WO2010047360A1 - Membrane semi-perméable composite de type feuille et son procédé de fabrication - Google Patents

Membrane semi-perméable composite de type feuille et son procédé de fabrication Download PDF

Info

Publication number
WO2010047360A1
WO2010047360A1 PCT/JP2009/068157 JP2009068157W WO2010047360A1 WO 2010047360 A1 WO2010047360 A1 WO 2010047360A1 JP 2009068157 W JP2009068157 W JP 2009068157W WO 2010047360 A1 WO2010047360 A1 WO 2010047360A1
Authority
WO
WIPO (PCT)
Prior art keywords
sheet
separation
semipermeable membrane
epoxy resin
composite semipermeable
Prior art date
Application number
PCT/JP2009/068157
Other languages
English (en)
Japanese (ja)
Inventor
憲章 原田
敦 廣
Original Assignee
日東電工株式会社
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 日東電工株式会社 filed Critical 日東電工株式会社
Publication of WO2010047360A1 publication Critical patent/WO2010047360A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • B01D63/08—Flat membrane modules
    • B01D63/082—Flat membrane modules comprising a stack of flat membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0086—Mechanical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/105—Support pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
    • 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
    • B01D71/52—Polyethers
    • B01D71/521—Aliphatic polyethers
    • B01D71/5211—Polyethylene glycol or polyethyleneoxide
    • 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
    • B01D71/56—Polyamides, e.g. polyester-amides
    • 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
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/40—Details relating to membrane preparation in-situ membrane formation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/06—Surface irregularities

Definitions

  • the present invention relates to a sheet-like composite semipermeable membrane that is used for separating components such as liquids and has irregularities on the surface, a manufacturing method thereof, and a separation membrane element using the sheet-like composite semipermeable membrane.
  • separation membranes that separate liquids, etc., depending on the pore size and separation function.
  • a fluid separation element used for reverse osmosis filtration, ultrafiltration, etc. a supply side flow path material that guides the supply side fluid (raw water) to the surface of the separation membrane, a separation membrane that separates the supply side fluid, and a separation membrane
  • a spiral-type membrane element in which a unit comprising a permeate-side channel material that guides a permeate-side fluid (permeate) that has permeated and separated from a supply-side fluid to a central tube (collection tube) is wound around a perforated central tube It is known (see, for example, Patent Document 1).
  • a flow path material of such a spiral membrane element As a flow path material of such a spiral membrane element, a resin net or the like is mainly used. However, as described in Patent Document 2 below, the surface of the resin sheet is uneven. It is also known that is formed. Any flow path material has a role of forming a flow path for flowing raw water or permeated water in the gap between the separation membranes along the separation membrane wound in a spiral shape.
  • Patent Document 3 discloses a composite semi-permeable membrane having a plurality of hollow passages that have irregularities on the supply side corresponding to the separation active layer side of the composite semipermeable membrane and extend in a direction parallel to the membrane surface in the membrane.
  • a permeable membrane has been proposed.
  • a supply-side flow path is formed by irregularities on the supply side surface, and a permeation-side flow path is secured by a plurality of hollow passages.
  • the membrane since the membrane has a hollow passage extending in a direction parallel to the membrane surface, the depth of the unevenness on the surface cannot be increased (in the example, a step of 0.15 mm), Compared with the case where the flow path material is provided, the flow path cross-sectional area of the supply side flow path is not sufficient. In addition, the unevenness of such a depth can be formed relatively easily after the production of the composite semipermeable membrane. However, when the depth becomes 0.3 mm or more, the separation active layer of the composite semipermeable membrane is damaged. As a result, there is a problem that the salt blocking performance is lowered.
  • an object of the present invention is to provide a sheet-like composite semipermeable membrane capable of sufficiently securing the flow passage cross-sectional area of the supply-side passage while maintaining the blocking performance, a method for manufacturing the same, and the sheet-like composite semipermeable membrane. It is in providing the separation membrane element using this.
  • the sheet-like composite semipermeable membrane of the present invention is a sheet-like composite semipermeable membrane comprising a porous support having irregularities and a separation active layer formed on the surface thereof, wherein the maximum unevenness of the irregularities on the surface is obtained. Is larger than the thickness of the flat portion.
  • the maximum step difference of the surface irregularities is larger than the thickness of the flat portion film, so that a sufficient channel cross-sectional area of the supply side channel can be secured.
  • the porous support itself has a structure with an uneven surface and a separation active layer formed on the surface thereof, there is no damage due to deformation of the separation active layer, and the blocking performance can be maintained.
  • the flow path is formed by providing irregularities on the membrane surface itself, the flow path material can be omitted when manufacturing the separation membrane element. Simplification and reduction of environmental load can be achieved.
  • the separation active layer is formed by spray-coating a raw material liquid on the surface of the porous support having irregularities.
  • the separation active layer thus formed is formed with a relatively uniform thickness along the irregularities by spray coating, so that the effective membrane area per sheet area is also increased, and the permeation flux can be improved. .
  • the maximum step of the unevenness on the surface is 0.1 to 1.2 mm. Within this range, it is possible to prevent an increase in the diameter of the element due to an excessively large maximum step and excessive tightening while ensuring a sufficient channel cross-sectional area of the supply-side channel.
  • the method for producing a sheet-shaped composite semipermeable membrane of the present invention includes a step of forming a separation active layer by applying a raw material solution so as to be along the surface of a porous support having irregularities.
  • applying the raw material solution along the surface means that the raw material solution is applied at an appropriate thickness along the surface irregularities, for example, by spray coating or after application by dipping etc. It can be carried out by a method of removing excess by airflow.
  • the separation active layer is formed by applying the raw material liquid along the surface of the porous support having irregularities, and thus the separation active layer is deformed after the formation.
  • the blocking performance can be maintained high.
  • the separation active layer is formed with a relatively uniform thickness along the unevenness, there is no extremely thick portion, the effective membrane area per sheet area is increased, and the permeation flux can be improved. it can.
  • the maximum level difference of the unevenness on the surface can be made larger than the thickness of the film of the flat portion, so that the channel cross-sectional area of the supply side channel can be sufficiently secured.
  • the step of forming the separation active layer includes a step of spraying one of the raw material liquids and then spraying the other of the raw material liquids to form the separation active layer by an interfacial polymerization method.
  • a separation active layer having a more uniform thickness can be formed along the unevenness, so that membrane performance such as permeation flux and blocking performance can be formed. Can be further improved.
  • the separation membrane element of the present invention is characterized by comprising any one of the sheet-like composite semipermeable membranes described above. According to the separation membrane element of the present invention, since the sheet-like composite semipermeable membrane having the above-described effects is provided, the flow path material can be omitted, so that the raw material cost is reduced, the manufacturing process is simplified, and the environmental load is reduced. Can be reduced.
  • the sheet-shaped composite semipermeable membrane may be spirally wound around a perforated central tube in a state where the transmission side surfaces or the supply side surfaces of the sheet-shaped composite semipermeable membrane are in contact with each other.
  • Spiral type separation membrane elements are widely used because of their large effective membrane area per unit volume.
  • the manufacturing process can be greatly simplified. Can do.
  • a plurality of cylindrical separation membrane units in which the permeation side surfaces or the supply side surfaces of the sheet-shaped composite semipermeable membrane are in contact with each other are stacked, and one or both ends of the separation membrane unit are connected to the permeation side flow path or the supply side flow. It is preferable that either one of the paths is sealed so as to open. According to the separation membrane element having such a structure, the raw material cost can be further reduced, the manufacturing process can be simplified, and the environmental load can be reduced as compared with the spiral type.
  • FIG. 1 is a view showing an example of a sheet-like composite semipermeable membrane of the present invention, (a) is a plan view seen from the supply side, (b) is a sectional view taken along line II, and (c) is a laminated state thereof.
  • FIG. 1 is a view showing an example of a sheet-like composite semipermeable membrane of the present invention, (a) is a plan view seen from the supply side, (b) is a sectional view taken along line II, and (c) is a laminated state thereof.
  • the sheet-like composite semipermeable membrane of the present invention comprises a porous support 5 having irregularities and a separation active layer 6 formed on the surface thereof.
  • the convex shape is embossed from the supply side surface Sb to form the convex portions 1a and 1ba on the transmission side surface Sa, and at the same time the convex shape is embossed from the transmission side surface Sa to the convex portion 1a and 1bb on the supply side surface Sb. Is forming.
  • the convex shape is embossed from the supply side surface Sb so that the concave portion 2b is formed on the supply side surface Sb. May be.
  • the shape of the convex portions 1a, 1ba, 1b may be any shape as long as it can form a flow path along the membrane surface.
  • the shape of the upper surface is a rhombus, a parallelogram, an ellipse, an oval, a circle, a square, Examples include triangles and other polygons. Among them, a rhombus, a parallelogram, an ellipse, an oval, or the like capable of setting the ratio of the major axis D1 / minor axis D2 to 2/1 to 4/1 is preferable.
  • the major axis D1 of the upper surfaces of the convex portions 1a, 1ba, 1b is preferably 0.3 to 1.0 mm, and more preferably 0.5 to 0.8 mm.
  • the minor axis D2 of the upper surface is preferably 0.3 to 1.0 mm, and more preferably 0.3 to 0.5 mm.
  • the protrusions 1a and 1b may be arranged in any way as long as they do not interfere with the flow path, are randomly arranged, a matrix-like arrangement in which the protrusions 1a and 1b are arranged vertically and horizontally, and the vertical portions of the protrusions 1a and 1b. There is a staggered arrangement in which the arrangement is alternated for each column. Among these, those arranged at a constant pitch in the oblique direction are preferable from the viewpoint that the oblique flow path can be formed and the pressure loss of the flow path can be minimized.
  • the area ratio of the concave portion 2 is preferably 55 to 70% when the upper surface of the convex portions 1a and 1b is used as a reference. This area ratio is effective in the case of staggered arrangement, and is particularly effective in the case where the rhombic protrusions 1a and 1b are arranged in a staggered manner.
  • the area ratio of the concave portion 2 is a value obtained by subtracting the ratio (percentage) occupied by the area of the upper surface of the convex portions 1a and 1b from 100%.
  • the sheet-like composite semipermeable membrane according to the present invention is characterized in that the maximum unevenness H0 on the surface (supply side surface Sb) is larger than the thickness t of the flat portion.
  • the maximum unevenness H0 of the unevenness may be about 0.1 to 1.2 mm from the viewpoint of practicality, preferably 0.2 to 0.8 mm, and preferably 0.3 to 0.00 mm. More preferably, it is 6 mm. If the step is too low, a sufficient flow path cannot be secured, and if it is too high, the flow path becomes too wide and sufficient processing performance is difficult to obtain.
  • the maximum unevenness H0 is the sum of the height H1 of the convex portion 1a of the transmission side surface Sa and the height H2 of the convex portion 1b of the supply side surface Sb.
  • the height H1 of the convex portion 1a of the transmission side surface Sa is preferably 0.3 to 0.5 mm. Further, the height H2 of the convex portion 1b of the supply side surface Sb is preferably 0.3 to 0.5 mm.
  • the sheet-like composite semipermeable membrane of the present invention is used in a state as shown in FIG.
  • the convex portion 1a and the convex portion 1a of the transmission side surface Sa are opposed to and in contact with each other
  • the convex portion 1b and the convex portion 1b of the supply side surface Sb are opposed to and in contact with each other.
  • the supply-side flow path 7b and the permeation-side flow path 7a are formed in the recess 2b and the recess 2a, respectively.
  • the sheet-like composite semipermeable membrane of the present invention can be produced using a material conventionally used as a reverse osmosis membrane or a nanofiltration membrane. That is, a conventionally well-known material can be used for both the porous support 5 having irregularities and the separation active layer 6 formed on the surface thereof.
  • Examples of the material of the porous support 5 having irregularities include a thermosetting resin, a thermoplastic resin, and a heat resistant resin.
  • examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, acrylic resin, fluororesin, polyester, and polyamide.
  • examples of the heat resistant resin include polysulfone, polyethersulfone, aromatic polyimide, polyamide, and polyester.
  • examples of the thermosetting resin include epoxy resins, unsaturated polyester resins, phenol resins, amino resins, polyurethane resins, silicone resins, and thermosetting polyimide resins.
  • a conventional support formed of polysulfone on a nonwoven fabric is preferably used from the viewpoint of versatility, and a thermosetting resin is preferable from the viewpoint of the stability of uneven processing, and particularly the raw material cost can be reduced, and uneven processing. From the viewpoint of easy handling, an epoxy resin is preferable.
  • the thickness of the porous support 5 is preferably 80 to 300 ⁇ m, more preferably 100 to 200 ⁇ m, from the viewpoint of forming irregularities and maintaining the shape.
  • the porous support 5 may include a reinforcing material such as a non-woven fabric, but from the viewpoint of maintaining the shape by forming irregularities, a material that does not include a reinforcing material such as a non-woven fabric is preferable.
  • the porous support 5 may be an asymmetric membrane having a different pore diameter in the thickness direction or a symmetric membrane. Further, from the viewpoint of forming the separation active layer on the surface, the average pore diameter on the surface is preferably 0.01 to 0.4 ⁇ m, and more preferably 0.05 to 0.2 ⁇ m.
  • the porous support is composed of a thermosetting resin porous sheet having pores communicating with a three-dimensional network skeleton, and the thermosetting
  • the porous resin porous sheet preferably has an average pore diameter of 0.01 to 0.4 ⁇ m.
  • thermosetting resin porous sheet As a raw material for the thermosetting resin porous sheet, a thermosetting resin composition containing a thermosetting resin, a curing agent, and a porogen is used.
  • thermosetting resin examples include epoxy resin, phenol resin, melamine resin, urea resin (urea resin), alkyd resin, unsaturated polyester resin, polyurethane, thermosetting polyimide, silicone resin, and diallyl.
  • a phthalate resin etc. are mentioned, It is especially preferable to use an epoxy resin.
  • thermosetting resin porous sheet is an epoxy resin porous sheet.
  • epoxy resin examples include bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, stilbene type epoxy resin, biphenyl type epoxy resin, bisphenol A novolak type epoxy resin, Contains cresol novolac type epoxy resin, diaminodiphenylmethane type epoxy resin, polyphenyl base epoxy resin such as tetrakis (hydroxyphenyl) ethane base, fluorene-containing epoxy resin, triglycidyl isocyanurate, heteroaromatic ring (eg triazine ring) Aromatic epoxy resins such as epoxy resins; aliphatic glycidyl ether type epoxy resins, aliphatic glycidyl ester type epoxy resins, alicyclic glycidyl Ether type epoxy resin, aromatic epoxy resins such as alicyclic glycidyl ester type epoxy resins. These may be used alone or in combination of two or more.
  • bisphenol A type epoxy resin brominated bisphenol A type epoxy resin, bisphenol F are used to form a uniform three-dimensional network skeleton and uniform pores, and to ensure chemical resistance and film strength.
  • a bisphenol A type epoxy resin from the group consisting of a bisphenol A type epoxy resin, a brominated bisphenol A type epoxy resin, a bisphenol AD type epoxy resin, a fluorene-containing epoxy resin, and a triglycidyl isocyanurate having an epoxy equivalent of 6000 or less and a melting point of 170 ° C. or less.
  • At least one aromatic epoxy resin selected selected from the group consisting of an alicyclic glycidyl ether type epoxy resin having an epoxy equivalent of 6000 or less and a melting point of 170 ° C. or less, and an alicyclic glycidyl ester type epoxy resin It is preferable to use at least one alicyclic epoxy resin.
  • curing agent examples include aromatic amines (for example, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzyldimethylamine, dimethylaminomethylbenzene), aromatic acid anhydrides (for example, phthalic anhydride).
  • aromatic amines for example, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzyldimethylamine, dimethylaminomethylbenzene
  • aromatic acid anhydrides for example, phthalic anhydride
  • Non-aromatic such as undecane adduct, bis (4-amino-3-
  • metaphenylenediamine having two or more primary amines in the molecule, diaminodiphenylmethane, And at least one aromatic amine curing agent selected from the group consisting of diaminodiphenylsulfone; bis (4-amino-3-methylcyclohexyl) methane having two or more primary amines in the molecule, and bis (4-amino) It is preferred to use at least one alicyclic amine curing agent selected from the group consisting of (cyclohexyl) methane.
  • the combination of the epoxy resin and the curing agent is preferably a combination of an aromatic epoxy resin and an alicyclic amine curing agent, or a combination of an alicyclic epoxy resin and an aromatic amine curing agent. These combinations increase the heat resistance of the resulting epoxy resin porous sheet and are suitably used as a porous support for a composite semipermeable membrane.
  • the porogen that can be used in the present invention refers to a solvent that can dissolve an epoxy resin and a curing agent, and can cause reaction-induced phase separation after the epoxy resin and the curing agent are polymerized, such as methyl cellosolve.
  • cellosolves such as ethyl cellosolve, esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, and glycols such as polyethylene glycol and polypropylene glycol. These may be used alone or in combination of two or more.
  • methyl cellosolve, ethyl cellosolve, polyethylene glycol having a molecular weight of 600 or less, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate should be used.
  • polyethylene glycol having a molecular weight of 200 or less and propylene glycol monomethyl ether acetate are preferably used.
  • a solvent in which a reaction product of the epoxy resin and the curing agent is soluble can be used as a porogen.
  • porogen include brominated bisphenol A type epoxy resin (“Epicoat 5058” manufactured by Japan Epoxy Resin Co., Ltd.).
  • the porosity, average pore size, pore size distribution, etc. of the epoxy resin porous sheet are based on the type and compounding ratio of raw materials such as epoxy resin, curing agent, porogen, etc., and reaction such as heating temperature and heating time during reaction-induced phase separation. Since it varies depending on the conditions, it is preferable to create a phase diagram of the system and select the optimum conditions in order to obtain the desired porosity, average pore diameter, and pore diameter distribution. In addition, by controlling the molecular weight, molecular weight distribution, system viscosity, crosslinking reaction rate, etc. of the crosslinked epoxy resin during phase separation, the co-continuous structure of the crosslinked epoxy resin and porogen is fixed in a specific state and stable. A porous structure can be obtained.
  • the type and blending ratio of the epoxy resin and the curing agent may be determined so that the ratio of carbon atoms derived from the aromatic ring to the total carbon atoms constituting the epoxy resin porous sheet is in the range of 0.1 to 0.65. preferable.
  • the recognizability of the planar structure of the separation medium which is a characteristic of the epoxy resin porous sheet, tends to decrease.
  • it exceeds 0.65 it becomes difficult to form a uniform three-dimensional network skeleton.
  • the blending ratio of the curing agent to the epoxy resin is preferably such that the curing agent equivalent is 0.6 to 1.5 with respect to 1 equivalent of the epoxy group.
  • the curing agent equivalent is less than 0.6, the crosslinking density of the cured product is lowered, and the heat resistance, solvent resistance and the like tend to be lowered. On the other hand, if it exceeds 1.5, unreacted curing agent remains or tends to hinder the improvement of the crosslinking density.
  • a curing accelerator may be added to the solution in order to obtain the desired porous structure.
  • known ones can be used.
  • tertiary amines such as triethylamine and tributylamine, 2-phenol-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenol- Examples thereof include imidazoles such as 4,5-dihydroxyimidazole.
  • the average pore diameter of the epoxy resin porous sheet is preferably 0.05 to 0.2 ⁇ m.
  • the average pore diameter of the epoxy resin porous sheet is preferably 0.05 to 0.2 ⁇ m.
  • the average pore diameter of the epoxy resin porous sheet is 0.01 to 0.4 ⁇ m.
  • a method in which two or more epoxy resins having different epoxy equivalents are mixed and used is also suitable. At that time, the difference in epoxy equivalent is preferably 100 or more.
  • the average pore diameter of the epoxy resin porous sheet can be adjusted to a desired range by appropriately setting various conditions such as the total epoxy equivalent and the porogen ratio and the curing temperature.
  • the epoxy resin porous sheet can be produced, for example, by the following method.
  • An epoxy resin composition containing an epoxy resin, a curing agent, and a porogen is applied on a substrate, and then the applied epoxy resin composition is heated to three-dimensionally crosslink the epoxy resin. At that time, a co-continuous structure is formed by phase separation of the crosslinked epoxy resin and the porogen. Thereafter, the porogen is washed and removed from the obtained epoxy resin sheet and dried to produce an epoxy resin porous sheet having pores communicating with the three-dimensional network skeleton.
  • the substrate to be used is not particularly limited, and examples thereof include a plastic substrate, a glass substrate, and a metal plate.
  • An epoxy resin composition containing an epoxy resin, a curing agent, and a porogen is applied onto a substrate, and then another substrate is covered on the applied epoxy resin composition to produce a sandwich structure.
  • spacers for example, double-sided tape
  • the sandwich structure is heated to cross-link the epoxy resin three-dimensionally.
  • a co-continuous structure is formed by phase separation of the crosslinked epoxy resin and the porogen.
  • the obtained epoxy resin sheet is taken out, the porogen is washed and removed, and dried to produce an epoxy resin porous sheet having pores communicating with the three-dimensional network skeleton.
  • the substrate to be used is not particularly limited, and examples thereof include a plastic substrate, a glass substrate, and a metal plate, and it is particularly preferable to use a glass substrate.
  • An epoxy resin composition containing an epoxy resin, a curing agent, and a porogen is filled in a mold having a predetermined shape, and then heated to three-dimensionally crosslink the epoxy resin to produce a cylindrical or columnar resin block. .
  • a co-continuous structure is formed by phase separation of the crosslinked epoxy resin and the porogen.
  • the surface of the block is cut with a predetermined thickness while rotating the block about the cylindrical axis or the columnar axis to produce a long epoxy resin sheet.
  • the porogen in the epoxy resin sheet is washed and removed, and dried to produce an epoxy resin porous sheet having pores communicating with the three-dimensional network skeleton.
  • the conditions for heating the epoxy resin composition are not particularly limited, but the temperature is about 100 to 150 ° C., and the heating time is about 10 minutes to 5 hours.
  • Post-cure may be performed to increase the degree of crosslinking of the crosslinked epoxy resin after the heat treatment.
  • Examples of the solvent used for removing the porogen from the obtained epoxy resin sheet include water, DMF, DMSO, THF, and mixed solvents thereof, and are appropriately selected according to the type of porogen.
  • the drying conditions of the epoxy resin porous sheet from which the porogen has been removed are not particularly limited, but the temperature is about 40 to 120 ° C., and the drying time is about 0.2 to 3 hours.
  • the thickness of the epoxy resin porous sheet is not particularly limited, but is about 50 to 250 ⁇ m from the viewpoint of strength, practical water permeability, and salt blocking property. Further, the back surface of the epoxy resin porous sheet may be reinforced with a woven fabric or a nonwoven fabric.
  • the material for forming the separation active layer is not particularly limited, and examples thereof include cellulose acetate, ethyl cellulose, polyether, polyester, and polyamide.
  • a separation active layer containing a polyamide resin formed by interfacial polymerization of a polyfunctional amine component and a polyfunctional acid halide component is preferable.
  • the polyfunctional amine component is a polyfunctional amine having two or more reactive amino groups, and examples thereof include aromatic, aliphatic, and alicyclic polyfunctional amines.
  • aromatic polyfunctional amines include m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, and 3,5-diamino.
  • aromatic polyfunctional amines include m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, and 3,5-diamino.
  • examples include benzoic acid, 2,4-diaminotoluene, 2,6-diaminotoluene, N, N′-dimethyl-m-phenylenediamine, 2,4-diaminoanisole, amidole, xylylenediamine and the like.
  • Examples of the aliphatic polyfunctional amine include ethylenediamine, propylenediamine, tris (2-aminoethyl) amine, and n-phenyl-ethylenediamine.
  • Examples of the alicyclic polyfunctional amine include 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine, 2,5-dimethylpiperazine, 4-aminomethylpiperazine, and the like.
  • polyfunctional amines may be used alone or in combination of two or more. In order to obtain a separation active layer having high salt blocking performance, it is preferable to use an aromatic polyfunctional amine.
  • the polyfunctional acid halide component is a polyfunctional acid halide having two or more reactive carbonyl groups.
  • polyfunctional acid halide examples include aromatic, aliphatic, and alicyclic polyfunctional acid halides.
  • aromatic polyfunctional acid halides include trimesic acid trichloride, terephthalic acid dichloride, isophthalic acid dichloride, biphenyldicarboxylic acid dichloride, naphthalene dicarboxylic acid dichloride, benzenetrisulfonic acid trichloride, benzenedisulfonic acid dichloride, chlorosulfonylbenzene dicarboxylic acid.
  • An acid dichloride etc. are mentioned.
  • Examples of the aliphatic polyfunctional acid halide include propanedicarboxylic acid dichloride, butanedicarboxylic acid dichloride, pentanedicarboxylic acid dichloride, propanetricarboxylic acid trichloride, butanetricarboxylic acid trichloride, pentanetricarboxylic acid trichloride, glutaryl halide, adipoid Examples include luhalides.
  • Examples of the alicyclic polyfunctional acid halide include cyclopropanetricarboxylic acid trichloride, cyclobutanetetracarboxylic acid tetrachloride, cyclopentanetricarboxylic acid trichloride, cyclopentanetetracarboxylic acid tetrachloride, cyclohexanetricarboxylic acid trichloride, and tetrahydrofuran.
  • Examples thereof include tetracarboxylic acid tetrachloride, cyclopentane dicarboxylic acid dichloride, cyclobutane dicarboxylic acid dichloride, cyclohexane dicarboxylic acid dichloride, and tetrahydrofurandicarboxylic acid dichloride.
  • polyfunctional acid halides may be used alone or in combination of two or more.
  • an aromatic polyfunctional acid halide it is preferable to use an aromatic polyfunctional acid halide.
  • a polymer such as polyvinyl alcohol, polyvinyl pyrrolidone, or polyacrylic acid, a polyhydric alcohol such as sorbitol, glycerin, or the like may be copolymerized.
  • the method for forming the separation active layer containing the polyamide resin on the surface of the epoxy resin porous sheet is not particularly limited, and any known method can be used. Examples thereof include an interfacial polymerization method, a phase separation method, and a thin film coating method.
  • the interfacial polymerization method is a method in which a separation active layer is formed by bringing an aqueous amine solution containing a polyfunctional amine component into contact with an organic solution containing a polyfunctional acid halide component to form an active separation layer.
  • an aqueous solution coating layer comprising an aqueous amine solution containing a polyfunctional amine component is formed on the epoxy resin porous sheet, and then an organic solution containing the polyfunctional acid halide component is contacted with the aqueous solution coating layer to perform interfacial polymerization. It is preferable to form the separation active layer by forming the separation active layer.
  • the concentration of the polyfunctional amine component in the aqueous amine solution is not particularly limited, but is preferably 0.1 to 5% by weight, more preferably 0.5 to 2% by weight.
  • concentration of the polyfunctional amine component is less than 0.1% by weight, defects such as pinholes are likely to occur in the separation active layer, and the salt blocking performance tends to be lowered.
  • concentration of the polyfunctional amine component exceeds 5% by weight, the film thickness becomes too thick and the permeation resistance tends to increase and the permeation flux tends to decrease.
  • the concentration of the polyfunctional acid halide component in the organic solution is not particularly limited, but is preferably 0.01 to 5% by weight, more preferably 0.05 to 3% by weight.
  • concentration of the polyfunctional acid halide component is less than 0.01% by weight, the unreacted polyfunctional amine component is likely to remain, or defects such as pinholes are likely to occur in the separation active layer, resulting in salt blocking performance. It tends to decrease.
  • concentration of the polyfunctional acid halide component exceeds 5% by weight, the unreacted polyfunctional acid halide component tends to remain, or the film thickness becomes too thick to increase the permeation resistance, thereby increasing the permeation flux. It tends to decrease.
  • the organic solvent used in the organic solution is not particularly limited as long as it has low solubility in water, does not deteriorate the epoxy resin porous sheet, and dissolves the polyfunctional acid halide component.
  • cyclohexane, heptane, octane And saturated hydrocarbons such as nonane, and halogen-substituted hydrocarbons such as 1,1,2-trichlorotrifluoroethane is preferred.
  • a saturated hydrocarbon having a boiling point of 300 ° C. or lower, more preferably a boiling point of 200 ° C. or lower.
  • additives can be added to the aqueous amine solution and the organic solution for the purpose of facilitating film formation and improving the performance of the resulting composite semipermeable membrane.
  • the additive include surfactants such as sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and sodium lauryl sulfate, sodium hydroxide that removes hydrogen halide generated by polymerization, trisodium phosphate, and triethylamine.
  • surfactants such as sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and sodium lauryl sulfate
  • sodium hydroxide that removes hydrogen halide generated by polymerization
  • trisodium phosphate triethylamine.
  • the time from applying the amine aqueous solution on the epoxy resin porous sheet to applying the organic solution is 15 seconds or less, depending on the composition of the aqueous amine solution, the viscosity, and the pore diameter of the surface of the epoxy resin porous sheet. Preferably, it is 5 seconds or less.
  • the application interval of the solution exceeds 15 seconds, the aqueous amine solution may penetrate and diffuse deep inside the epoxy resin porous sheet, and a large amount of unreacted polyfunctional amine component may remain in the epoxy resin porous sheet. .
  • the unreacted polyfunctional amine component that has penetrated deep inside the epoxy resin porous sheet tends to be difficult to remove even in the subsequent film cleaning treatment.
  • the aqueous solution coating layer composed of the aqueous amine solution and the organic solution containing the polyfunctional acid halide component are brought into contact with each other, an excessive solution on the epoxy resin porous sheet is removed to form a film on the epoxy resin porous sheet.
  • the heating temperature is more preferably 70 to 200 ° C., particularly preferably 100 to 150 ° C.
  • the heating time is preferably about 30 seconds to 10 minutes, more preferably about 40 seconds to 7 minutes.
  • the thickness of the separation active layer formed on the epoxy resin porous sheet is not particularly limited, but is usually about 0.05 to 2 ⁇ m, preferably 0.1 to 1 ⁇ m.
  • the irregularities are formed after the porous support 5 is formed, and then spray coating or dipping is used.
  • a method of forming a separation active layer by a method of removing excess with an air flow after coating is used. That is, the sheet-like composite semipermeable membrane of the present invention is produced by the production method of the present invention, which includes a step of forming a separation active layer by applying a raw material solution along the surface of the porous support having irregularities. can do.
  • the porous support 5 having irregularities can be obtained by a method of forming irregularities during film formation or a method of forming irregularities after film formation.
  • Examples of the method for forming irregularities during film formation include a method of providing irregularities on a substrate on which a film-forming solution is cast, and a method of providing irregularities on both sides of a substrate when sandwiching the substrates from both sides.
  • Examples of the method for forming irregularities after film formation include heat press, pressure press, continuous lamination, roll embossing, etc., but roll embossing is performed from the viewpoint of easily maintaining the porous structure of the separation membrane. Is preferred.
  • the conditions for roll embossing can be appropriately determined according to the melting point and heat distortion temperature of the porous support 5.
  • the feed rate is 1.0 to 20 m / min, A heating temperature of 80 to 130 ° C. is preferred.
  • a feed rate of 0.5 to 20 m / min and a roll heating temperature of 100 to 150 ° C. are preferable.
  • the step of forming the separation active layer by applying the raw material liquid to the porous support having irregularities is not only when the separation active layer is formed by the interfacial polymerization method, but also when the separation active layer is formed by the phase separation method.
  • a separation active layer formed by a phase separation method a method of forming a separation active layer by applying a raw material liquid that is a dope by spray coating or the like and then immersing it in a coagulation bath is an example. . Except for such a coating method, any conventionally known conditions can be adopted.
  • a separation active layer formed by the interfacial polymerization method it is preferable to spray-coat one of the raw material liquids and then spray-coat the other of the raw material liquids to form a separation active layer by the interfacial polymerization method.
  • a polyamide separation active layer is formed by a reaction between an amine monomer and an acid monomer
  • a method of removing an excess amine solution with (air knife) or the like is preferably used.
  • the separation membrane element of the present invention is characterized by including the sheet-like composite semipermeable membrane as described above.
  • the separation membrane element of the present invention may be any as long as a sheet-like composite semipermeable membrane can be used, for example, any of spiral type, disk type, flat membrane type, and the like.
  • the sheet-shaped composite semipermeable membrane is wound around the perforated central tube in a spiral shape with the permeation side surfaces or the supply side surfaces of the sheet-like composite semipermeable membrane in contact with each other.
  • the present invention is particularly effective when the transmission side surfaces and the supply side surfaces of the sheet-like composite semipermeable membrane are brought into contact with each other.
  • a flat membrane type separation membrane element is formed by laminating a plurality of cylindrical separation membrane units U in which the transmission side surfaces Sa or the supply side surfaces Sb of the sheet-like composite semipermeable membrane are in contact with each other. It is preferable that one or both ends of the membrane unit U are sealed so that either the permeate side flow path or the supply side flow path opens. In the illustrated example, both ends of the separation membrane unit U are sealed by the resin sealing member 3 so that the permeate-side flow path is opened.
  • the cylindrical separation membrane unit U is formed by folding one sheet-shaped composite semipermeable membrane in half, or stacking two sheet-shaped composite semipermeable membranes, and using an adhesive on one or both sides. It can be manufactured by sealing by conventional bonding or heat fusion.
  • sealing resin a thermosetting resin such as an epoxy resin or a urethane resin is preferably used.
  • one end part or both end parts of each separation membrane unit U are sealed in advance by sealing or bonding when sealing with resin.
  • a method is preferred in which the end of the separation membrane unit U is cut and opened after sealing the whole and sealing the whole.
  • the other end portion of the separation membrane unit U is not opened. Occlude.
  • an all-filtration type separation membrane element can be produced.
  • a raw solution is supplied from one opening 3a and a permeate separated by the separation membrane is separated. Separation by total filtration is possible while taking out the membrane unit U.
  • Example 1 A film-forming dope in which 18% by weight of polysulfone (manufactured by Solvay, P-3500) was dissolved in N, N-dimethylformamide (DMF) was uniformly applied on a nonwoven fabric substrate with a wet thickness of 200 ⁇ m. Thereafter, the porous substrate was solidified by immediately immersing it in water at 40 to 50 ° C. and completely extracted and washed with DMF as a solvent to prepare a porous support having a polysulfone microporous layer on the nonwoven fabric substrate. .
  • DMF N, N-dimethylformamide
  • the thickness of the flat part was 110 ⁇ m.
  • porous support Using this porous support, m-phenylenediamine 3 parts by weight, sodium lauryl sulfate 0.2 parts by weight, camphorsulfonic acid 8 parts by weight, triethylamine 4 parts by weight, isopropyl alcohol 10 parts by weight, and water 74.85 parts by weight Aqueous amine solution containing parts was spray-coated on the porous support to form an aqueous solution coating layer. Spray coating was performed so as to cover the entire surface, and then dry air was blown to remove excess aqueous amine solution.
  • an isooctane solution containing 0.25% by weight of trimesic acid chloride is spray-coated on the surface of the aqueous solution coating layer and heated to 100 ° C. to cause an interfacial polymerization reaction to form a separation active layer (thickness 0.01 ⁇ m).
  • a separation active layer thickness 0.01 ⁇ m
  • the produced dry composite semipermeable membrane is cut into a predetermined shape and size and set in a cell for flat membrane evaluation.
  • An aqueous solution (25 ° C.) containing 1500 mg / L NaCl and adjusted to pH 6.5 with NaOH is brought into contact with the membrane by applying a differential pressure of 1.5 MPa between the supply side and the permeation side of the membrane.
  • the permeation rate and conductivity of the permeated water obtained by this operation were measured, and the permeation flux (m 3 / m 2 ⁇ d) and the salt rejection (%) were calculated.
  • the salt rejection was calculated in advance using a correlation (calibration curve) between NaCl concentration and aqueous solution conductivity in advance.
  • Salt rejection (%) ⁇ 1 ⁇ (NaCl concentration in the permeate [mg / L]) / (NaCl concentration in the feed liquid [mg / L]) ⁇ ⁇ 100
  • the rejection was 88.4%
  • the permeation flux was 1.03 m 3 / m 2 ⁇ d.
  • Example 2 Add 53 g of polyethylene glycol 200 (Tokyo Kasei Co., Ltd.) to 23.3 g of bisphenol A type epoxy resin (Toto Kasei Co., Ltd., trade name “YD-128”, epoxy equivalent: 184 to 194 (g / eq)), The mixture was stirred for 5 minutes at 2000 rpm using a rotating / revolving mixer (trade name “Awatori Nertaro” ARE-250) and dissolved to obtain an epoxy resin / polyethylene glycol solution.
  • a rotating / revolving mixer trade name “Awatori Nertaro” ARE-250
  • the above-mentioned epoxy resin / polyethylene glycol / curing agent solution was applied onto a soda glass plate provided with double-sided tape at the four corners, and another soda glass plate was laminated thereon to obtain a sandwich structure. Thereafter, the sandwich structure was placed in a dryer and reaction-cured at 120 ° C. for 3 hours. After cooling, the epoxy resin sheet was taken out and immersed in water for 12 hours to remove polyethylene glycol. Thereafter, it was dried in a dryer at 50 ° C. for about 4 hours to obtain an epoxy resin porous sheet.
  • the thickness of the flat part was 132 ⁇ m.
  • an aqueous amine solution containing 1% by weight of m-phenylenediamine, 3% by weight of triethylamine, and 6% by weight of camphorsulfonic acid was spray-coated on the porous epoxy resin sheet, and then dried air Was sprayed to remove excess amine aqueous solution to form an aqueous solution coating layer.
  • an isooctane solution containing 0.2% by weight of trimesic acid chloride was spray-coated on the surface of the aqueous solution coating layer. Thereafter, the excess solution is removed by blowing dry air, and further kept in a hot air dryer at 120 ° C. for 3 minutes, and a separation active layer containing polyamide resin on the epoxy resin porous sheet (thickness 0.01 ⁇ m) To form a composite semipermeable membrane.
  • FIG. 2 is a diagram showing an example of a sheet-like composite semipermeable membrane according to the present invention, where (a) is a plan view seen from the supply side, (b) is a sectional view taken along line II, and (c) is a sectional view showing a laminated state thereof.
  • Figure The perspective view which shows an example of the separation membrane element of this invention

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L’invention concerne une membrane semi-perméable composite de type feuille, selon laquelle l’aire de section transversale d’un canal d’écoulement du côté de l’alimentation peut être suffisamment assurée, tout en maintenant les performances de rejet. L’invention concerne également un procédé de fabrication de la membrane semi-perméable composite de type feuille, et un élément membranaire de séparation qui utilise la membrane semi-perméable composite de type feuille. La membrane semi-perméable composite de type feuille est munie d’un corps de support poreux (5) comprenant des sections en protubérance et des sections en retrait, et d’une couche active de séparation (6) formée sur la surface du corps de support poreux. Selon l’invention, la différence de niveau maximale (HO) entre les sections en protubérance et les sections en retrait sur la surface (surface du côté de l’alimentation (Sb)) est supérieure à une épaisseur (t) d’une section plate.
PCT/JP2009/068157 2008-10-23 2009-10-22 Membrane semi-perméable composite de type feuille et son procédé de fabrication WO2010047360A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008-273463 2008-10-23
JP2008273463A JP2010099590A (ja) 2008-10-23 2008-10-23 シート状複合半透膜及びその製造方法

Publications (1)

Publication Number Publication Date
WO2010047360A1 true WO2010047360A1 (fr) 2010-04-29

Family

ID=42119397

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/068157 WO2010047360A1 (fr) 2008-10-23 2009-10-22 Membrane semi-perméable composite de type feuille et son procédé de fabrication

Country Status (2)

Country Link
JP (1) JP2010099590A (fr)
WO (1) WO2010047360A1 (fr)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2578303A1 (fr) * 2010-06-03 2013-04-10 Toray Industries, Inc. Élément de membrane de séparation
WO2013125505A1 (fr) * 2012-02-24 2013-08-29 東レ株式会社 Membrane de séparation et élément de membrane de séparation
EP2633901A1 (fr) * 2010-10-26 2013-09-04 Toray Industries, Inc. Membrane de séparation, élément de membrane de séparation et procédé de production de membrane de séparation
CN108079796A (zh) * 2017-12-26 2018-05-29 北京碧水源膜科技有限公司 一种波纹膜及其制作方法和应用
CN109070019A (zh) * 2017-03-01 2018-12-21 株式会社村田制作所 过滤滤除器
US10471391B2 (en) 2016-11-19 2019-11-12 Aqua Membranes, Inc. Flow directing devices for spiral-wound elements
CN110691639A (zh) * 2017-03-20 2020-01-14 Bl 科技公司 具有经压印非织造基材的离子交换膜
US11083997B2 (en) 2017-04-20 2021-08-10 Aqua Membranes Inc. Non-nesting, non-deforming patterns for spiral-wound elements
US11090612B2 (en) 2017-04-12 2021-08-17 Aqua Membranes Inc. Graded spacers for filtration wound elements
CN114558451A (zh) * 2022-02-23 2022-05-31 泰州清润环保科技有限公司 一种三维梯形凹凸结构peg脱硫膜及其制备方法
US11376552B2 (en) 2016-09-20 2022-07-05 Aqua Membranes Inc. Permeate flow paterns
US11633700B2 (en) 2020-04-07 2023-04-25 Aqua Membranes Inc. Independent spacers and methods
US11745144B2 (en) 2017-10-13 2023-09-05 Aqua Membranes Inc. Bridge support and reduced feed spacers for spiral-wound elements
US11745143B2 (en) 2017-04-20 2023-09-05 Aqua Membranes, Inc. Mixing-promoting spacer patterns for spiral-wound elements

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2614881A1 (fr) 2010-09-07 2013-07-17 Toray Industries, Inc. Membrane de séparation, élément de membrane de séparation et procédé de production d'une membrane de séparation
EP2659952A4 (fr) 2010-12-28 2014-09-17 Toray Industries Élément de séparation membranaire
TW201247297A (en) 2011-03-29 2012-12-01 Toray Industries Spiral type separation membrane element and method for producing the same
JP2012217871A (ja) * 2011-04-04 2012-11-12 Nitto Denko Corp 複合半透膜及びその製造方法
JP6111668B2 (ja) 2011-07-07 2017-04-12 東レ株式会社 分離膜エレメント、および分離膜エレメントの製造方法
JP6136269B2 (ja) 2011-09-29 2017-05-31 東レ株式会社 水処理用分離膜エレメント
JPWO2013047746A1 (ja) 2011-09-29 2015-03-26 東レ株式会社 分離膜、分離膜エレメントおよび分離膜の製造方法
US9597640B2 (en) * 2011-12-02 2017-03-21 Toray Industries, Inc. Separation membrane element and production method for same
US20150321148A1 (en) 2012-06-28 2015-11-12 Toray Industries, Inc. Separation membrane and separation membrane element
WO2019023690A1 (fr) * 2017-07-28 2019-01-31 University Of Connecticut Membranes polymères lisses et leurs procédés de fabrication par impression par électropulvérisation
KR101979567B1 (ko) * 2017-09-01 2019-05-20 고려대학교 산학협력단 내오염 특화 패턴 구조를 가지는 박막 복합체 분리막의 제조 공정

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6115705A (ja) * 1984-07-02 1986-01-23 Daicel Chem Ind Ltd 半透膜補強用支持体
JPS6369503A (ja) * 1986-08-29 1988-03-29 アドバンスド・ポリマ−・テクノロジ−・インコ−ポレ−テド 高流束密度、低汚れ傾向の透過性膜
JPH06277463A (ja) * 1993-03-26 1994-10-04 Kurita Water Ind Ltd 膜分離装置
JPH07328397A (ja) * 1994-06-15 1995-12-19 Nitto Denko Corp 液体分離装置
JPH11114381A (ja) * 1997-10-16 1999-04-27 Nitto Denko Corp スパイラル型膜エレメント
JP2000117071A (ja) * 1998-10-16 2000-04-25 Daicen Membrane Systems Ltd 平膜エレメント
JP2001179061A (ja) * 1999-12-22 2001-07-03 Toray Ind Inc 複合半透膜およびその製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6115705A (ja) * 1984-07-02 1986-01-23 Daicel Chem Ind Ltd 半透膜補強用支持体
JPS6369503A (ja) * 1986-08-29 1988-03-29 アドバンスド・ポリマ−・テクノロジ−・インコ−ポレ−テド 高流束密度、低汚れ傾向の透過性膜
JPH06277463A (ja) * 1993-03-26 1994-10-04 Kurita Water Ind Ltd 膜分離装置
JPH07328397A (ja) * 1994-06-15 1995-12-19 Nitto Denko Corp 液体分離装置
JPH11114381A (ja) * 1997-10-16 1999-04-27 Nitto Denko Corp スパイラル型膜エレメント
JP2000117071A (ja) * 1998-10-16 2000-04-25 Daicen Membrane Systems Ltd 平膜エレメント
JP2001179061A (ja) * 1999-12-22 2001-07-03 Toray Ind Inc 複合半透膜およびその製造方法

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2578303A4 (fr) * 2010-06-03 2015-02-18 Toray Industries Élément de membrane de séparation
EP2578303A1 (fr) * 2010-06-03 2013-04-10 Toray Industries, Inc. Élément de membrane de séparation
EP2633901A1 (fr) * 2010-10-26 2013-09-04 Toray Industries, Inc. Membrane de séparation, élément de membrane de séparation et procédé de production de membrane de séparation
EP2633901A4 (fr) * 2010-10-26 2014-09-17 Toray Industries Membrane de séparation, élément de membrane de séparation et procédé de production de membrane de séparation
KR101938611B1 (ko) 2012-02-24 2019-01-15 도레이 카부시키가이샤 분리막 및 분리막 엘리먼트
WO2013125505A1 (fr) * 2012-02-24 2013-08-29 東レ株式会社 Membrane de séparation et élément de membrane de séparation
JPWO2013125505A1 (ja) * 2012-02-24 2015-07-30 東レ株式会社 分離膜および分離膜エレメント
US11376552B2 (en) 2016-09-20 2022-07-05 Aqua Membranes Inc. Permeate flow paterns
US11040311B2 (en) 2016-11-19 2021-06-22 Aqua Membranes Inc. Interference patterns for spiral wound elements
US10471391B2 (en) 2016-11-19 2019-11-12 Aqua Membranes, Inc. Flow directing devices for spiral-wound elements
CN109070019B (zh) * 2017-03-01 2021-06-08 株式会社村田制作所 过滤滤除器
CN109070019A (zh) * 2017-03-01 2018-12-21 株式会社村田制作所 过滤滤除器
US11766638B2 (en) 2017-03-20 2023-09-26 Bl Technologies, Inc. Ion-exchange membrane having an imprinted non-woven substrate
CN110691639A (zh) * 2017-03-20 2020-01-14 Bl 科技公司 具有经压印非织造基材的离子交换膜
US11135551B2 (en) 2017-03-20 2021-10-05 Bl Technologies, Inc. Ion-exchange membrane having an imprinted non-woven substrate
US11090612B2 (en) 2017-04-12 2021-08-17 Aqua Membranes Inc. Graded spacers for filtration wound elements
US11612862B2 (en) 2017-04-12 2023-03-28 Aqua Membranes Inc. Graded spacers in spiral wound elements
US11083997B2 (en) 2017-04-20 2021-08-10 Aqua Membranes Inc. Non-nesting, non-deforming patterns for spiral-wound elements
US11896933B2 (en) 2017-04-20 2024-02-13 Aqua Membranes Inc. Non-nesting, non-deforming patterns for spiral-wound elements
US11745143B2 (en) 2017-04-20 2023-09-05 Aqua Membranes, Inc. Mixing-promoting spacer patterns for spiral-wound elements
US11745144B2 (en) 2017-10-13 2023-09-05 Aqua Membranes Inc. Bridge support and reduced feed spacers for spiral-wound elements
CN108079796B (zh) * 2017-12-26 2021-07-23 北京碧水源膜科技有限公司 一种波纹膜及其制作方法和应用
CN108079796A (zh) * 2017-12-26 2018-05-29 北京碧水源膜科技有限公司 一种波纹膜及其制作方法和应用
US11633700B2 (en) 2020-04-07 2023-04-25 Aqua Membranes Inc. Independent spacers and methods
CN114558451A (zh) * 2022-02-23 2022-05-31 泰州清润环保科技有限公司 一种三维梯形凹凸结构peg脱硫膜及其制备方法
CN114558451B (zh) * 2022-02-23 2023-06-23 泰州禾益新材料科技有限公司 一种三维梯形凹凸结构peg脱硫膜及其制备方法

Also Published As

Publication number Publication date
JP2010099590A (ja) 2010-05-06

Similar Documents

Publication Publication Date Title
WO2010047360A1 (fr) Membrane semi-perméable composite de type feuille et son procédé de fabrication
JP5921344B2 (ja) 正浸透膜流動システム及び正浸透膜流動システム用複合半透膜
US20180345228A1 (en) Forward osmosis membranes
JP5798714B2 (ja) 複合半透膜及びその製造方法
JP4484635B2 (ja) スパイラル型逆浸透膜エレメント、およびその製造方法
JP5377452B2 (ja) 複合半透膜の製造方法
WO2010047383A1 (fr) Procédé de production d’une feuille poreuse en résine thermodurcissable, feuille poreuse en résine thermodurcissable, et membrane composite semi-perméable utilisant celle-ci
JP5707254B2 (ja) 熱硬化性樹脂多孔シートの製造方法
KR20160079080A (ko) 복합 반투막
WO2018049013A1 (fr) Membranes à couches sélectives alternatives
JP2012055858A (ja) 複合半透膜の製造方法
JPWO2017057378A1 (ja) 複合半透膜
JP2011083664A (ja) 複合半透膜又は膜エレメントの保存方法
JP2012011293A (ja) 複合分離膜の製造方法
JP2012005967A (ja) 多孔性支持体及びその製造方法
AU2015227384A1 (en) Forward osmosis membranes
KR20230138883A (ko) 복합 반투막 및 스파이럴형 막 엘리먼트
JP2012005968A (ja) 多孔性支持体及びその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09822057

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09822057

Country of ref document: EP

Kind code of ref document: A1