WO2019216148A1 - Module de membrane à fibres creuses de type à pression externe - Google Patents

Module de membrane à fibres creuses de type à pression externe Download PDF

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Publication number
WO2019216148A1
WO2019216148A1 PCT/JP2019/016558 JP2019016558W WO2019216148A1 WO 2019216148 A1 WO2019216148 A1 WO 2019216148A1 JP 2019016558 W JP2019016558 W JP 2019016558W WO 2019216148 A1 WO2019216148 A1 WO 2019216148A1
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Prior art keywords
fiber membrane
hollow fiber
membrane bundle
cylindrical housing
membrane module
Prior art date
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PCT/JP2019/016558
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English (en)
Japanese (ja)
Inventor
弘幸 古屋
熊見　和久
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株式会社ダイセル
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Priority claimed from JP2018169875A external-priority patent/JP2019195800A/ja
Application filed by 株式会社ダイセル filed Critical 株式会社ダイセル
Publication of WO2019216148A1 publication Critical patent/WO2019216148A1/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
    • B01D63/031—Two or more types of hollow fibres within one bundle or within one potting or tube-sheet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • 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
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • B01D71/14—Esters of organic acids
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof

Definitions

  • the present invention relates to an external pressure type hollow fiber membrane module that can be used for water treatment in various fields.
  • Hollow fiber membrane modules are widely used in various water treatment fields. Generally, a casing having a fluid inlet / outlet, a cap, a hollow fiber membrane bundle, and a resin-sealed resin-fixed end portion of the hollow fiber membrane bundle. Many of them are composed of parts (FIG. 1 of US Patent Publication No. 2003/0150807).
  • the filtration performance deteriorates due to clogging of the membrane or the formation of an adhesion layer on the membrane surface. Fouling may occur. When such fouling occurs, the filtration performance is recovered by washing the membrane by air scrubbing washing or back pressure washing.
  • Japanese Patent No. 6264508 discloses a cylindrical case having a first end and a second end in the height direction, a plurality of hollow fiber membranes accommodated in the cylindrical case, and the first of the cylindrical case.
  • a first potting part that is bonded in a state where the ends of a plurality of hollow fiber membranes located on one end side are opened, and the hollow fiber membrane has a breaking strength of 23 MPa or more, and the filling rate of the hollow fiber membranes Discloses a hollow fiber membrane module having a ratio of 40% to 80%.
  • FIG. 1 of Japanese Patent No. 4882173 a hollow fiber membrane bundle 3 is accommodated in a case 1, and one end A of the hollow fiber membrane bundle 3 is resin so that the end of the hollow fiber membrane 2 is open.
  • the hollow fiber membrane module 50 is bonded and fixed at 20 and bonded to the inner wall of the case, and the other end B is bonded and fixed with a resin 20 so that the end of the hollow fiber membrane 2 is sealed and bonded to the inner wall of the case.
  • the raw water supply port 5 corresponding to the end B and the air discharge port 6 corresponding to the end A are formed on the side surface of the filtration zone 4 sandwiched between the ends A and B.
  • a hollow fiber membrane module in which an air dispersion hole / drainage hole 11 penetrating the end B is provided in the end B.
  • FIG. 6 of Japanese Patent No. 4498373 shows a rack type filtration device module.
  • One end of the multiple hollow fiber membranes 3a is integrated with an adhesive fixing layer 14 having a through hole 14a.
  • raw water is supplied to the supply water inlet 2c, enters the lower ring 13, and then is guided to the outer peripheral surface of the hollow fiber membrane 3a through the through hole 14a (paragraph number 0046).
  • gas bubbling the hollow fiber membrane 3a gas is supplied from the gas supply port to the lower ring 13, and the hollow fiber membrane 3a is vibrated through the through hole 14a of the adhesive fixing portion 14 (paragraph number 0047).
  • 7 and 8 show the positional relationship between the hollow fiber membrane 3a and the through hole 14a.
  • FIG. 1 of Japanese Patent No. 3686225 shows a hollow fiber membrane module in which a rectifying tube 6 is disposed near the center of the hollow fiber membrane bundle 1.
  • the liquid to be treated enters from the raw water inlet 7, is filtered by the hollow fiber membrane 1 through the outer periphery of the hollow fiber membrane bundle and the rectifying pipe 6, and goes out of the hollow fiber membrane module through the filtered water outlet 8.
  • the air supplied from the air inlet 10 which also serves as a drain outlet is distributed by the air nozzle 5 and released to the hollow fiber membrane 1 (paragraph 0011).
  • the present invention is a cylindrical housing having a liquid inlet / outlet including at least a raw water supply port and a permeate outlet, and a hollow fiber membrane module in which a hollow fiber membrane bundle is accommodated in the cylindrical housing,
  • the hollow fiber membrane bundle is fixed with an adhesive together with the inner wall surface of the cylindrical housing in a state where the first end surface side which is the raw water supply port side of the hollow fiber membrane bundle is closed.
  • the filling rate of the hollow fiber membrane bundle is 40% to 70%,
  • An external pressure type hollow fiber membrane module is provided in which the length of the hollow fiber membrane bundle from the first end surface side to the second end surface side is 2 m or less.
  • the present invention provides a cylindrical housing in which a cap having a liquid inlet / outlet including a raw water supply port and a permeate outlet is fixed to each of both end openings, and a hollow fiber in which a hollow fiber membrane bundle is accommodated in the cylindrical housing A membrane module,
  • the hollow fiber membrane bundle is The first end side of the raw water supply port side is fixed by an adhesive together with the inner wall surface of the cylindrical housing or the inner wall surface of the cap in a state where the first end surface side of the hollow fiber membrane bundle is closed.
  • the filling rate of the hollow fiber membrane bundle is 40% to 70%,
  • An external pressure type hollow fiber membrane module is provided in which the length of the hollow fiber membrane bundle from the first end surface side to the second end surface side is 2 m or less.
  • the present invention is a filtration operation method using the external pressure hollow fiber membrane module,
  • the filtration operation method has a filtration step and a washing step;
  • a filtration operation method in which the cleaning step performs back pressure cleaning and does not perform air scrubbing cleaning.
  • the external pressure type hollow fiber membrane module of the present invention makes it difficult for a sediment layer derived from suspended solids to be formed on the hollow fiber membrane surface, and clogging is less likely to occur. You can drive.
  • FIG. 1 is a cross-sectional view in the major axis direction of an external pressure type hollow fiber membrane module of the present invention.
  • (A) is the elements on larger scale of the 1st edge part side of FIG. 1
  • (b) is the elements on larger scale of the 2nd edge part side of FIG.
  • fixed part by the adhesive agent in the 1st end part side of the hollow fiber membrane module shown in FIG. The graph which shows transition of the filtration inlet pressure of Example 2.
  • FIG. The graph which shows transition of the filtration inlet pressure of the comparative example 1.
  • a hollow fiber membrane bundle 60 is accommodated in a cylindrical housing 10.
  • the cross-sectional shape of the cylindrical housing 10 in the width direction can be a circle, a polygon (preferably a polygon close to a circle), or the like.
  • the material of the cylindrical housing 10 can be metal, synthetic resin, or the like.
  • the size of the cylindrical housing 10 (the size of the inner volume) can be determined according to the total number of hollow fiber membrane bundles used corresponding to the filtration performance.
  • a first end side cap 20 is attached to the first end 10a side of the cylindrical housing 10 from the outside.
  • the first end side cap 20 is preferably made of the same material as the cylindrical housing 10.
  • the first end portion side cap 20 is composed of a combination of a first a cap portion 21 and a second a cap portion 30 having a raw water supply port (also serving as a counter pressure washing water outlet) 22.
  • the first a cap portion 21 and the second a cap portion 30 may be a single unit in which they are integrated.
  • the 1a cap portion 21 includes a raw water supply port (1a small diameter portion) 22 and a 1a annular large diameter portion 23 having a larger outer diameter than the raw water supply port 22 on the opposite side of the raw water supply port 22 in the axial X direction. Furthermore, between the raw
  • the size of the first a-annular large-diameter portion 23 is approximately the same as the outer diameter of the second-a cap portion 30 (second-a thin portion 33).
  • the inner surface of the 1a annular large diameter part 23 has an inner thread part.
  • An annular groove is formed in the annular end surface inside the 1a annular flat surface portion 25, and an O-ring 26 is fitted therein.
  • the second a cap portion 30 has such a size that the second end portion 30b side can be fitted into the first end portion 10a side of the cylindrical housing 10 from the outside, and the opposite first end portion 30a side is a hollow fiber membrane bundle. It is a cylindrical thing of the magnitude
  • the second a cap portion 30 has a second a annular step surface 31 on the inner surface side, a second a thick portion 32 having a small inner diameter on the second end portion 30b side from the second a annular step surface 31, and a second a. It has the 2a thin part 33 with a large internal diameter by the side of the 1st end part 30a from the cyclic
  • the outer surface of the 2a thick portion 32 is an inclined surface, but it may be a flat surface.
  • the outer surface of the second-a thin portion 33 has an outer screw portion that can be screwed together with the inner screw portion of the first-a annular large-diameter portion 23.
  • the second a cap portion 30 may be integrally formed with the first end portion 10a side of the cylindrical housing 10.
  • the 1a cap part 21 is a separate member.
  • the second a cap portion 30 is fitted from the outside to the first end portion 10a side of the cylindrical housing 10 on the first end portion 30b side, and the second end portion 30a side is fitted to the first end face 60a (first fixed surface) of the hollow fiber membrane bundle 60.
  • Layer 61) is connected in a state fitted from the outside.
  • the connection between the first end portion 10a of the cylindrical housing 10 and the cylindrical second a cap portion 30 can be applied by a method such as screwing, bonding with an adhesive, welding, or the like according to the respective materials.
  • the first a cap portion 21 and the second a cap portion 30 are connected by screwing together the inner screw portion of the annular large diameter portion 23 of the first a cap portion 21 and the outer screw portion of the second a thin portion 33 of the second a cap portion 30. It is fixed.
  • a second end side cap 40 is attached to the second end 10b side of the cylindrical housing 10 from the outside.
  • the second end side cap 40 is preferably made of the same material as the cylindrical housing 10.
  • the second end side cap 40 is composed of a combination of a 1b cap part 41 having a permeate outlet 42 and a second b cap part 50 having a concentrated water outlet 55.
  • the first b cap portion 41 and the second b cap portion 50 may be a single unit in which they are integrated.
  • the first b cap portion 41 includes a permeate outlet (first b small diameter portion) 42 and a first b annular large diameter portion 43 having a larger outer diameter than the permeate outlet 42 on the opposite side of the permeate outlet 42 in the axis X direction.
  • the permeate outlet (first b small diameter part) 42 and the second b annular large diameter part 43 the 1b annular inclined surface part in order from the permeate outlet 42 side to the 1b annular large diameter part 43 side. 44 and a 1b annular flat surface portion 45.
  • the size of the 1b annular large-diameter portion 43 is approximately the same as the outer diameter of the second b cap portion 50 (second b thin portion 53).
  • the inner surface of the 1b annular large-diameter portion 43 has an inner screw portion.
  • An annular groove is formed in the annular end surface inside the 1b annular flat surface portion 45, and an O-ring 46 is fitted therein.
  • the second end 50b has a size such that the first end 50b side can be fitted into the first end 10b side of the cylindrical housing 10 from the outside, and the opposite second end 50a side is a hollow fiber membrane bundle. It is a cylindrical thing of the magnitude
  • the second b cap portion 50 has a second b annular step surface 51 on the inner surface side, a second b thick portion 52 having a small inner diameter on the first end portion 50b side from the second b annular step surface 51, and a second b.
  • the 2b thin part 53 has a big internal diameter by the side of the 1b cap part 41 from the cyclic
  • the outer surface of the second b thick portion 52 is an inclined surface, but it may be a flat surface.
  • the outer surface of the second b thin portion 53 has an outer screw portion that can be screwed together with the inner screw portion of the first b annular large diameter portion 43.
  • the second b cap portion 50 of the second end side cap 40 may be integrally formed with the first end portion 10 b side of the cylindrical housing 10.
  • the first b cap portion 41 is a separate member.
  • the second end portion 50b of the second end portion 50b is fitted from the outside to the first end portion 10b side of the cylindrical housing 10, and the second end portion 50a side is fitted to the second end face 60b of the hollow fiber membrane bundle 60 (second fixing).
  • Layer 62) is connected in a state of being fitted from the outside.
  • the connection between the first end portion 10b of the cylindrical housing 10 and the cylindrical second b cap portion 50 can be applied by a method such as screwing, bonding with an adhesive, or welding according to the respective materials.
  • the first b cap portion 41 and the second b cap portion 50 are formed by screwing together the inner screw portion of the first b annular large-diameter portion 43 of the first b cap portion 41 and the outer screw portion of the second b thin portion 53 of the second b cap portion 50.
  • the connection at is fixed.
  • the hollow fiber membrane bundle 60 is a bundle of several hundred to several thousand known hollow fiber membranes.
  • Hollow fiber membranes are known and have a hydrophilic membrane (cellulose membrane such as cellulose acetate) or hydrophobic membrane (polyvinylidene fluoride) having an outer diameter of preferably 1 to 3 mm, more preferably 1.3 to 1.6 mm. , Polysulfone, polyethersulfone, etc.) can be used.
  • the hollow fiber membrane of the present invention is preferably a hydrophilic membrane that is less prone to fouling, and is preferably a cellulose ester membrane.
  • hydrophilic membranes such as cellulose ester membranes are suitable because sludge hardly adheres to the surface of the hollow fiber membrane, and stable filtration is possible only by back washing without air scrubbing. It is.
  • cellulose ester film one or more selected from cellulose acetate, cellulose propionate, cellulose butyrate, and cellulose benzoate can be used.
  • cellulose ester film a cellulose mixed ester represented by the structural formula of the following general formula (I) can be used.
  • the acyl group is preferably selected from a benzoyl group which may have a substituent and an aromatic acyl group containing a carboxyl group or a carboxyl group salt.
  • the benzoyl group which may have a substituent is a benzoyl group or an alkyl group such as a methyl group, a trifluoromethyl group, a tert-butyl group or a phenyl group at one or more positions in the ortho position, meta position and para position.
  • a benzoyl group having one or more substituents such as an alkoxy group such as a methoxy group and a phenoxy group, a hydroxy group, an amino group, an imino group, a halogeno group, a cyano group and a nitro group.
  • benzoyl group, para-methylbenzoyl group, ortho-methylbenzoyl group, para-methoxybenzoyl group, ortho-methoxybenzoyl group, dimethylbenzoyl group are both highly resistant to chlorine and alkali and easily available. Those selected from the group are preferred.
  • aromatic acyl group containing a carboxyl group or a salt of a carboxyl group is substituted with a hydroxy group of cellulose, an optionally substituted phthalic anhydride, an optionally substituted naphthalic anhydride, or the like. What is selected from what is an aromatic acyl group produced
  • Specific examples of the aromatic dicarboxylic acid monoanhydride include phthalic anhydride, 3-methylphthalic anhydride, 4-methylphthalic anhydride, 3-nitrophthalic anhydride, 4-ethoxycarbonyl-3,5-dimethylphthalate.
  • Acid anhydride 1,2-naphthalic anhydride, 1,8-naphthalic anhydride, 2,3-naphthalenedicarboxylic anhydride, 4-bromo-1,8-naphthalic anhydride, 2,3-anthracene
  • dicarboxylic acid anhydrides 1,2-naphthalic anhydride, 1,8-naphthalic anhydride, 2,3-naphthalenedicarboxylic anhydride, 4-bromo-1,8-naphthalic anhydride, 2,3-anthracene
  • dicarboxylic acid anhydrides 1,2-naphthalic anhydride, 1,8-naphthalic anhydride, 2,3-naphthalenedicarboxylic anhydride, 4-bromo-1,8-naphthalic anhydride, 2,3-anthracene
  • dicarboxylic acid anhydrides 1,2-naphthalic anhydride, 1,8-naphthalic anhydride, 2,3-naphthalenedicarboxylic an
  • X is an acyl group and is not selected from a benzoyl group which may have a substituent and an aromatic acyl group including a carboxyl group or a salt of a carboxyl group, an aliphatic acyl group having 2 or more carbon atoms and It can be selected from aromatic acyl groups having 5 or more carbon atoms.
  • the aliphatic acyl group having 2 or more carbon atoms is preferably one selected from an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group, a pentanoyl group, a hexanoyl group, a decanoyl group, and an octadecanoyl group.
  • the aromatic acyl group having 5 or more carbon atoms is preferably selected from an acyl group having a pyrrole ring, an acyl group having a pyridine ring, (picolinyl group, nicotinyl group) and an acyl group having a naphthalene ring.
  • the substitution degree of X with an acyl group is preferably 1.5 to 3.0, more preferably 2.0 to 3.0, and still more preferably 2.3 to 3.0.
  • the degree of substitution corresponding to a hydroxy group when X is a hydrogen atom is preferably 0 to 1.5, more preferably 0 to 1.0, and still more preferably 0 to 0.7.
  • n is preferably an integer of 20 to 20,000, more preferably 40 to 10,000, and still more preferably 60 to 8,000.
  • the hollow fiber membrane bundle 60 has a first end side cap 20 (second a cap portion 30) on the first end surface 60a side on the first end portion 10a side (first end side cap 20 side) of the cylindrical housing 10. Are fixed together with a known adhesive (potting agent) together with the inner wall surface (first fixing layer 61).
  • the hollow fiber membrane bundle 60 has a second end side cap 40 (second b cap portion 50) on the second end surface 60b side on the second end portion 10b side (second end side cap 40 side) of the cylindrical housing 10.
  • second end side cap 40 second b cap portion 50
  • potting agent second fixing layer 62
  • the first end surface 60a side of the hollow fiber membrane bundle 60 is closed with an adhesive and is not opened.
  • the length of the first fixed layer 61 in the major axis X direction is approximately the same as the length of the second fixed layer 62 in the major axis X direction.
  • the second end face 60b side of the hollow fiber membrane bundle 60 is not closed with an adhesive but is opened.
  • the length of the second fixed layer 62 in the major axis X direction is a range from the second end surface 60 b of the hollow fiber membrane bundle 60 to a position not in contact with the concentrated water outlet 55.
  • the length (L) from the first end surface 60a side to the second end surface 60b side of the hollow fiber membrane bundle 60 is 2 m or less, preferably 1.8 m or less, More preferably, it is 1.6 m or less, and preferably 0.8 m or more, more preferably 1.0 m or more.
  • the minimum diameter (D) in the inner peripheral part of the cylindrical housing 10 in which the hollow fiber membrane bundle 60 is accommodated, the 2a cap part 30, and the 2b cap part 50 is the filtration performance of the hollow fiber membrane module and the hollow fiber membrane. From the viewpoint of the balance with the module installation floor area, it is preferably 14 cm or more, more preferably 18 cm or more, further preferably 20 cm or more, and preferably 40 cm or less, more preferably 35 cm or less, still more preferably 30 cm or less, and even more preferably. Is 25 cm or less.
  • the minimum diameter (D) is the diameter of the portion where the diameter in the direction perpendicular to the X-axis in the inner peripheral portion of the cylindrical housing 10, the second a cap portion 30, and the second b cap portion 50 is the smallest, and The diameter obtained from the cross section of the space in which the hollow fiber membrane excluding members other than the hollow fiber membrane bundle such as a porous tube for introducing raw water is used.
  • the ratio (L / D) to (D) is preferably 4 to 13, more preferably 4.5, from the viewpoint of the balance between the filtration performance of the hollow fiber membrane module and the floor area of the hollow fiber membrane module. To 11, more preferably 7 to 10.
  • the differential pressure between the hollow fiber membranes is large, so that even a highly water-permeable hollow fiber membrane may reduce the substantial amount of filtered water.
  • the ratio (L / D) is within the above range (that is, when the hollow fiber membrane module is thick and short)
  • the permeated water after filtration permeates through the hollow fiber membrane. Since there is little pressure loss when flowing to the water outlet side and the differential pressure between the hollow fiber membranes is small, a higher water transmission rate can be obtained.
  • the filling rate of the hollow fiber membrane bundle 60 is 40% to 70%, preferably 42% to 65%, more preferably 45% to 60% from the viewpoint of preventing fouling of the hollow fiber membrane. .
  • the filling rate of the hollow fiber membrane bundle 60 is calculated from the product of the average cross-sectional area in the width direction per hollow fiber membrane and the number of hollow fiber membranes accommodated in the cylindrical housing 10.
  • the cross-sectional area of the thread membrane bundle is S2
  • the minimum cross-sectional area in the width direction at the inner peripheral portions of the cylindrical housing 10 the second a cap portion 30, and the second b cap portion 50 is S1
  • the following calculation is performed. .
  • Filling rate [%] S2 / S1 ⁇ 100
  • the minimum cross-sectional area S1 is the cross-sectional area of the smallest portion in the cross-sectional area in the direction perpendicular to the X axis in the inner peripheral part of the cylindrical housing 10, the second a cap part 30, and the second b cap part 50, And it shall mean the cross-sectional area of the space where the hollow fiber membrane except the members other than the hollow fiber membrane bundle such as a porous tube for introducing raw water is used.
  • the average cross-sectional area in the width direction per hollow fiber membrane is obtained by arbitrarily collecting a total of 100 hollow fiber membranes from the hollow fiber membrane bundle accommodated in the cylindrical housing 10, and measuring each hollow fiber membrane. The cross-sectional area is calculated by measuring the outer diameter of the thread membrane, and the average of those values is used.
  • the second b cap portion 50 of the second end side cap 40 includes a second b thick portion 52, a second b annular step surface 51, and a second b thin portion 53, and the second b annular step surface 51 and second b thin wall portion.
  • a concentrated water outlet 55 is formed between the portions 53. For this reason, between the concentrated water outlet 55 and the hollow fiber membrane bundle 60 facing the concentrated water outlet 55, the difference in thickness between the 2b thick portion (small inner diameter) 52 and the second b thin portion (large inner diameter) 53.
  • An annular space 56 having an interval corresponding to (difference in inner diameter) is formed. Since the concentrated water outlet 55 faces the annular space 56, the concentrated water is discharged smoothly.
  • the first fixed layer 61 has a plurality of raw water introduction holes 65 formed penetrating in the thickness direction.
  • the plurality of raw water introduction holes 65 are formed so as to penetrate the first fixing layer 61, and reach the inside of the hollow fiber membrane bundle 60 in which the leading ends of the raw water introduction holes are not fixed with an adhesive. It may be.
  • the ratio (A2 / A1 ⁇ 100) of the total opening area (A2) of the plurality of raw water introduction holes 65 in the radial cross-sectional area (A1) of the first fixed layer 61 on the first end face 60a side is the hollow fiber membrane From the viewpoint of preventing fouling, 5 to 20% is preferable, and 10 to 15% is more preferable.
  • the hollow fiber membrane module 1 of the present invention includes a porous tube or a net-like pipe for introducing raw water, a partition plate for internal arrangement, a reinforcing rod-like body (preferably made of synthetic resin), etc., as necessary. Can be used.
  • the hollow fiber membrane module 1 having the first fixed layer 61 having a plurality of raw water introduction holes 65 and the second fixed layer 62 not having the plurality of raw water introduction holes 65 is manufactured by the following method. be able to. First, as a potting container, a first container having a bottom surface and a peripheral wall portion, and a plurality of rod-shaped molded bodies are suspended from the bottom surface at intervals, and a second container that is the same except that the rod-shaped molded body is not provided. prepare. The number, the forming position, the outer diameter, and the length of the rod-shaped molded body coincide with the number, the forming position, the inner diameter, and the depth of the plurality of raw water introduction holes 65. The length of the rod-shaped molded body is equal to or longer than the length of the raw water introduction hole 65.
  • the second a cap 30 of the first end cap 20 and the second b cap 50 of the second end cap 40 is disposed inside the connected ones.
  • the length of the hollow membrane bundle 60 is adjusted in consideration of the subsequent cutting step.
  • the first container is attached to the second a cap portion 30 side of the first end side cap 20, and the second container is attached to the second b cap portion 50 side of the second end side cap 40.
  • an adhesive (potting agent) is poured into the first container and the second container by an adhesion method including a known centrifugal adhesion method, and then solidified.
  • an adhesion method including a known centrifugal adhesion method
  • the centrifugal bonding method or the stationary bonding method described in paragraph No. 21 of Japanese Patent No. 4498373 and paragraph No. 11 of Japanese Patent No. 3686225 can be applied.
  • the second a cap part 30 side of the first end part side cap 20 is in the state shown in FIG. 3, and the first end face 60a of the hollow fiber membrane bundle 60 is Blocked with adhesive.
  • the required length is cut and opened. In this way, the first fixed layer 61 and the second fixed layer 62 are formed.
  • the hollow fiber membrane module 1 of the present invention preferably has a membrane area (effective membrane area) of 10 m 2 or more, more preferably a membrane area (effective membrane area) of 30 to 45 m 2 .
  • the hollow fiber membrane module 1 will be described in the case where the first end 10a side of the cylindrical housing 10 is in the state shown in FIG.
  • the hollow fiber membrane module 1 can be used either vertically or horizontally. However, even when the hollow fiber membrane module 1 is used vertically, the hollow fiber membrane bundle 60 separated from the first fixed layer 61 and the second fixed layer 62 is used. It is conceivable that the central part is bent. Even in such a case, since the plurality of raw water introduction holes 65 are formed in the first fixed layer 61, the raw water easily flows in the extending direction of the long axis X direction of the plurality of raw water introduction holes 65.
  • raw water When raw water is supplied from the raw water supply port 22 of the hollow fiber membrane module 1, it enters a space between the first a cap portion 21 of the first end side cap 20 and the first fixed layer 61. Thereafter, the water is supplied to the central portion or the periphery of the hollow fiber membrane bundle 60 through the plurality of raw water introduction holes 65 shown in FIG. Then, after external pressure filtration from the outside to the inside of the hollow fiber membrane, the hollow fiber membrane is discharged from the permeate outlet 42 through the inside of the hollow fiber membrane. The concentrated water is discharged from the concentrated water outlet 55 through the annular space 56.
  • Example 1 of the invention of Japanese Patent No. 4498373 backwashing and gas bubbling are performed every 28.5 minutes of filtration operation (paragraph number 0056), and the embodiment of the invention of Japanese Patent No. 3686225 (paragraph number) [0019]
  • air scrubbing cleaning is carried out once every 30 minutes in the filtration operation, air scrubbing can be made unnecessary in the present invention, and the number of times can be reduced when it is carried out.
  • the filtration operation method of the present invention includes a filtration step and a washing step, and the washing step can be a filtration operation method in which back-pressure washing is performed and air scrubbing washing is not performed. If the number of times of air scrubbing is increased, there is a risk of oscillating hollow fiber membrane bundles being repeatedly contacted with each other, but the present invention can reduce the number of times even when performing air scrubbing, As mentioned above, the film is hardly damaged.
  • back pressure washing is performed.
  • Back pressure washing is performed by pressing back pressure washing water added with chemicals as needed from the concentrated water outlet 55 side.
  • the reverse pressure washing wastewater passes between the hollow fiber membrane bundles 60 and is discharged from the raw water supply port 22 that also serves as the reverse pressure washing water outlet.
  • the raw water introduction hole 65 is formed in the first fixed layer 61, the raw water easily flows in the extending direction of the long axis X direction of the raw water introduction hole 65. It is easy to be discharged.
  • Example Example 1 Filtration operation for 100 days was carried out using the hollow fiber membrane module 1 shown in FIGS.
  • the hollow fiber membrane module of Example 1 is referred to as a hollow fiber membrane module 1A.
  • the detailed conditions of the hollow fiber membrane module 1A and the filtration operation are as follows.
  • Hollow fiber membrane module 1A (Hollow fiber membrane module 1A) Hollow fiber membrane module 1A: total length 1,600mm, outer diameter 284mm Tubular housing 10: made of ABS resin (material), outer diameter 284mm, inner diameter (minimum diameter (D)) 265mm, length in X-axis direction 1,400mm Hollow fiber membrane bundle 60: made of cellulose benzoate having a degree of substitution of 2.4, filling rate 60% (filling rate is measured by the method described below), hollow fiber outer diameter 1.4 mm, hollow fiber inner diameter 0.8 mm, Length from the first end face 60a side to the second end face 60b side (L) 1,245 mm, ratio (L / D) 4.7
  • Raw water introduction hole 65 19 raw water introduction holes 65 having an opening area of 2.2 cm 2 are formed in the hollow fiber membrane bundle of the first fixed layer 61 as shown in FIG.
  • the filling rate of the hollow fiber membrane bundle 60 is calculated based on the product of the average cross-sectional area in the width direction per hollow fiber membrane and the number of hollow fiber membranes accommodated in the cylindrical housing 10.
  • the cross-sectional area was calculated by the following formula, with S2 being the minimum cross-sectional area in the width direction at the inner peripheral portions of the cylindrical housing 10, the second a cap portion 30, and the second b cap portion 50.
  • Filling rate [%] S2 / S1 ⁇ 100
  • the minimum cross-sectional area S1 is the cross-sectional area of the smallest portion in the cross-sectional area in the direction perpendicular to the X axis in the inner peripheral part of the cylindrical housing 10, the second a cap part 30, and the second b cap part 50, And it is the cross-sectional area of the space where the hollow fiber membrane except the members other than the hollow fiber membrane bundle such as a porous tube for introducing raw water is used.
  • the average cross-sectional area in the width direction per hollow fiber membrane is obtained by arbitrarily collecting a total of 100 hollow fiber membranes from the hollow fiber membrane bundle accommodated in the cylindrical housing 10, and measuring each hollow fiber membrane. The cross-sectional area was calculated by measuring the outer diameter of the thread membrane, and the average of those values was used.
  • the hollow fiber membrane module was disassembled and the state of the hollow fiber membrane bundle was confirmed. As a result, the amount of sludge adhered to the hollow fiber membrane was relatively small, and no sludge sticking was observed.
  • Example 2 Filtration operation was performed using the hollow fiber membrane module 1 shown in FIGS. 1, 2, and 3 while changing the standard membrane filtration flux.
  • the hollow fiber membrane module of Example 2 is referred to as a hollow fiber membrane module 1B.
  • the detailed conditions of the hollow fiber membrane module 1B and the filtration operation are as follows.
  • Hollow fiber membrane module 1B Hollow fiber membrane module 1B: total length 1,600mm, outer diameter 160mm Tubular housing 10: made of ABS resin (material), outer diameter 160mm, inner diameter (minimum diameter (D)) 147mm, length in the X-axis direction 1,400mm
  • Hollow fiber membrane bundle 60 Made of cellulose acetate with a substitution degree of 2.87, filling rate 42% (filling rate is measured by the method described above), hollow fiber outer diameter 1.3 mm, hollow fiber inner diameter 0.8 mm, hollow fiber membrane Effective filtration membrane area 27.1 m 2 on the outer surface, length (L) 1245 mm from the first end face 60 a side to the second end face 60 b side, ratio (L / D) 8.5
  • Raw water introduction hole 65 19 raw water introduction holes 65 having an opening area of 1.15 cm 2 are formed in the hollow fiber membrane bundle of the first fixed layer 61 as shown in FIG.
  • the drive pump is driven to feed the river water in the raw water tank (Kayabo River), supply from the raw water supply port 22 of the hollow fiber membrane module 1B and start filtration, and near the raw water supply port 22, the water temperature and the filtration inlet pressure was observed, and the filtration inlet pressure converted at a water temperature of 20 ° C. was determined.
  • the results are shown in FIG.
  • the conditions for the filtration operation were as follows. Filtration operation period: 50 days (continuous operation possible) Standard membrane filtration flux: As shown in FIG. 4, the filtration flux was increased while observing the increasing tendency of the filtration inlet pressure.
  • the membrane filtration flux was adjusted to 3 m 3 / m 2 / day when the operating days were 47 days, and the water temperature up to 50 days was 20 ° C.
  • the filtration inlet pressure converted in terms of was stable at about 80 kPa. Therefore, the membrane filtration flux could be continuously operated at 3 m 3 / m 2 / day after 50 days.
  • Comparative Example 1 Filtration operation was carried out using the hollow fiber membrane module 1 shown in FIGS. 1, 2, and 3 while changing the standard membrane filtration flow rate.
  • the hollow fiber membrane module of Comparative Example 1 is referred to as a hollow fiber membrane module 1C.
  • the detailed conditions of the hollow fiber membrane module 1C and the filtration operation are as follows.
  • Hollow fiber membrane module 1C (Hollow fiber membrane module 1C) Hollow fiber membrane module 1C: total length 2,400mm, outer diameter 160mm Cylindrical housing 10: made of ABS resin (material), outer diameter 160mm, inner diameter (minimum diameter (D)) 147mm, X-axis length 2,200mm Hollow fiber membrane bundle 60: made of cellulose acetate having a substitution degree of 3, filling rate 35% (filling rate is measured by the method described above), hollow fiber outer diameter 1.3 mm, hollow fiber inner diameter 0.8 mm, hollow fiber membrane Filtration effective membrane area 35.7 m 2 on the outer surface, length (L) 2,055 mm, ratio (L / D) 14 from the first end face 60 a side to the second end face 60 b side
  • Raw water introduction hole 65 19 raw water introduction holes 65 having an opening area of 1.15 cm 2 are formed in the hollow fiber membrane bundle of the first fixed layer 61 as shown in FIG.
  • the drive pump is driven to feed the river water in the raw water tank (Kayabo River), supply from the raw water supply port 22 of the hollow fiber membrane module 1C to start filtration, and near the raw water supply port 22, the water temperature and the filtration inlet pressure was observed, and the filtration inlet pressure converted at a water temperature of 20 ° C. was determined.
  • the results are shown in FIG.
  • the conditions for the filtration operation were as follows. Filtration operation period: 46 days Standard membrane filtration flux: As shown in FIG. 5, the filtration flux was increased while observing the increasing tendency of the filtration inlet pressure.
  • the hollow fiber membrane module 1B of Example 2 has a higher hollow fiber membrane filling rate than the hollow fiber membrane module 1C of Comparative Example 1, and thus the shear force due to the flow of water to be treated is stronger. This is considered to be because the sludge adhering to the outer surface of the hollow fiber membrane is peeled off and the amount of sludge adhering to the hollow fiber membrane generated by the filtration operation is small.
  • the hollow fiber membrane module 1C of Comparative Example 1 has a length (L) from the first end surface side to the second end surface side of the hollow fiber membrane bundle of more than 2 m, which is more than the hollow fiber membrane module 1B of Example 2. Therefore, as the filtration inlet pressure increases, the water permeation rate (membrane filtration flux) per unit membrane area decreases significantly when compared with the hollow fiber membrane module 1B of Example 2. This means that due to the large length (L), the filtration inlet pressure has to be increased in order to obtain the same membrane filtration flux, resulting in poor energy efficiency.
  • the hollow fiber membrane module of the present invention can be used in water purification plant facilities, sewage treatment facilities, seawater desalination facilities, and the like.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne un module de membrane à fibres creuses qui, pendant des opérations de filtration, est moins susceptible de provoquer l'encrassement d'une membrane à fibres creuses, permet une filtration stable, et a une excellente aptitude au lavage de la membrane à fibres creuses. Dans ce module de membrane à fibres creuses de type à pression externe, un premier côté d'extrémité ou un second côté d'extrémité de faisceau de membranes à fibres creuses 60 sont fixés, par un adhésif, ensemble à une surface de paroi interne d'un boîtier cylindrique 10 ou à des surfaces de paroi interne de capuchons. La partie sur le côté première extrémité fixée par l'adhésif a une pluralité de trous d'introduction d'eau brute 65 qui sont formés de façon à pénétrer dans ladite partie dans la direction de l'épaisseur. Le taux de remplissage du faisceau de membranes à fibres creuses 60 est de 40 à 70 %. La longueur (L) du côté de la première surface d'extrémité au côté de la seconde surface d'extrémité du faisceau de membranes à fibres creuses n'est pas supérieure à 2 m.
PCT/JP2019/016558 2018-05-07 2019-04-18 Module de membrane à fibres creuses de type à pression externe WO2019216148A1 (fr)

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JP2018-089313 2018-05-07
JP2018089313 2018-05-07
JP2018-169875 2018-09-11
JP2018169875A JP2019195800A (ja) 2018-05-07 2018-09-11 外圧式中空糸膜モジュール

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114425240A (zh) * 2020-10-29 2022-05-03 旭化成株式会社 外压式中空纤维膜组件及其制造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009202112A (ja) * 2008-02-28 2009-09-10 Mitsubishi Rayon Eng Co Ltd 中空糸膜モジュール
WO2014007138A1 (fr) * 2012-07-05 2014-01-09 東レ株式会社 Module membranes à fibres creuses
JP2017164658A (ja) * 2016-03-14 2017-09-21 株式会社ダイセル 外圧式中空糸膜モジュール
WO2017209150A1 (fr) * 2016-05-31 2017-12-07 東レ株式会社 Module de membranes à fibres creuses

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009202112A (ja) * 2008-02-28 2009-09-10 Mitsubishi Rayon Eng Co Ltd 中空糸膜モジュール
WO2014007138A1 (fr) * 2012-07-05 2014-01-09 東レ株式会社 Module membranes à fibres creuses
JP2017164658A (ja) * 2016-03-14 2017-09-21 株式会社ダイセル 外圧式中空糸膜モジュール
WO2017209150A1 (fr) * 2016-05-31 2017-12-07 東レ株式会社 Module de membranes à fibres creuses

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114425240A (zh) * 2020-10-29 2022-05-03 旭化成株式会社 外压式中空纤维膜组件及其制造方法

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