyl rings.
  • the alicyclic polyamine containing two or more cyclohexyl rings include 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and 4,4'-diaminodicyclohexylmethane. Of these, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane is preferable.
  • the alicyclic polyamine containing two or more cyclohexyl rings is preferably contained in an aliphatic amine-based curing agent in an amount of 50% by mass or more, more preferably 60% by mass or more, and contained in an amount of 95% by mass or less. Is preferable, and 90% by mass or less is more preferable.
  • the epoxy resin composition forming the outer layer potting portion of the present embodiment contains an alicyclic polyamine composed of one cyclohexyl ring, has a viscosity at 25 ° C. of 1200 mPa ⁇ s or less, and is a glass of a cured product of the epoxy resin composition.
  • the transition temperature Tg2 is 110 ° C. or higher and 160 ° C. or lower (condition (q)).
  • the viscosity By setting the viscosity to 1200 mPa ⁇ s or less, it is possible to suppress the residual of air bubbles in the outer layer potting portion even when manufactured by static potting, and it is possible to secure the sealing property. It is more preferably 1000 mPa ⁇ s or less, and further preferably 800 mPa ⁇ s or less.
  • the glass transition temperature Tg2 When the glass transition temperature Tg2 is 110 ° C or higher, it can be used under high temperature conditions such as high temperature liquid filtration, hot water sterilization, and steam sterilization. Further, when the glass transition temperature Tg2 is 160 ° C. or lower, the residual stress of the epoxy resin composition forming the outer layer potting portion is reduced, and the mechanical properties of the potting portion tend to be improved.
  • the glass transition temperature Tg2 is more preferably 115 ° C. or higher, further preferably 120 ° C. or higher, still more preferably 155 ° C. or lower, still more preferably 150 ° C. or lower.
  • the curing calorific value Q2 of the epoxy resin composition forming the outer layer potting portion of the present embodiment is preferably 1000 mJ / mg or less.
  • the curing heat generation amount of the epoxy resin composition is preferably 1000 mJ / mg or less.
  • the curing calorific value Q2 [mJ / mg] ⁇ mass W2 [g] (hereinafter, Q2 ⁇ W2 value) of the epoxy resin composition forming the outer layer potting portion of the present embodiment is preferably 400 kJ or less.
  • Q2 ⁇ W2 value The curing calorific value Q2 [mJ / mg] ⁇ mass W2 [g] (hereinafter, Q2 ⁇ W2 value) of the epoxy resin composition forming the outer layer potting portion of the present embodiment is preferably 400 kJ or less.
  • the Q2 ⁇ W2 value is more preferably 300 kJ or less.
  • the bending fracture strain of the cured product of the epoxy resin composition forming the outer layer potting portion of the present embodiment is preferably 4% or more. By setting the bending fracture strain to 4% or more, it is possible to suppress the generation of cracks due to fatigue when the hollow fiber membrane module is repeatedly used, and it becomes easy to obtain a hollow fiber membrane module having excellent durability.
  • the bending strength of the cured product of the epoxy resin composition forming the outer layer potting portion of the present embodiment is preferably 90 MPa or more.
  • the flange portion 9C of the first potting portion is sandwiched between the flange portion 3A of the housing body 3 and the step portion 4A of the upper cap 4, so that the first potting portion can be moved in the axial direction.
  • stress is generated that pushes the flange portion 9C of the first potting portion upward or downward.
  • the epoxy resin composition forming the outer layer potting portion is preferably an epoxy resin composition containing at least the following component [A] and the following component [B].
  • the component [A] is a bisphenol type epoxy resin.
  • the bisphenol type epoxy resin is not particularly limited as long as it is converted into a glycidyloxy group by reacting two phenolic hydroxyl groups of the bisphenol compound with epichlorohydrin, and the bisphenol type epoxy resin is, for example, bisphenol A type. Examples thereof include epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, and bisphenol S type epoxy resin.
  • the bisphenol type epoxy resin is preferably used because it has an excellent balance between toughness and heat resistance of the cured product of the obtained epoxy resin composition. In particular, a liquid bisphenol type epoxy resin is preferable because it can suppress the residual air bubbles in the outer layer potting portion.
  • liquid means that the viscosity at 25 ° C. is 1000 Pa ⁇ s or less
  • solid state means that there is no fluidity at 25 ° C. or extremely low fluidity. It means that the viscosity at 25 ° C. is larger than 1000 Pa ⁇ s.
  • This embodiment preferably includes the following component [A1] as the component [A].
  • [A1] Bisphenol F type epoxy resin
  • the bisphenol F type epoxy resin is preferable because it can reduce the viscosity of the epoxy resin composition while maintaining heat resistance and can effectively suppress the residual air bubbles in the outer layer potting portion.
  • the content of the component [A1] is preferably in the range of 10% by mass or more and 60% by mass or less in 100% by mass of the total bisphenol type epoxy resin.
  • an epoxy resin other than the component [A] may be contained as long as the effect of the present invention is not impaired.
  • Epoxy resins other than the component [A] can be preferably used because the process compatibility such as mechanical properties, heat resistance and viscosity can be adjusted according to the purpose.
  • Examples of the epoxy resin other than the component [A] include phenylglycidyl ether type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, aminophenol type epoxy resin, phenol novolac type epoxy resin, and epoxy resin containing dicyclopentadiene skeleton.
  • Examples thereof include a phenylglycidyl ether type epoxy resin and a reactive diluent having an epoxy group. These may be used alone or in combination of two or more.
  • the component [B] is an aliphatic amine-based curing agent.
  • the aliphatic amine-based curing agent is a compound having one or more primary or secondary amino groups in the molecule.
  • Examples of the aliphatic amine-based curing agent include isophoronediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, N-aminoethylpiperazine, 4,4'-methylenebiscyclohexylamine, and 2,2'-dimethyl-4,4.
  • '-Diaminodicyclohexylmethane, cyclohexanediamine, 1,3-bisaminomethylcyclohexane, aliphatic polyamines having an alkylene glycol structure and the like can be mentioned.
  • the aliphatic amine-based curing agent of the component [B] contains an alicyclic polyamine composed of one cyclohexyl ring.
  • the alicyclic polyamine containing a cyclohexyl ring has a more rigid molecular chain than the chain polyamine, and the alicyclic polyamine consisting of one cyclohexyl ring has a smaller molecular weight between cross-linking points than the polyamine consisting of two or more cyclohexyl rings.
  • Examples of the alicyclic polyamine composed of one cyclohexyl ring include isophorone diamine, cyclohexanediamine and 1,3-bisaminomethylcyclohexane.
  • the alicyclic polyamine composed of one cyclohexyl ring is preferably contained in an amount of 50% by mass or more, more preferably 60% by mass or more, and 90% by mass or less with respect to the total aliphatic amine-based curing agent component. Is preferable.
  • This embodiment preferably contains an aliphatic polyamine having an alkylene glycol structure in addition to the alicyclic polyamine composed of one cyclohexyl ring as the component [B].
  • Aliphatic polyamines having an alkylene glycol structure are preferably used because the viscosity of the obtained epoxy resin composition can be lowered and the residual air bubbles in the outer layer potting portion can be suppressed.
  • the alkylene glycol structure include polyoxyethylene, polyoxypropylene, and a copolymer of polyoxyethylene and polyoxypropylene.
  • the aliphatic polyamine having an alkylene glycol structure is preferably contained in an amount of 10% by mass or more, more preferably 20% by mass or more.
  • the component [B] preferably contains isophorone diamine and an aliphatic polyamine having an alkylene glycol structure.
  • the total amount of amine used as a curing agent is preferably such that the active hydrogen equivalent is 0.6 equivalents or more and 1.2 equivalents or less with respect to the epoxy groups of all the epoxy resin components contained in the epoxy resin composition. Within this range, it becomes easy to obtain an epoxy resin composition that provides an outer layer potting portion having an excellent balance between heat resistance and mechanical properties.
  • the epoxy resin composition of the present embodiment can contain a thermoplastic resin as long as the effects of the present invention are not impaired.
  • the thermoplastic resin may contain a thermoplastic resin soluble in an epoxy resin, organic particles such as rubber particles and thermoplastic resin particles, and the like.
  • thermoplastic resin soluble in the epoxy resin examples include polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, polyvinyl alcohol, phenoxy resin, polyamide, polyimide, polyvinylpyrrolidone, and polysulfone.
  • polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, polyvinyl alcohol, phenoxy resin, polyamide, polyimide, polyvinylpyrrolidone, and polysulfone.
  • Examples of the rubber particles include crosslinked rubber particles and core-shell rubber particles obtained by graft-polymerizing a dissimilar polymer on the surface of the crosslinked rubber particles.
  • This embodiment includes a second potting portion that bundles the hollow fiber membrane in a sealed state on the facing surface of the first potting portion, and the second potting portion is formed of the hollow fiber membrane and the potting agent.
  • a second potting portion 10 which is a lower end side of the hollow fiber membrane cartridge 100 is arranged on the stock solution inlet 6 side of the housing.
  • the second potting portion 10 where the second end portion of the hollow fiber membrane 1 is located is formed by adhering a hollow fiber membrane bundle 2 composed of a large number of hollow fiber membranes 1 and a second potting portion case 11 with a potting agent.
  • the hollow portion of the hollow fiber membrane 1 is sealed with a potting agent so that it does not open.
  • the second potting portion case 11 has a cylindrical shape having a bottom portion below, and its outer diameter is smaller than the inner diameter of the housing body 3.
  • the second potting portion 10 has a through hole 12 and plays a role of a flow path of the undiluted solution.
  • the type of potting agent used in the second potting portion of the cartridge type hollow fiber membrane module is not particularly limited as long as it satisfies the adhesive strength, heat resistance, chemical durability, etc. with the member to be bonded, but for example, epoxy resin or polyurethane resin. Etc. can be used.
  • FIG. 9 is a sectional view taken along line BB at the second potting position of the module of FIG. 7.
  • the cartridge type hollow fiber membrane module of the present embodiment includes a hollow fiber membrane as a separation membrane.
  • the structure of the hollow fiber membrane is a symmetric membrane with a uniform pore diameter as a whole, an asymmetric membrane whose pore diameter changes in the thickness direction of the membrane, and a support membrane layer for maintaining strength and a target substance for separation.
  • the material of the separation film is not particularly limited, but the separation film is, for example, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, ethylene tetrafluoride / propylene hexafluoride copolymer, ethylene / ethylene tetrafluoride copolymer.
  • Fluoro-based resins such as, cellulose acetate, cellulose acetate propionate, cellulose esters such as cellulose acetate butyrate, polysulfone-based resins such as polysulfone and polyethersulfone, and resins such as polyacrylonitrile, polyimide and polypropylene can be contained. ..
  • the separation membrane made of a fluorine-based resin or a polysulfone-based resin has high heat resistance, physical strength, and chemical durability, and thus can be suitably used for a cartridge type hollow fiber module.
  • the hollow fiber membrane may further contain a hydrophilic resin in addition to the fluororesin and the polysulfone resin.
  • the hydrophilic resin can increase the hydrophilicity of the separation membrane and improve the water permeability of the membrane.
  • the hydrophilic resin may be any resin that can impart hydrophilicity to the separation film, and is not limited to a specific compound, but for example, cellulose ester, fatty acid vinyl ester, vinylpyrrolidone, ethylene oxide, and the like.
  • a propylene oxide, a polymethacrylic acid ester-based resin, a polyacrylic acid ester-based resin, and the like are preferably used.
  • the material of the sealing material such as the O-ring and the gasket used in the cartridge type hollow thread film module is not particularly limited as long as it satisfies heat resistance, chemical durability, etc., but for example, fluororubber, silicone rubber, ethylene propylene diene rubber (EPDM) Etc. can be used.
  • the material of the housing used in the cartridge type hollow thread film module is not particularly limited as long as it satisfies heat resistance, chemical durability, etc., but for example, fluororesins such as polysulfone resin, polytetrafluoroethylene, perfluoroalkoxy fluororesin, etc. Examples thereof include polycarbonate, polypropylene, polymethylpentene, polyphenylene sulfide, polyether ketone, stainless steel, and aluminum.
  • the material of the tubular case and the second potting portion case used in the cartridge type hollow fiber membrane module is not particularly limited, but can be selected from, for example, the same materials as the housing.
  • ⁇ Viscosity measurement of epoxy resin composition> The viscosity of the epoxy resin composition prepared according to the above ⁇ Preparation method of epoxy resin composition> is adjusted to the standard cone rotor (1 ° 34'in accordance with the "viscosity measurement method using a cone-plate type rotational viscometer" in JIS Z8803 (2011). Using a TVE-30H manufactured by an E-type viscometer (Toki Sangyo Co., Ltd.) equipped with ⁇ R24), the measurement was performed at a rotation speed of 10 rotations / minute. The viscosity was read 1 minute after the epoxy resin composition was put into an apparatus set at 25 ° C.
  • ⁇ Measurement of curing calorific value of epoxy resin composition> Weigh 3 mg of the epoxy resin composition prepared according to the above ⁇ Preparation method of epoxy resin composition> into a sample pan, and use a differential scanning calorimeter (DSC-60 Plus: manufactured by Shimadzu Corporation) from 0 ° C. to 200 ° C. The measurement was carried out under the condition of constant rate temperature rise up to 10 ° C./min. The calorific value of curing was calculated from the obtained DSC curve according to JIS K0129 (1994).
  • ⁇ Method for producing a cured product of an epoxy resin composition> The epoxy resin composition prepared according to the above ⁇ Method for preparing an epoxy resin composition> is defoamed in a vacuum and then poured into a silicon sheet hollowed out to a width of 10 mm, a length of 80 mm and a thickness of 4 mm to form a plate-shaped epoxy resin composition. A cured product was obtained. The curing conditions were that the mixture was allowed to stand at room temperature for 24 hours and then cured at 100 ° C. for 5 hours.
  • ⁇ Measurement method of glass transition temperature of cured product of epoxy resin composition> Small pieces (5 mg to 10 mg) were collected from the cured product of the epoxy resin composition prepared according to the above ⁇ Method for producing a cured product of the epoxy resin composition>, and the intermediate point glass transition temperature was measured according to JIS K7121 (1987). A differential scanning calorimeter DSC-60 Plus (manufactured by Shimadzu Corporation) was used for the measurement, and the measurement was performed at a heating rate of 10 ° C./min under a nitrogen gas atmosphere.
  • the hollow fiber membrane As the hollow fiber membrane, a hollow fiber membrane having a bubble point of 200 kPa or more is used, and since the pores are filled with water, air does not permeate through the pores of the hollow fiber membrane.
  • the bubble point is the pressure at which the solvent in the pores of the membrane is pushed out and the air permeates when the pressure is applied to the hollow fiber membrane with compressed air.
  • Example 1 ⁇ Preparation of polyvinylidene fluoride microfiltration hollow fiber membrane> 38 parts by mass of vinylidene fluoride homopolymer having a weight average molecular weight of 417,000 and 62 parts by mass of ⁇ -butyrolactone were mixed and dissolved at 160 ° C. This polymer solution was discharged from the mouthpiece of a double tube with an 85% by mass ⁇ -butyrolactone aqueous solution as a hollow fiber forming liquid, and an 85% by mass ⁇ -butyrolactone aqueous solution having a temperature of 5 ° C. was placed 30 mm below the mouthpiece.
  • PVDF polyvinylidene fluoride
  • ⁇ Making a hollow fiber membrane cartridge> The hollow fiber membrane was cut to a length of 1800 mm, immersed in a 30 mass% glycerin aqueous solution for 1 hour, and then air-dried. This hollow fiber membrane was heat-treated with steam at 125 ° C. for 1 hour, then air-dried, and cut into a length of 1200 mm. The 5400 hollow fiber membrane bundles thus obtained were bundled into one bundle. The first end side of the hollow fiber membrane bundle was sealed with a silicone adhesive (manufactured by Toray Dow Corning Co., Ltd., SH850A / B, which was a mixture of two agents so that the mass ratio was 50:50).
  • a silicone adhesive manufactured by Toray Dow Corning Co., Ltd., SH850A / B, which was a mixture of two agents so that the mass ratio was 50:50.
  • the hollow fiber membrane sealing the first end side was inserted into a polypropylene first potting cap 15A (inner diameter 139.3 mm, inner length 92 mm).
  • Liquid bisphenol A type epoxy resin (“jER®” 828, manufactured by Mitsubishi Chemical Corporation) and 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (“Baxxodur®” EC331, BASF Japan Co., Ltd.) and polyetheramine (“JEFFAMIN (registered trademark)” D230) were mixed so as to have a mass ratio of 100: 19.2: 12.8.
  • the obtained epoxy resin composition was injected into the first potting cap 15A at a rate of 10 g / min using a tube pump. 1020 g of a potting agent was put into the first potting cap 15A. After charging, the potting agent was cured by allowing it to stand at room temperature for 24 hours.
  • the first potting cap 15A was removed, and further heat treatment was performed at 100 ° C. for 5 hours. As a result, the inner layer potting portion 9A of the first potting portion 9 was formed. Then, the surface of the inner layer potting portion 9A was sanded with sandpaper (# 80) and degreased with ethanol.
  • the inner layer potting portion 9A of the first potting portion is inserted into the polypropylene first potting caps 15B and 15C as shown in FIG. 4, and 10 g / min using a tube pump as in the case of the inner layer potting portion 9A.
  • the epoxy resin composition was injected at the speed of.
  • the minimum inner diameter portion of the first potting cap 15B shown in FIG. 4 is 149.3 mm, and the maximum inner diameter portion is 167 mm.
  • the minimum inner diameter portion of the first potting cap 15B is an O-ring seal surface forming portion.
  • the maximum outer diameter portion of the first potting cap 15C is the forming portion of the flange portion 9C of the outer layer potting portion.
  • the second end side of the hollow fiber membrane was inserted into the second potting part case 11 (inner diameter 149 mm, outer diameter 155 mm, inner length 40 mm) made of polysulfone.
  • the inside of the second potting portion case 11 made of polysulfone was sanded in advance with sandpaper (# 80) and degreased with ethanol.
  • a second potting cap 16 was attached to the outside of the second potting portion case 11.
  • 36 pins for forming through holes were inserted into the holes at the bottom of the second potting portion case 11 and fixed.
  • the pins were cylindrical with a diameter of 8 mm and a length of 100 mm, respectively.
  • Bisphenol A type epoxy resin (“jER (registered trademark)” 828, manufactured by Mitsubishi Chemical Corporation) and 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (“Baxxodur (registered trademark)” EC331, BASF Japan Co., Ltd.) and polyether amine (“JEFFAMIN®” D230) were mixed so that the mass ratio was 100: 19.2: 12.8.
  • the obtained epoxy resin composition was poured into the second potting cap 16 at a speed of 10 g / min using a tube pump.
  • the first potting portion was cut with a tip saw type rotary blade along the CC line of FIG. 6, and the first end portion of the hollow fiber membrane was opened to obtain a hollow fiber membrane cartridge.
  • the viscosity of the epoxy resin composition forming the inner layer potting portion of the hollow fiber membrane cartridge at 25 ° C. was 1420 mPa ⁇ s, and the glass transition temperature Tg1 of the cured product of the epoxy resin composition was 110 ° C.
  • the calorific value for curing was 240 mJ / mg, which satisfied the condition (p).
  • the viscosity of the epoxy resin composition forming the outer layer potting portion at 25 ° C. was 1050 mPa ⁇ s
  • the glass transition temperature Tg2 of the cured product of the epoxy resin composition was 121 ° C., which satisfied the condition (q). ..
  • the bending strength was 122 MPa and the bending breaking strain was 4.1%.
  • the difference between Tg2 and Tg1 was 11 ° C., which satisfied the formula (i) of the condition (r).
  • This cartridge type hollow fiber membrane module 101A was steam-heated (125 ° C., 60 minutes) 50 times by the above-mentioned method, and then an air leak test was performed by the above-mentioned method. As a result, the decrease in pressure was 0 kPa in 5 minutes, and it was confirmed that the sealing property was secured.
  • Example 2 The resin compositions of the outer layer potting portion and the inner layer potting portion were set as shown in Table 1, respectively, and a hollow fiber membrane cartridge was produced by the same method as in Example 1.
  • the evaluation results are shown in Table 1.
  • the viscosity of the outer layer potting portion at 25 ° C. was 1200 mPa ⁇ s or less in all the examples, and the glass transition temperature Tg2 of the cured product of the epoxy resin composition was contained in the range of 110 ° C. or higher and 160 ° C. or lower. , The condition (q) was satisfied. Further, the difference between Tg2 and Tg1 was 5 ° C. or higher and 15 ° C. or lower, satisfying the condition (r). All of the obtained hollow fiber membrane cartridges had good heat resistance and air bubble removal property of the outer layer potting portion, as in Example 1. In addition, the sealing performance of the obtained cartridge-type hollow fiber membrane module was also good.
  • Example 1 A hollow fiber membrane cartridge was produced by the same method as in Example 1 except that the resin composition of the outer layer potting portion was changed as shown in Table 2.
  • the viscosity of the epoxy resin composition forming the outer layer potting portion was as high as 1420 mPa ⁇ s, and bubbles remained in the outer layer potting portion.
  • the decrease in pressure was 100 kPa in 5 minutes.
  • the air bubbles remaining in the outer layer potting portion deteriorated the sealing property of the O-ring seal portion and caused a leak.
  • Example 3 A hollow fiber membrane cartridge was produced by the same method as in Example 1 except that the resin composition of the inner layer potting portion was changed as shown in Table 2.
  • the glass transition temperature Tg1 of the cured product of the epoxy resin composition forming the inner layer potting portion was 47 ° C.
  • the decrease in pressure was 100 kPa in 5 minutes.
  • Example 4 A hollow fiber membrane cartridge was produced by the same method as in Example 1 except that the resin composition of the inner layer potting portion was changed as shown in Table 2.
  • the epoxy resin composition forming the inner layer potting portion had a low viscosity of 320 mPa ⁇ s at 25 ° C., and over-penetration occurred, so that filtration could not be performed.
  • Example 5 A hollow fiber membrane cartridge was produced in the same manner as in Example 1 except that the resin composition of the outer layer potting portion was changed as shown in Table 2.
  • the glass transition temperature Tg2 of the cured product of the epoxy resin composition forming the outer layer potting portion was 47 ° C.
  • the decrease in pressure was 100 kPa in 5 minutes.
  • Example 6 A hollow fiber membrane cartridge was produced in the same manner as in Example 1 except that the resin compositions of the inner layer potting portion and the outer layer potting portion were changed as shown in Table 2. The difference in glass transition temperature between the epoxy resin composition forming the inner layer potting portion and the cured product of the epoxy resin composition forming the outer layer potting portion was as large as -19 ° C. As a result of an air leak test of the obtained cartridge type hollow fiber membrane module, the decrease in pressure was 100 kPa in 5 minutes. A leak occurred because a crack was generated in the first potting portion when steam heating was performed.
  • Example 7 A hollow fiber membrane cartridge was produced by the same method as in Example 1 except that the resin composition of the inner layer potting portion was changed as shown in Table 2.
  • the glass transition temperature Tg1 of the cured product of the epoxy resin composition forming the inner layer potting portion was 69 ° C.
  • the decrease in pressure was 100 kPa in 5 minutes.
  • Example 8 A hollow fiber membrane cartridge was produced in the same manner as in Example 1 except that the resin composition of the outer layer potting portion was changed as shown in Table 2.
  • the glass transition temperature Tg2 of the cured product of the epoxy resin composition forming the outer layer potting agent was 69 ° C.
  • the decrease in pressure was 100 kPa in 5 minutes.
  • Example 9 A hollow fiber membrane cartridge was produced in the same manner as in Example 1 except that the amounts of resin in the inner layer potting portion and the outer layer potting portion were changed as shown in Table 2.
  • the Q2 ⁇ W2 value of the epoxy resin composition forming the outer layer potting portion is as large as 729 kJ, and the maximum heat generation temperature of the epoxy resin composition reached at the time of curing becomes 260 ° C., the polyacetal potting case is deformed, and the inner layer potting portion is formed.
  • the hollow fiber membrane of the above was partially melted.
  • Example 10 A hollow fiber membrane cartridge was produced in the same manner as in Example 1 except that the resin composition of the outer layer potting portion was changed as shown in Table 2.
  • the glass transition temperature Tg2 of the cured product of the epoxy resin composition forming the outer layer potting agent was 107 ° C.
  • the decrease in pressure was 100 kPa in 5 minutes.
  • the method for producing a hollow fiber membrane module of the present invention is to be filtered in various fields such as drinking water production, water purification treatment, water treatment such as wastewater treatment, fermentation field involving cultivation of microorganisms and cultured cells, and food industry field. It is preferably applied to the filtration treatment of liquids.
  • Hollow Fiber Membrane Cartridge 101A Cartridge-type Hollow Fiber Membrane Module 1 Hollow Fiber Membrane 2 Hollow Fiber Membrane Bundle 3 Housing Body 3A Gasket 3B Gasket 4 Upper Cap 4A Step 5 Lower Cap 6 Stock Solution Inlet 7 Filter Solution Outlet 8 Stock Solution Outlet 9 1st potting part 9A Inner layer potting part 9B Outer layer potting part 9C Filtration part 9D Step part 10 2nd potting part 11 2nd potting part Case 12 Through hole 13 O ring 14 Gasket 15A 1st potting cap 15B 1st potting cap 15C 1st potting cap 16 2nd potting cap 17 pin

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  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'un module de membrane à fibres creuses de type cartouche comprenant : un boîtier ; un faisceau de membranes à fibres creuses comprenant une pluralité de membranes à fibres creuses positionnées dans le boîtier ; une première partie d'enrobage pour lier les membranes à fibres creuses, de sorte que les membranes à fibres creuses soient ouvertes sur au moins une extrémité de la pluralité de membranes à fibres creuses ; et un joint pour fixer la première partie d'enrobage au boîtier de manière étanche aux liquides. La première partie d'enrobage comprend au moins une partie d'enrobage de couche interne et une partie d'enrobage de couche externe La viscosité à 25 °C et la valeur calorifique de durcissement d'une composition de résine époxy formant chacune des parties d'enrobage, ainsi que la température de transition vitreuse d'un produit durci de la composition de résine époxy, se trouvent dans des plages numériques spécifiques.
PCT/JP2021/017219 2020-05-15 2021-04-30 Procédé de fabrication d'un module de membrane à fibres creuses de type cartouche WO2021230112A1 (fr)

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