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WO2016121599A1 - Ship transport method for spiral separation membrane element - Google Patents

Ship transport method for spiral separation membrane element Download PDF

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Publication number
WO2016121599A1
WO2016121599A1 PCT/JP2016/051583 JP2016051583W WO2016121599A1 WO 2016121599 A1 WO2016121599 A1 WO 2016121599A1 JP 2016051583 W JP2016051583 W JP 2016051583W WO 2016121599 A1 WO2016121599 A1 WO 2016121599A1
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WO
WIPO (PCT)
Prior art keywords
ether
separation membrane
membrane element
skin layer
alcohol
Prior art date
Application number
PCT/JP2016/051583
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French (fr)
Japanese (ja)
Inventor
かずさ 松井
伸明 丸岡
Original Assignee
日東電工株式会社
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Publication of WO2016121599A1 publication Critical patent/WO2016121599A1/en

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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
    • B01D63/10—Spiral-wound membrane modules
    • 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
    • B01D69/107—Organic support material
    • B01D69/1071—Woven, non-woven or net mesh
    • 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
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Definitions

  • the present invention relates to a ship transportation method for a spiral separation membrane element including a composite semipermeable membrane in which a skin layer containing a polyamide-based resin is formed on the surface of a porous support.
  • a spiral separation membrane element is suitable for the production of ultrapure water, brine or desalination of seawater, etc., and is also included in dirt, which is a cause of pollution such as dye wastewater and electrodeposition paint wastewater. It can contribute to the closure of wastewater by removing and collecting pollution sources or effective substances. Moreover, it can be used for advanced treatments such as concentration of active ingredients in food applications and removal of harmful components in water purification and sewage applications. It can also be used for wastewater treatment in oil fields, shale gas fields, and the like.
  • Composite semipermeable membranes are called RO (reverse osmosis) membranes, NF (nanofiltration) membranes, and FO (forward osmosis) membranes depending on their filtration performance and treatment methods.
  • RO reverse osmosis
  • NF nanofiltration
  • FO forward osmosis
  • Patent Literature a composite semipermeable membrane in which a skin layer containing a polyamide resin obtained by interfacial polymerization of a polyfunctional amine and a polyfunctional acid halide is formed on a porous support.
  • the composite semipermeable membrane is usually processed into a spiral separation membrane element and used for water treatment or the like.
  • a supply-side flow channel material that guides the supply-side fluid to the separation membrane surface
  • a separation membrane that separates the supply-side fluid
  • a permeate-side flow that passes through the separation membrane and guides the permeation-side fluid separated from the supply-side fluid to the central tube
  • Patent Documents 2 and 3 A spiral type separation membrane element in which a unit made of road material is wound around a perforated central tube is known.
  • the manufactured spiral separation membrane element Since the manufactured spiral separation membrane element is usually transported by ship, it is exposed to a high temperature environment near the equator. In addition, when the spiral separation membrane element is exposed to a high temperature environment for a long time, there is a problem that water permeability is lowered. Therefore, when the spiral separation membrane element is transported by ship, it is necessary to transport it while refrigerated. However, in order to store the spiral separation membrane element in a refrigerated state, a refrigeration facility is required, which has a demerit that a ship having a refrigeration facility must be used. In addition, when the spiral separation membrane element is refrigerated, there is a demerit that extra labor and cost are required. Therefore, it has been desired to develop a spiral separation membrane element that does not need to be refrigerated when transported by ship and does not deteriorate water permeability even when exposed to a high temperature environment for a long time.
  • Patent Document 4 describes that a polyamide thin film is brought into contact with an aqueous solution at a temperature of 40 to 100 ° C. in order to obtain a composite reverse osmosis membrane having excellent water permeability, organic matter blocking performance and salt blocking performance. .
  • Patent Document 5 describes that the membrane is heated in water at 40 to 100 ° C. for 30 seconds to 24 hours in order to reduce salt passage.
  • the crosslinked polyamide thin film layer is subjected to a heat treatment within a range of 60 to 100 ° C. for 15 minutes or more. Is described.
  • the object of the present invention is to provide a method for transporting a spiral separation membrane element that does not require refrigeration storage of the spiral separation membrane element when the spiral separation membrane element is transported by boat.
  • the present invention relates to a ship transportation method of a spiral type separation membrane element that incorporates a composite semipermeable membrane having a skin layer containing a polyamide-based resin on a porous support.
  • the skin layer has been subjected to warm water flow treatment,
  • the skin layer has an elastic modulus calculated by a force curve measurement with an underwater AFM of 100 MPa or more,
  • the present invention relates to a ship transportation method of a spiral separation membrane element, wherein the spiral separation membrane element is transported in a storage state that is not refrigerated.
  • the spiral separation membrane element is used in the presence of water, but the physical properties of the skin layer in water, which is the actual usage environment, has not been studied so far.
  • the present inventor has studied the physical properties of the skin layer in water by adopting a new analysis method.
  • the elastic modulus calculated by the force curve measurement with an underwater AFM is 100 MPa.
  • the skin layer whose elasticity modulus computed by the force curve measurement by underwater AFM is 100 Mpa or more is obtained by performing warm water flow treatment to a skin layer.
  • the reason why the elastic modulus of the skin layer in the force curve measurement with the underwater AFM becomes 100 MPa or more by performing the warm water flow treatment on the skin layer is not clear, but the crosslinked structure of the polyamide-based resin by the warm water flow treatment This is thought to be due to shrinkage and regular arrangement.
  • the spiral separation membrane element containing the composite semipermeable membrane having the skin layer whose elastic modulus calculated by the force curve measurement with the underwater AFM is 100 MPa or more is exposed to a high temperature environment for a long time.
  • the spiral separation membrane element since the water permeability is not easily lowered, when the spiral separation membrane element is transported by ship, the spiral separation membrane element does not need to be refrigerated, and is transported in an unrefrigerated storage state. be able to.
  • the warm water flow treatment is preferably performed for 1 to 5 hours using warm water of 40 to 60 ° C.
  • the elastic modulus of the skin layer tends not to be 100 MPa or more.
  • the temperature of the hot water exceeds 60 ° C.
  • the water permeability of the spiral separation membrane element There is a tendency for the properties to be greatly reduced.
  • the treatment time is less than 1 hour
  • the elastic modulus of the skin layer tends not to be 100 MPa or more.
  • even if the treatment time exceeds 5 hours the effect is not affected. It is disadvantageous.
  • the skin layer is formed by bringing an amine solution containing a polyfunctional amine component into contact with an organic solution containing a polyfunctional acid halide component on a porous support and interfacially polymerizing the ethanol, propanol, Butanol, butyl alcohol, 1-pentanol, 2-pentanol, t-amyl alcohol, isoamyl alcohol, isobutyl alcohol, isopropyl alcohol, undecanol, 2-ethylbutanol, 2-ethylhexanol, octanol, cyclohexanol, tetrahydrofurfuryl alcohol , T-butanol, benzyl alcohol, 4-methyl-2-pentanol, 3-methyl-2-butanol, pentyl alcohol, allyl alcohol, anisole, ethyl isoamyl ether, ethyl-t-butyl ether , Ethyl benzyl ether
  • the water permeability of the spiral separation membrane element is reduced by about 10 to 20% due to heat. Therefore, the initial water permeability of the spiral separation membrane element is improved by forming the skin layer in the presence of a substance having a solubility parameter of 8 to 14 (cal / cm 3 ) 1/2 , and thereby the skin layer It is preferable to compensate for a decrease in the water permeability of the spiral separation membrane element that occurs by performing a hot water flow treatment.
  • the ship transportation method of the spiral separation membrane element of the present invention it is not necessary to refrigerate and store the spiral separation membrane element when transporting by ship, so that the labor and cost for ship transportation can be reduced.
  • the spiral separation membrane element of the present invention incorporates a composite semipermeable membrane having a skin layer containing a polyamide resin on a porous support.
  • the polyamide resin is obtained by reacting a polyfunctional amine component and a polyfunctional acid halide component.
  • 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.
  • piperazine, 2,5-dimethylpiperazine, or 4-aminomethylpiperazine is preferably used, and piperazine is more preferably used from the viewpoint of reactivity with the polyfunctional acid halide component.
  • the polyfunctional acid halide component is a polyfunctional acid halide having two or more reactive carbonyl groups.
  • polyfunctional acid halides include aromatic, aliphatic and alicyclic polyfunctional acid halides.
  • aromatic polyfunctional acid halides include trimesic acid trichloride, terephthalic acid dichloride, isophthalic acid dichloride, biphenyl dicarboxylic acid dichloride, naphthalene dicarboxylic acid dichloride, benzene trisulfonic acid trichloride, benzene disulfonic acid dichloride, and 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 cyclopropane tricarboxylic acid trichloride, cyclobutane tetracarboxylic acid tetrachloride, cyclopentane tricarboxylic acid trichloride, cyclopentane tetracarboxylic acid tetrachloride, cyclohexane tricarboxylic 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.
  • trimesic acid trichloride is preferably used.
  • a polymer such as polyvinyl alcohol, polyvinyl pyrrolidone or polyacrylic acid, a polyhydric alcohol such as sorbitol or glycerin may be copolymerized.
  • the porous support for supporting the skin layer is not particularly limited as long as it can support the skin layer, and usually an ultrafiltration membrane having micropores with an average pore diameter of about 10 to 500 mm is preferably used.
  • the material for forming the porous support include polysulfone, polyarylethersulfone such as polyethersulfone, polyimide, polyvinylidene fluoride, and the like. Polysulfone and polyarylethersulfone are preferably used from the viewpoint of stability.
  • the thickness of such a porous support is usually about 25 to 125 ⁇ m, preferably about 40 to 75 ⁇ m, but is not necessarily limited thereto.
  • the porous support is reinforced by backing with a base material such as a woven fabric or a non-woven fabric.
  • the method for forming the skin layer containing the polyamide-based resin on the surface of the porous support is not particularly limited, and any known method can be used.
  • an interfacial condensation method is a method in which a skin layer is formed by bringing an amine solution containing a polyfunctional amine component into contact with an organic solution containing a polyfunctional acid halide component to cause interfacial polymerization.
  • a polyamide resin skin layer is directly formed on a porous support by interfacial polymerization on the porous support. Details of the conditions of the interfacial condensation method are described in JP-A-58-24303 and JP-A-1-180208, and those known techniques can be appropriately employed.
  • a method of forming a skin layer by bringing an amine solution containing a polyfunctional amine component and an organic solution containing a polyfunctional acid halide component into contact with each other on a porous support to cause interfacial polymerization is preferable.
  • the concentration of the polyfunctional amine component in the amine solution is not particularly limited, but is preferably 0.1 to 5% by weight, and more preferably 0.5 to 4% 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 skin layer, and the salt blocking performance tends to decrease.
  • concentration of the polyfunctional amine component exceeds 5% by weight, the polyfunctional amine component is likely to penetrate into the porous support, or the film thickness becomes too thick to increase the permeation resistance and increase the permeation flow. The bundle 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. If the concentration of the polyfunctional acid halide component is less than 0.01% by weight, the unreacted polyfunctional amine component tends to remain, or defects such as pinholes are likely to occur in the skin layer, resulting in a decrease in salt blocking performance. Tend to. On the other hand, when the 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.
  • Examples of the solvent for the amine solution include water, alcohol (for example, ethanol, isopropyl alcohol, ethylene glycol, and the like), and a mixed solvent of water and alcohol.
  • the solvent of the organic solution is not particularly limited as long as it has low solubility in water, does not degrade the porous support, and dissolves the polyfunctional acid halide component.
  • saturated hydrocarbons such as 1,2-halogenated hydrocarbons such as 1,1,2-trichlorotrifluoroethane.
  • a saturated hydrocarbon or naphthenic solvent having a boiling point of 300 ° C. or lower, more preferably 200 ° C. or lower is preferable.
  • the organic solvent may be used alone or as a mixed solvent of two or more.
  • the amine solution and the organic solution are preferably contacted in the presence of a substance having a solubility parameter of 8 to 14 (cal / cm 3 ) 1/2 .
  • the solubility parameter is the amount defined by ( ⁇ H / V) 1/2 (cal / cm 3 ) 1/2 when the heat of vaporization of the liquid is ⁇ Hcal / mol and the molar volume is Vcm 3 / mol.
  • Examples of the substance having a solubility parameter of 8 to 14 (cal / cm 3 ) 1/2 include alcohols, ethers, ketones, esters, halogenated hydrocarbons, and sulfur-containing compounds.
  • alcohols examples include ethanol, propanol, butanol, butyl alcohol, 1-pentanol, 2-pentanol, t-amyl alcohol, isoamyl alcohol, isobutyl alcohol, isopropyl alcohol, undecanol, 2-ethylbutanol, and 2-ethyl.
  • ethers examples include anisole, ethyl isoamyl ether, ethyl-t-butyl ether, ethyl benzyl ether, crown ether, cresyl methyl ether, diisoamyl ether, diisopropyl ether, diethyl ether, dioxane, diglycidyl ether, cineol, diphenyl ether.
  • ketones include ethyl butyyl ketone, diacetone alcohol, diisobutyl ketone, cyclohexanone, 2-heptanone, methyl isobutyl ketone, methyl ethyl ketone, and methylcyclohexane.
  • esters examples include methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, isoamyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, and amyl acetate.
  • halogenated hydrocarbons examples include allyl chloride, amyl chloride, dichloromethane, dichloroethane and the like.
  • sulfur-containing compounds include dimethyl sulfoxide, sulfolane, thiolane and the like.
  • alcohols and ethers are particularly preferable. These may be used alone or in combination of two or more.
  • a substance having a solubility parameter of 8 to 14 (cal / cm 3 ) 1/2 may be added to an amine solution, an organic solution, or both solutions. Further, the porous support may be impregnated with the substance in advance. Moreover, you may make an amine solution and an organic solution contact on a porous support body in the gas atmosphere of the said substance.
  • the addition amount is preferably 10 to 50% by weight. If it is less than 10% by weight, the effect of increasing the permeation flux is insufficient, and if it exceeds 50% by weight, the rejection rate tends to decrease.
  • the addition amount is preferably 0.001 to 10% by weight. If it is less than 0.001% by weight, the effect of increasing the permeation flux is insufficient, and if it exceeds 10% by weight, the rejection rate tends to decrease.
  • additives can be added to the amine solution or the organic solution for the purpose of facilitating film formation or improving the performance of the resulting composite semipermeable membrane.
  • the additive include surfactants such as sodium dodecylbenzenesulfonate, sodium dodecylsulfate, and sodium laurylsulfate, sodium hydroxide that removes hydrogen halide generated by polymerization, trisodium phosphate, and triethylamine. And basic compounds, acylation catalysts, and the like.
  • the time from application of the amine solution on the porous support to application of the organic solution depends on the composition of the amine solution, the viscosity, and the pore size of the surface layer of the porous support, but is 15 seconds or less. It is preferable that it is 5 seconds or less. If the application interval of the solution exceeds 15 seconds, the amine solution may penetrate and diffuse deep inside the porous support, and a large amount of unreacted polyfunctional amine component may remain in the porous support. . Further, the unreacted polyfunctional amine component that has penetrated deep inside the porous support tends to be difficult to remove even in the subsequent membrane cleaning treatment. In addition, you may remove an excess amine solution after coat
  • 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 skin layer formed on the porous support is not particularly limited, but is usually about 0.05 to 2 ⁇ m, preferably 0.1 to 1 ⁇ m.
  • the skin layer is subjected to warm water flow treatment.
  • the temperature of the hot water used for the hot water flow treatment is not particularly limited, but is usually about 40 to 65 ° C., preferably 40 to 60.
  • the time for the hot water flow treatment is not particularly limited, but is preferably 1 to 5 hours, and more preferably 3 to 5 hours.
  • the hot water flow treatment may be performed on a membrane-shaped composite semipermeable membrane, or may be performed on a spiral separation membrane element obtained by processing the composite semipermeable membrane into a spiral shape.
  • Spiral separation membrane elements for example, stack a supply-side channel material with a composite semipermeable membrane folded in two and a permeate-side channel material to mix the supply-side fluid and permeate-side fluid.
  • a separation membrane unit is manufactured by applying an adhesive for forming a sealing portion to be prevented to the periphery (three sides) of the composite semipermeable membrane, and one or more separation membrane units are spirally formed around the central tube. And is further manufactured by sealing the periphery of the separation membrane unit.
  • the skin layer obtained by the above manufacturing method has an elastic modulus of 100 MPa or more calculated by a force curve measurement with an underwater AFM.
  • the elastic modulus is preferably 110 MPa or more, more preferably 130 MPa or more, and further preferably 150 MPa or more.
  • the calculation of the elastic modulus of the skin layer by the force curve measurement with the underwater AFM is performed by the method described in the examples.
  • the sample 1 is moved in the vertical direction, the spherical probe 6 is pushed into the skin layer of the sample 1 while applying a load, and the deflection or warpage (displacement) of the cantilever 7 at the time of separation is defined as the displacement of the laser beam 8.
  • the force curve was measured by detecting with a photodiode, and converted to load and skin layer deformation using the program attached to the device. A region having a measurement area of 90 ⁇ m ⁇ 90 ⁇ m was divided into 20 ⁇ 20, and a force curve was measured at a total of 400 points. And the average value of the deformation amount of the skin layer when the load was 3 ⁇ N was obtained.
  • the measurement apparatus and measurement conditions are as follows.
  • Measurement device MFP-3D (manufactured by Asylum Technology)
  • Cantilever Spring constant 40N / m -Spherical probe: manufactured by Nanosensors, radius of curvature of the tip 0.4 ⁇ m, Silicon (100), Poisson's ratio 0.17, elastic modulus 150 GPa
  • Measurement environment Ultra pure water
  • the elastic modulus E sample (MPa) of the skin layer is obtained by substituting each numerical value into the following Hertz elastic contact theoretical formula.
  • Comparative Example 1 An amine solution was prepared by dissolving 3.6% by weight of piperazine heptahydrate, 0.15% by weight of sodium lauryl sulfate, 6% by weight of camphorsulfonic acid, and 1.48% by weight of sodium hydroxide in water. And after making an amine solution contact the surface of a porous support body, the excess amine solution was removed. Thereafter, the amine solution on the surface of the porous support was brought into contact with an organic solution in which 0.42% by weight of trimesic acid chloride and 0.5% by weight of t-butanol were dissolved in IP1016 (boiling point 106 ° C.). Then, the excess organic solution was removed, and it hold
  • Example 1 The composite semipermeable membrane produced in Comparative Example 1 was passed through 40 ° C. warm water for 5 hours, and the skin layer was subjected to warm water passing treatment.
  • Example 2 The composite semipermeable membrane produced in Comparative Example 1 was passed through warm water at 50 ° C. for 5 hours, and the skin layer was subjected to warm water passing treatment.
  • Example 3 The composite semipermeable membrane produced in Comparative Example 1 was allowed to pass hot water at 60 ° C. for 5 hours, and the skin layer was subjected to hot water flow treatment.
  • Example 4 A spiral separation membrane element was produced using the composite semipermeable membrane produced in Comparative Example 1. Hot water at 60 ° C. was passed through the produced spiral separation membrane element for 3 hours, and the skin layer was subjected to hot water passage treatment. In the measurement of the elastic modulus and permeation flux, the composite semipermeable membrane was taken out from the element and measured.
  • the spiral separation membrane element of the present invention is suitable for the production of ultrapure water, desalination of brackish water or seawater, etc., and from contamination that causes pollution such as dyeing waste water and electrodeposition paint waste water. It can contribute to the closure of wastewater by removing and recovering contained pollution sources or effective substances. Moreover, it can be used for advanced treatments such as concentration of active ingredients in food applications and removal of harmful components in water purification and sewage applications. It can also be used for wastewater treatment in oil fields, shale gas fields, and the like.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Laminated Bodies (AREA)
  • Polyamides (AREA)

Abstract

The purpose of the present invention is to provide a ship transport method for a spiral separation membrane element that does not require refrigerated storage of the spiral separation membrane element when transporting the spiral separation membrane element by ship. The present invention relates to a ship transport method for a spiral separation membrane element that incorporates a composite semipermeable membrane having a skin layer that contains a polyamide resin on a porous support body and is characterized by the skin layer undergoing hot water pass-through processing, by the skin layer having a modulus of elasticity of 100 MPa calculated by force curve measurements by AFM in water, and by the spiral separation membrane element being transported in a storage state without refrigeration.

Description

スパイラル型分離膜エレメントの船輸送方法Shipment method of spiral separation membrane element
　本発明は、ポリアミド系樹脂を含むスキン層が多孔性支持体の表面に形成されている複合半透膜を内蔵するスパイラル型分離膜エレメントの船輸送方法に関する。かかるスパイラル型分離膜エレメントは、超純水の製造、かん水または海水の脱塩などに好適であり、また染色排水や電着塗料排水などの公害発生原因である汚れなどから、その中に含まれる汚染源あるいは有効物質を除去・回収し、排水のクローズ化に寄与することができる。また、食品用途などで有効成分の濃縮、浄水や下水用途等での有害成分の除去などの高度処理に用いることができる。また、油田やシェールガス田などにおける排水処理に用いることができる。 The present invention relates to a ship transportation method for a spiral separation membrane element including a composite semipermeable membrane in which a skin layer containing a polyamide-based resin is formed on the surface of a porous support. Such a spiral separation membrane element is suitable for the production of ultrapure water, brine or desalination of seawater, etc., and is also included in dirt, which is a cause of pollution such as dye wastewater and electrodeposition paint wastewater. It can contribute to the closure of wastewater by removing and collecting pollution sources or effective substances. Moreover, it can be used for advanced treatments such as concentration of active ingredients in food applications and removal of harmful components in water purification and sewage applications. It can also be used for wastewater treatment in oil fields, shale gas fields, and the like.
　複合半透膜はその濾過性能や処理方法に応じてＲＯ（逆浸透）膜、ＮＦ（ナノ濾過）膜、ＦＯ（正浸透）膜と呼ばれ、超純水製造、海水淡水化、かん水の脱塩処理、排水の再利用処理などに用いることができる。 Composite semipermeable membranes are called RO (reverse osmosis) membranes, NF (nanofiltration) membranes, and FO (forward osmosis) membranes depending on their filtration performance and treatment methods. Ultrapure water production, seawater desalination, dewatering of brine It can be used for salt treatment, wastewater reuse treatment, and the like.
　現在、複合半透膜としては、多官能アミンと多官能酸ハロゲン化物との界面重合によって得られるポリアミド樹脂を含むスキン層が多孔性支持体上に形成されたものが提案されている（特許文献１）。 Currently, a composite semipermeable membrane has been proposed in which a skin layer containing a polyamide resin obtained by interfacial polymerization of a polyfunctional amine and a polyfunctional acid halide is formed on a porous support (Patent Literature). 1).
　複合半透膜は、通常、スパイラル型分離膜エレメントに加工して水処理等に用いられている。例えば、供給側流体を分離膜表面へ導く供給側流路材、供給側流体を分離する分離膜、分離膜を透過し供給側流体から分離された透過側流体を中心管へと導く透過側流路材からなるユニットを有孔の中心管の周りに巻き付けたスパイラル型分離膜エレメントが知られている（特許文献２、３）。 The composite semipermeable membrane is usually processed into a spiral separation membrane element and used for water treatment or the like. For example, a supply-side flow channel material that guides the supply-side fluid to the separation membrane surface, a separation membrane that separates the supply-side fluid, and a permeate-side flow that passes through the separation membrane and guides the permeation-side fluid separated from the supply-side fluid to the central tube A spiral type separation membrane element in which a unit made of road material is wound around a perforated central tube is known (Patent Documents 2 and 3).
　製造したスパイラル型分離膜エレメントは、通常、船で輸送するため、赤道付近では高温環境下に曝されることになる。そして、スパイラル型分離膜エレメントが高温環境下に長期間曝されると水透過性が低下するという問題があった。そのため、スパイラル型分離膜エレメントを船で輸送する場合には、冷蔵保管しながら輸送する必要があった。しかし、スパイラル型分離膜エレメントを冷蔵保管するためには冷蔵設備が必要になるため、冷蔵設備を有する船を用いなければならないというデメリットがあった。また、スパイラル型分離膜エレメントを冷蔵保管すると手間やコストが余計にかかるというデメリットがあった。そのため、船で輸送する際に冷蔵保管する必要がなく、高温環境下に長期間曝された場合でも水透過性が低下することのないスパイラル型分離膜エレメントの開発が望まれていた。 Since the manufactured spiral separation membrane element is usually transported by ship, it is exposed to a high temperature environment near the equator. In addition, when the spiral separation membrane element is exposed to a high temperature environment for a long time, there is a problem that water permeability is lowered. Therefore, when the spiral separation membrane element is transported by ship, it is necessary to transport it while refrigerated. However, in order to store the spiral separation membrane element in a refrigerated state, a refrigeration facility is required, which has a demerit that a ship having a refrigeration facility must be used. In addition, when the spiral separation membrane element is refrigerated, there is a demerit that extra labor and cost are required. Therefore, it has been desired to develop a spiral separation membrane element that does not need to be refrigerated when transported by ship and does not deteriorate water permeability even when exposed to a high temperature environment for a long time.
　一方、特許文献４では、水透過性、有機物阻止性能および塩阻止性能に優れた複合逆浸透膜を得るために、ポリアミド製薄膜を温度４０～１００℃の水溶液に接触させることが記載されている。 On the other hand, Patent Document 4 describes that a polyamide thin film is brought into contact with an aqueous solution at a temperature of 40 to 100 ° C. in order to obtain a composite reverse osmosis membrane having excellent water permeability, organic matter blocking performance and salt blocking performance. .
　また、特許文献５では、塩通過を低くするために、膜を水中にて４０～１００℃にて３０秒～２４時間加熱することが記載されている。 Patent Document 5 describes that the membrane is heated in water at 40 to 100 ° C. for 30 seconds to 24 hours in order to reduce salt passage.
　また、特許文献６では、高温安定性と高いイオン分離性能を併せ有する複合半透膜を得るために、架橋ポリアミドの薄膜層に対して６０～１００℃の範囲内でかつ１５分以上の加熱処理を施すことが記載されている。 Further, in Patent Document 6, in order to obtain a composite semipermeable membrane having both high-temperature stability and high ion separation performance, the crosslinked polyamide thin film layer is subjected to a heat treatment within a range of 60 to 100 ° C. for 15 minutes or more. Is described.
特開２００５－１０３５１７号公報JP 2005-103517 A 特開２０００－３５４７４３号公報JP 2000-354743 A 特開２００６－６８６４４号公報JP 2006-68644 A 特開平１０－１６５７９０号公報Japanese Patent Laid-Open No. 10-165790 特表２００１－５２１８０８号公報JP 2001-521808 A 特開２００５－１４４２１１号公報JP-A-2005-144221
　本発明は、スパイラル型分離膜エレメントを船で輸送する際に、スパイラル型分離膜エレメントを冷蔵保管する必要がないスパイラル型分離膜エレメントの船輸送方法を提供することを目的とする。 The object of the present invention is to provide a method for transporting a spiral separation membrane element that does not require refrigeration storage of the spiral separation membrane element when the spiral separation membrane element is transported by boat.
　本発明者らは、前記課題を解決すべく鋭意検討を重ねた結果、以下に示す船輸送方法により上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by the ship transportation method described below, and have completed the present invention.
　すなわち、本発明は、多孔性支持体上にポリアミド系樹脂を含むスキン層を有する複合半透膜を内蔵するスパイラル型分離膜エレメントの船輸送方法において、
　前記スキン層は、温水通水処理が施されており、
　前記スキン層は、水中ＡＦＭでのフォースカーブ測定により算出される弾性率が１００ＭＰａ以上であり、
　前記スパイラル型分離膜エレメントを、冷蔵していない保管状態で輸送することを特徴とするスパイラル型分離膜エレメントの船輸送方法、に関する。 That is, the present invention relates to a ship transportation method of a spiral type separation membrane element that incorporates a composite semipermeable membrane having a skin layer containing a polyamide-based resin on a porous support.
The skin layer has been subjected to warm water flow treatment,
The skin layer has an elastic modulus calculated by a force curve measurement with an underwater AFM of 100 MPa or more,
The present invention relates to a ship transportation method of a spiral separation membrane element, wherein the spiral separation membrane element is transported in a storage state that is not refrigerated.
　スパイラル型分離膜エレメントは水の存在下で使用されるが、これまで実際の使用環境である水中でのスキン層の物性は検討されていなかった。本発明者は、新たな分析手法を採用して、水中でのスキン層の物性を検討したところ、意外にも、水中ＡＦＭ（Atomic Force Microscope）でのフォースカーブ測定により算出される弾性率が１００ＭＰａ以上であるスキン層を用いた場合には、高温環境下（４０℃以上）に長期間（３００日以上）曝された場合であっても水透過性が低下しにくいスパイラル型分離膜エレメントが得られることを見出した。空気中でスキン層の弾性率を測定した場合には、水透過性の低下とスキン層の弾性率の相関関係ははっきりしなかったが、水中ＡＦＭでのフォースカーブ測定による新たな分析手法を採用することにより、水透過性の低下とスキン層の弾性率の相関関係が明確になった。 The spiral separation membrane element is used in the presence of water, but the physical properties of the skin layer in water, which is the actual usage environment, has not been studied so far. The present inventor has studied the physical properties of the skin layer in water by adopting a new analysis method. Surprisingly, the elastic modulus calculated by the force curve measurement with an underwater AFM (Atomic Force Microscope) is 100 MPa. When the skin layer as described above is used, a spiral separation membrane element is obtained in which water permeability is unlikely to deteriorate even when exposed to a high temperature environment (40 ° C. or higher) for a long period (300 days or longer). I found out that When the elastic modulus of the skin layer was measured in the air, the correlation between the decrease in water permeability and the elastic modulus of the skin layer was not clear, but a new analysis method using force curve measurement with an underwater AFM was adopted. As a result, the correlation between the decrease in water permeability and the elastic modulus of the skin layer became clear.
　そして、本発明者は、スキン層に温水通水処理を施すことにより、水中ＡＦＭでのフォースカーブ測定により算出される弾性率が１００ＭＰａ以上であるスキン層が得られることを見出した。なお、スキン層に温水通水処理を施すことにより、水中ＡＦＭでのフォースカーブ測定におけるスキン層の弾性率が１００ＭＰａ以上になる理由は明らかではないが、温水通水処理によりポリアミド系樹脂の架橋構造が収縮して規則正しく配列するためと考えられる。 And this inventor discovered that the skin layer whose elasticity modulus computed by the force curve measurement by underwater AFM is 100 Mpa or more is obtained by performing warm water flow treatment to a skin layer. The reason why the elastic modulus of the skin layer in the force curve measurement with the underwater AFM becomes 100 MPa or more by performing the warm water flow treatment on the skin layer is not clear, but the crosslinked structure of the polyamide-based resin by the warm water flow treatment This is thought to be due to shrinkage and regular arrangement.
　上記の通り、水中ＡＦＭでのフォースカーブ測定により算出される弾性率が１００ＭＰａ以上であるスキン層を有する複合半透膜を内蔵するスパイラル型分離膜エレメントは、高温環境下に長期間曝された場合であっても水透過性が低下しにくいため、当該スパイラル型分離膜エレメントを船で輸送する際に、当該スパイラル型分離膜エレメントを冷蔵保管する必要はなく、冷蔵していない保管状態で輸送することができる。 As described above, the spiral separation membrane element containing the composite semipermeable membrane having the skin layer whose elastic modulus calculated by the force curve measurement with the underwater AFM is 100 MPa or more is exposed to a high temperature environment for a long time. However, since the water permeability is not easily lowered, when the spiral separation membrane element is transported by ship, the spiral separation membrane element does not need to be refrigerated, and is transported in an unrefrigerated storage state. be able to.
　前記温水通水処理は、４０～６０℃の温水を用いて１～５時間行うことが好ましい。温水の温度が４０℃未満の場合には、スキン層の弾性率が１００ＭＰａ以上になり難くなる傾向にあり、一方、温水の温度が６０℃を超える場合には、スパイラル型分離膜エレメントの水透過性が大きく低下しやすくなる傾向にある。また、処理時間が１時間未満の場合には、スキン層の弾性率が１００ＭＰａ以上になり難くなる傾向にあり、一方、処理時間が５時間を超えても効果に影響しないため、製造効率の面で不利である。 The warm water flow treatment is preferably performed for 1 to 5 hours using warm water of 40 to 60 ° C. When the temperature of the hot water is less than 40 ° C., the elastic modulus of the skin layer tends not to be 100 MPa or more. On the other hand, when the temperature of the hot water exceeds 60 ° C., the water permeability of the spiral separation membrane element There is a tendency for the properties to be greatly reduced. Further, when the treatment time is less than 1 hour, the elastic modulus of the skin layer tends not to be 100 MPa or more. On the other hand, even if the treatment time exceeds 5 hours, the effect is not affected. It is disadvantageous.
　前記スキン層は、多官能アミン成分を含むアミン溶液と多官能酸ハライド成分を含む有機溶液とを多孔性支持体上で接触させて界面重合させることにより形成され、前記接触は、エタノール、プロパノール、ブタノール、ブチルアルコール、１－ペンタノール、２－ペンタノール、ｔ－アミルアルコール、イソアミルアルコール、イソブチルアルコール、イソプロピルアルコール、ウンデカノール、２－エチルブタノール、２－エチルヘキサノール、オクタノール、シクロヘキサノール、テトラヒドロフルフリルアルコール、ｔ－ブタノール、ベンジルアルコール、４－メチル－２－ペンタノール、３－メチル－２－ブタノール、ペンチルアルコール、アリルアルコール、アニソール、エチルイソアミルエーテル、エチル－ｔ－ブチルエーテル、エチルベンジルエーテル、クラウンエーテル、クレジルメチルエーテル、ジイソアミルエーテル、ジイソプロピルエーテル、ジグリシジルエーテル、シネオール、ジフェニルエーテル、ジブチルエーテル、ジプロピルエーテル、ジベンジルエーテル、ジメチルエーテル、テトラヒドロピラン、トリオキサン、ジクロロエチルエーテル、ブチルフェニルエーテル、フラン、モノジクロロジエチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジブチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレンクロロヒドリンから選ばれる少なくとも一つの溶解度パラメーターが８～１４（cal／cm3)1/2の物質の存在下で行われることが好ましい。 The skin layer is formed by bringing an amine solution containing a polyfunctional amine component into contact with an organic solution containing a polyfunctional acid halide component on a porous support and interfacially polymerizing the ethanol, propanol, Butanol, butyl alcohol, 1-pentanol, 2-pentanol, t-amyl alcohol, isoamyl alcohol, isobutyl alcohol, isopropyl alcohol, undecanol, 2-ethylbutanol, 2-ethylhexanol, octanol, cyclohexanol, tetrahydrofurfuryl alcohol , T-butanol, benzyl alcohol, 4-methyl-2-pentanol, 3-methyl-2-butanol, pentyl alcohol, allyl alcohol, anisole, ethyl isoamyl ether, ethyl-t-butyl ether , Ethyl benzyl ether, crown ether, cresyl methyl ether, diisoamyl ether, diisopropyl ether, diglycidyl ether, cineol, diphenyl ether, dibutyl ether, dipropyl ether, dibenzyl ether, dimethyl ether, tetrahydropyran, trioxane, dichloroethyl ether, Butyl phenyl ether, furan, monodichlorodiethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, di Chi glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, lines in the presence of diethylene glycol monobutyl ether, at least one solubility parameter selected from diethylene chlorohydrin is 8 ~ 14 (cal / cm 3 ) 1/2 of a substance Are preferred.
　スキン層に温水通水処理を施すと熱によってスパイラル型分離膜エレメントの水透過性が１０～２０％程度低下する。そのため、溶解度パラメーターが８～１４（cal／cm3)1/2の物質の存在下でスキン層を形成することによってスパイラル型分離膜エレメントの初期の水透過性を向上させ、それにより、スキン層に温水通水処理を施すことによって起こるスパイラル型分離膜エレメントの水透過性の低下を補うことが好ましい。 When the skin layer is subjected to warm water flow treatment, the water permeability of the spiral separation membrane element is reduced by about 10 to 20% due to heat. Therefore, the initial water permeability of the spiral separation membrane element is improved by forming the skin layer in the presence of a substance having a solubility parameter of 8 to 14 (cal / cm 3 ) 1/2 , and thereby the skin layer It is preferable to compensate for a decrease in the water permeability of the spiral separation membrane element that occurs by performing a hot water flow treatment.
　本発明のスパイラル型分離膜エレメントの船輸送方法によれば、船で輸送する際にスパイラル型分離膜エレメントを冷蔵保管する必要がないため、船輸送にかかる手間やコストを削減することができる。 According to the ship transportation method of the spiral separation membrane element of the present invention, it is not necessary to refrigerate and store the spiral separation membrane element when transporting by ship, so that the labor and cost for ship transportation can be reduced.
サンプルの固定方法を示す概略構成図Schematic configuration diagram showing sample fixing method
　以下、本発明の実施の形態について説明する。本発明のスパイラル型分離膜エレメントは、多孔性支持体上にポリアミド系樹脂を含むスキン層を有する複合半透膜を内蔵している。 Hereinafter, embodiments of the present invention will be described. The spiral separation membrane element of the present invention incorporates a composite semipermeable membrane having a skin layer containing a polyamide resin on a porous support.
　ポリアミド系樹脂は、多官能アミン成分と多官能酸ハライド成分とを反応させることにより得られる。 The polyamide resin is obtained by reacting a polyfunctional amine component and a polyfunctional acid halide component.
　多官能アミン成分とは、２以上の反応性アミノ基を有する多官能アミンであり、芳香族、脂肪族及び脂環式の多官能アミンが挙げられる。 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.
　芳香族多官能アミンとしては、例えば、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、ｏ－フェニレンジアミン、１，３，５－トリアミノベンゼン、１，２，４－トリアミノベンゼン、３，５－ジアミノ安息香酸、２，４－ジアミノトルエン、２，６－ジアミノトルエン、Ｎ，Ｎ’－ジメチル－ｍ－フェニレンジアミン、２，４－ジアミノアニソール、アミドール、キシリレンジアミン等が挙げられる。 Examples of 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.
　脂肪族多官能アミンとしては、例えば、エチレンジアミン、プロピレンジアミン、トリス（２－アミノエチル）アミン、ｎ－フェニル－エチレンジアミン等が挙げられる。 Examples of the aliphatic polyfunctional amine include ethylenediamine, propylenediamine, tris (2-aminoethyl) amine, and n-phenyl-ethylenediamine.
　脂環式多官能アミンとしては、例えば、１，３－ジアミノシクロヘキサン、１，２－ジアミノシクロヘキサン、１，４－ジアミノシクロヘキサン、ピペラジン、２，５－ジメチルピペラジン、４－アミノメチルピペラジン等が挙げられる。 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. .
　これらの多官能アミンは１種で用いてもよく、２種以上を併用してもよい。これらのうち、多官能酸ハライド成分との反応性の観点からピペラジン、２，５－ジメチルピペラジン、又は４－アミノメチルピペラジンを用いることが好ましく、ピペラジンを用いることがより好ましい。 These polyfunctional amines may be used alone or in combination of two or more. Of these, piperazine, 2,5-dimethylpiperazine, or 4-aminomethylpiperazine is preferably used, and piperazine is more preferably used from the viewpoint of reactivity with the polyfunctional acid halide component.
　多官能酸ハライド成分とは、反応性カルボニル基を２個以上有する多官能酸ハライドである。 The polyfunctional acid halide component is a polyfunctional acid halide having two or more reactive carbonyl groups.
　多官能酸ハライドとしては、芳香族、脂肪族及び脂環式の多官能酸ハライドが挙げられる。 Examples of polyfunctional acid halides include aromatic, aliphatic and alicyclic polyfunctional acid halides.
　芳香族多官能酸ハライドとしては、例えば、トリメシン酸トリクロライド、テレフタル酸ジクロライド、イソフタル酸ジクロライド、ビフェニルジカルボン酸ジクロライド、ナフタレンジカルボン酸ジクロライド、ベンゼントリスルホン酸トリクロライド、ベンゼンジスルホン酸ジクロライド、クロロスルホニルベンゼンジカルボン酸ジクロライド等が挙げられる。 Examples of aromatic polyfunctional acid halides include trimesic acid trichloride, terephthalic acid dichloride, isophthalic acid dichloride, biphenyl dicarboxylic acid dichloride, naphthalene dicarboxylic acid dichloride, benzene trisulfonic acid trichloride, benzene disulfonic acid dichloride, and chlorosulfonylbenzene dicarboxylic acid. An acid dichloride etc. are mentioned.
　脂肪族多官能酸ハライドとしては、例えば、プロパンジカルボン酸ジクロライド、ブタンジカルボン酸ジクロライド、ペンタンジカルボン酸ジクロライド、プロパントリカルボン酸トリクロライド、ブタントリカルボン酸トリクロライド、ペンタントリカルボン酸トリクロライド、グルタリルハライド、アジポイルハライド等が挙げられる。 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.
　脂環式多官能酸ハライドとしては、例えば、シクロプロパントリカルボン酸トリクロライド、シクロブタンテトラカルボン酸テトラクロライド、シクロペンタントリカルボン酸トリクロライド、シクロペンタンテトラカルボン酸テトラクロライド、シクロヘキサントリカルボン酸トリクロライド、テトラハイドロフランテトラカルボン酸テトラクロライド、シクロペンタンジカルボン酸ジクロライド、シクロブタンジカルボン酸ジクロライド、シクロヘキサンジカルボン酸ジクロライド、テトラハイドロフランジカルボン酸ジクロライド等が挙げられる。 Examples of the alicyclic polyfunctional acid halide include cyclopropane tricarboxylic acid trichloride, cyclobutane tetracarboxylic acid tetrachloride, cyclopentane tricarboxylic acid trichloride, cyclopentane tetracarboxylic acid tetrachloride, cyclohexane tricarboxylic 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.
　これら多官能酸ハライドは１種で用いてもよく、２種以上を併用してもよい。高塩阻止性能のスキン層を得るためには、芳香族多官能酸ハライドを用いることが好ましい。また、多官能酸ハライド成分の少なくとも一部に３価以上の多官能酸ハライドを用いて、架橋構造を形成するのが好ましい。特に、トリメシン酸トリクロライドを用いることが好ましい。 These polyfunctional acid halides may be used alone or in combination of two or more. In order to obtain a skin layer having a high salt inhibition performance, it is preferable to use an aromatic polyfunctional acid halide. Moreover, it is preferable to form a crosslinked structure by using a trifunctional or higher polyfunctional acid halide as at least a part of the polyfunctional acid halide component. In particular, trimesic acid trichloride is preferably used.
　また、ポリアミド系樹脂を含むスキン層の性能を向上させるために、ポリビニルアルコール、ポリビニルピロリドン、ポリアクリル酸などのポリマー、ソルビトール、グリセリンなどの多価アルコールなどを共重合させてもよい。 Further, in order to improve the performance of the skin layer containing a polyamide-based resin, a polymer such as polyvinyl alcohol, polyvinyl pyrrolidone or polyacrylic acid, a polyhydric alcohol such as sorbitol or glycerin may be copolymerized.
　スキン層を支持する多孔性支持体は、スキン層を支持しうるものであれば特に限定されず、通常平均孔径１０～５００Å程度の微孔を有する限外濾過膜が好ましく用いられる。多孔性支持体の形成材料としては、例えば、ポリスルホン、ポリエーテルスルホンのようなポリアリールエーテルスルホン、ポリイミド、ボリフッ化ビニリデンなど種々のものをあげることができるが、特に化学的、機械的、熱的に安定である点からポリスルホン、ポリアリールエーテルスルホンが好ましく用いられる。かかる多孔性支持体の厚さは、通常約２５～１２５μｍ、好ましくは約４０～７５μｍであるが、必ずしもこれらに限定されるものではない。なお、多孔性支持体は織布、不織布等の基材による裏打ちにて補強されていている。 The porous support for supporting the skin layer is not particularly limited as long as it can support the skin layer, and usually an ultrafiltration membrane having micropores with an average pore diameter of about 10 to 500 mm is preferably used. Examples of the material for forming the porous support include polysulfone, polyarylethersulfone such as polyethersulfone, polyimide, polyvinylidene fluoride, and the like. Polysulfone and polyarylethersulfone are preferably used from the viewpoint of stability. The thickness of such a porous support is usually about 25 to 125 μm, preferably about 40 to 75 μm, but is not necessarily limited thereto. The porous support is reinforced by backing with a base material such as a woven fabric or a non-woven fabric.
　ポリアミド系樹脂を含むスキン層を多孔性支持体の表面に形成する方法は特に制限されず、あらゆる公知の手法を用いることができる。例えば、界面縮合法、相分離法、薄膜塗布法などが挙げられる。界面縮合法とは、具体的に、多官能アミン成分を含有するアミン溶液と、多官能酸ハライド成分を含有する有機溶液とを接触させて界面重合させることによりスキン層を形成し、該スキン層を多孔性支持体上に載置する方法や、多孔性支持体上での前記界面重合によりポリアミド系樹脂のスキン層を多孔性支持体上に直接形成する方法である。かかる界面縮合法の条件等の詳細は、特開昭５８－２４３０３号公報、特開平１－１８０２０８号公報等に記載されており、それらの公知技術を適宜採用することができる。 The method for forming the skin layer containing the polyamide-based resin on the surface of the porous support is not particularly limited, and any known method can be used. For example, an interfacial condensation method, a phase separation method, a thin film coating method, and the like can be given. Specifically, the interfacial condensation method is a method in which a skin layer is formed by bringing an amine solution containing a polyfunctional amine component into contact with an organic solution containing a polyfunctional acid halide component to cause interfacial polymerization. Is a method in which a polyamide resin skin layer is directly formed on a porous support by interfacial polymerization on the porous support. Details of the conditions of the interfacial condensation method are described in JP-A-58-24303 and JP-A-1-180208, and those known techniques can be appropriately employed.
　本発明においては、多官能アミン成分を含むアミン溶液と多官能酸ハライド成分を含む有機溶液とを多孔性支持体上で接触させて界面重合させることによりスキン層を形成する方法が好ましい。 In the present invention, a method of forming a skin layer by bringing an amine solution containing a polyfunctional amine component and an organic solution containing a polyfunctional acid halide component into contact with each other on a porous support to cause interfacial polymerization is preferable.
　アミン溶液中の多官能アミン成分の濃度は特に制限されないが、０．１～５重量％であることが好ましく、さらに好ましくは０．５～４重量％である。多官能アミン成分の濃度が０．１重量％未満の場合にはスキン層にピンホール等の欠陥が生じやすくなり、また塩阻止性能が低下する傾向にある。一方、多官能アミン成分の濃度が５重量％を超える場合には、多官能アミン成分が多孔性支持体中に浸透しやすくなったり、膜厚が厚くなりすぎて透過抵抗が大きくなって透過流束が低下する傾向にある。 The concentration of the polyfunctional amine component in the amine solution is not particularly limited, but is preferably 0.1 to 5% by weight, and more preferably 0.5 to 4% by weight. When the concentration of the polyfunctional amine component is less than 0.1% by weight, defects such as pinholes are likely to occur in the skin layer, and the salt blocking performance tends to decrease. On the other hand, when the concentration of the polyfunctional amine component exceeds 5% by weight, the polyfunctional amine component is likely to penetrate into the porous support, or the film thickness becomes too thick to increase the permeation resistance and increase the permeation flow. The bundle tends to decrease.
　有機溶液中の多官能酸ハライド成分の濃度は特に制限されないが、０．０１～５重量％であることが好ましく、さらに好ましくは０．０５～３重量％である。多官能酸ハライド成分の濃度が０．０１重量％未満の場合には、未反応多官能アミン成分が残留しやすくなったり、スキン層にピンホール等の欠陥が生じやすくなって塩阻止性能が低下する傾向にある。一方、多官能酸ハライド成分の濃度が５重量％を超える場合には、未反応多官能酸ハライド成分が残留しやすくなったり、膜厚が厚くなりすぎて透過抵抗が大きくなり、透過流束が低下する傾向にある。 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. If the concentration of the polyfunctional acid halide component is less than 0.01% by weight, the unreacted polyfunctional amine component tends to remain, or defects such as pinholes are likely to occur in the skin layer, resulting in a decrease in salt blocking performance. Tend to. On the other hand, when the 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.
　アミン溶液の溶媒としては、例えば、水、アルコール（例えば、エタノール、イソプロピルアルコール、及びエチレングリコールなど）、及び水とアルコールとの混合溶媒などが挙げられる。 Examples of the solvent for the amine solution include water, alcohol (for example, ethanol, isopropyl alcohol, ethylene glycol, and the like), and a mixed solvent of water and alcohol.
　有機溶液の溶媒としては、水に対する溶解度が低く、多孔性支持体を劣化させず、多官能酸ハライド成分を溶解するものであれば特に限定されず、例えば、シクロヘキサン、ヘプタン、オクタン、及びノナン等の飽和炭化水素、１，１，２－トリクロロトリフルオロエタン等のハロゲン置換炭化水素などを挙げることができる。好ましくは沸点が３００℃以下、さらに好ましくは沸点が２００℃以下の飽和炭化水素またはナフテン系溶媒である。有機溶媒は１種単独で用いてもよく、２種以上の混合溶媒として用いてもよい。 The solvent of the organic solution is not particularly limited as long as it has low solubility in water, does not degrade the porous support, and dissolves the polyfunctional acid halide component. For example, cyclohexane, heptane, octane, nonane, etc. And saturated hydrocarbons such as 1,2-halogenated hydrocarbons such as 1,1,2-trichlorotrifluoroethane. A saturated hydrocarbon or naphthenic solvent having a boiling point of 300 ° C. or lower, more preferably 200 ° C. or lower is preferable. The organic solvent may be used alone or as a mixed solvent of two or more.
　本発明においては、溶解度パラメーターが８～１４（cal／cm3)1/2の物質の存在下でアミン溶液と有機溶液とを接触させることが好ましい。 In the present invention, the amine solution and the organic solution are preferably contacted in the presence of a substance having a solubility parameter of 8 to 14 (cal / cm 3 ) 1/2 .
　溶解度パラメーターとは、液体のモル蒸発熱を△Hcal/mol、モル体積をVcm3 /molとするとき、（△H／V）1/2 （cal／cm3 )1/2で定義される量をいう。溶解度パラメーターが８～１４（cal／cm3)1/2の物質としては、例えば、アルコール類、エーテル類、ケトン類、エステル類、ハロゲン化炭化水素類、及び含硫黄化合物類などが挙げられる。 The solubility parameter is the amount defined by (△ H / V) 1/2 (cal / cm 3 ) 1/2 when the heat of vaporization of the liquid is ΔHcal / mol and the molar volume is Vcm 3 / mol. Say. Examples of the substance having a solubility parameter of 8 to 14 (cal / cm 3 ) 1/2 include alcohols, ethers, ketones, esters, halogenated hydrocarbons, and sulfur-containing compounds.
　アルコール類としては、例えば、エタノール、プロパノール、ブタノール、ブチルアルコール、１－ペンタノール、２－ペンタノール、ｔ－アミルアルコール、イソアミルアルコール、イソブチルアルコール、イソプロピルアルコール、ウンデカノール、２－エチルブタノール、２－エチルヘキサノール、オクタノール、シクロヘキサノール、テトラヒドロフルフリルアルコール、ネオペンチルグリコール、ｔ－ブタノール、ベンジルアルコール、４－メチル－２－ペンタノール、３－メチル－２－ブタノール、ペンチルアルコール、アリルアルコール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール等が挙げられる。 Examples of alcohols include ethanol, propanol, butanol, butyl alcohol, 1-pentanol, 2-pentanol, t-amyl alcohol, isoamyl alcohol, isobutyl alcohol, isopropyl alcohol, undecanol, 2-ethylbutanol, and 2-ethyl. Hexanol, octanol, cyclohexanol, tetrahydrofurfuryl alcohol, neopentyl glycol, t-butanol, benzyl alcohol, 4-methyl-2-pentanol, 3-methyl-2-butanol, pentyl alcohol, allyl alcohol, ethylene glycol, diethylene glycol , Triethylene glycol, tetraethylene glycol and the like.
　エーテル類としては、例えば、アニソール、エチルイソアミルエーテル、エチル－ｔ－ブチルエーテル、エチルベンジルエーテル、クラウンエーテル、クレジルメチルエーテル、ジイソアミルエーテル、ジイソプロピルエーテル、ジエチルエーテル、ジオキサン、ジグリシジルエーテル、シネオール、ジフェニルエーテル、ジブチルエーテル、ジプロピルエーテル、ジベンジルエーテル、ジメチルエーテル、テトラヒドロピラン、テトラヒドロフラン、トリオキサン、ジクロロエチルエーテル、ブチルフェニルエーテル、フラン、メチル－ｔ－ブチルエーテル、モノジクロロジエチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジブチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレンクロロヒドリン等が挙げられる。 Examples of ethers include anisole, ethyl isoamyl ether, ethyl-t-butyl ether, ethyl benzyl ether, crown ether, cresyl methyl ether, diisoamyl ether, diisopropyl ether, diethyl ether, dioxane, diglycidyl ether, cineol, diphenyl ether. , Dibutyl ether, dipropyl ether, dibenzyl ether, dimethyl ether, tetrahydropyran, tetrahydrofuran, trioxane, dichloroethyl ether, butylphenyl ether, furan, methyl-t-butyl ether, monodichlorodiethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether , Ethylene glycol dibutyl ether, ethylene glycol mono Chirueteru, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether include diethylene chlorohydrin like.
　ケトン類としては、例えば、エチルブチイルケトン、ジアセトンアルコール、ジイソブチルケトン、シクロヘキサノン、２－ヘプタノン、メチルイソブチルケトン、メチルエチルケトン、メチルシクロヘキサン等が挙げられる。 Examples of ketones include ethyl butyyl ketone, diacetone alcohol, diisobutyl ketone, cyclohexanone, 2-heptanone, methyl isobutyl ketone, methyl ethyl ketone, and methylcyclohexane.
　エステル類としては、例えば、ギ酸メチル、ギ酸エチル、ギ酸プロピル、ギ酸ブチル、ギ酸イソブチル、ギ酸イソアミル、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、酢酸イソブチル、酢酸アミル等が挙げられる。 Examples of the esters include methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, isoamyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, and amyl acetate.
　ハロゲン化炭化水素類としては、例えば、アリルクロライド、塩化アミル、ジクロロメタン、ジクロロエタン等が挙げられる。 Examples of halogenated hydrocarbons include allyl chloride, amyl chloride, dichloromethane, dichloroethane and the like.
　含硫黄化合物類としては、例えば、ジメチルスルホキシド、スルホラン、チオラン等が挙げられる。 Examples of sulfur-containing compounds include dimethyl sulfoxide, sulfolane, thiolane and the like.
　これらのうち、特にアルコール類、エーテル類が好ましい。これらは１種で用いてもよく、２種以上を併用してもよい。 Of these, alcohols and ethers are particularly preferable. These may be used alone or in combination of two or more.
　溶解度パラメーターが８～１４（cal／cm3)1/2の物質は、アミン溶液に添加してもよく、有機溶液に添加してもよく、両溶液に添加してもよい。また、当該物質を予め多孔性支持体に含浸させておいてもよい。また、当該物質のガス雰囲気中で、アミン溶液と有機溶液とを多孔性支持体上で接触させてもよい。 A substance having a solubility parameter of 8 to 14 (cal / cm 3 ) 1/2 may be added to an amine solution, an organic solution, or both solutions. Further, the porous support may be impregnated with the substance in advance. Moreover, you may make an amine solution and an organic solution contact on a porous support body in the gas atmosphere of the said substance.
　アミン溶液に当該物質を添加する場合、添加量は１０～５０重量％であることが好ましい。１０重量％未満では透過流束を上げる効果は不十分であり、５０重量％を超えると阻止率が低下する傾向となる。有機溶液に当該物質を添加する場合、添加量は０．００１～１０重量％であることが好ましい。０．００１重量％未満では透過流束を上げる効果は不十分であり、１０重量％を超えると阻止率が低下する傾向となる。 When the substance is added to the amine solution, the addition amount is preferably 10 to 50% by weight. If it is less than 10% by weight, the effect of increasing the permeation flux is insufficient, and if it exceeds 50% by weight, the rejection rate tends to decrease. When the substance is added to the organic solution, the addition amount is preferably 0.001 to 10% by weight. If it is less than 0.001% by weight, the effect of increasing the permeation flux is insufficient, and if it exceeds 10% by weight, the rejection rate tends to decrease.
　アミン溶液又は有機溶液には、製膜を容易にしたり、得られる複合半透膜の性能を向上させるための目的で各種の添加剤を加えることができる。前記添加剤としては、例えば、ドデシルベンゼンスルホン酸ナトリウム、ドデシル硫酸ナトリウム、及びラウリル硫酸ナトリウム等の界面活性剤、重合により生成するハロゲン化水素を除去する水酸化ナトリウム、リン酸三ナトリウム、及びトリエチルアミン等の塩基性化合物、アシル化触媒などが挙げられる。 Various additives can be added to the amine solution or the organic solution for the purpose of facilitating film formation or improving the performance of the resulting composite semipermeable membrane. Examples of the additive include surfactants such as sodium dodecylbenzenesulfonate, sodium dodecylsulfate, and sodium laurylsulfate, sodium hydroxide that removes hydrogen halide generated by polymerization, trisodium phosphate, and triethylamine. And basic compounds, acylation catalysts, and the like.
　多孔性支持体上に前記アミン溶液を塗布してから前記有機溶液を塗布するまでの時間は、アミン溶液の組成、粘度及び多孔性支持体の表面層の孔径にもよるが、１５秒以下であることが好ましく、さらに好ましくは５秒以下である。前記溶液の塗布間隔が１５秒を超える場合には、アミン溶液が多孔性支持体の内部深くまで浸透・拡散し、未反応多官能アミン成分が多孔性支持体中に大量に残存する恐れがある。また、多孔性支持体の内部深くまで浸透した未反応多官能アミン成分は、その後の膜洗浄処理でも除去し難い傾向にある。なお、前記多孔性支持体上に前記アミン溶液を被覆した後、余分なアミン溶液を除去してもよい。 The time from application of the amine solution on the porous support to application of the organic solution depends on the composition of the amine solution, the viscosity, and the pore size of the surface layer of the porous support, but is 15 seconds or less. It is preferable that it is 5 seconds or less. If the application interval of the solution exceeds 15 seconds, the amine solution may penetrate and diffuse deep inside the porous support, and a large amount of unreacted polyfunctional amine component may remain in the porous support. . Further, the unreacted polyfunctional amine component that has penetrated deep inside the porous support tends to be difficult to remove even in the subsequent membrane cleaning treatment. In addition, you may remove an excess amine solution after coat | covering the said amine solution on the said porous support body.
　本発明においては、アミン溶液と有機溶液との接触後、多孔性支持体上の過剰な有機溶液を除去し、多孔性支持体上の形成膜を７０℃以上で加熱乾燥してスキン層を形成することが好ましい。形成膜を加熱処理することによりその機械的強度や耐熱性等を高めることができる。加熱温度は７０～２００℃であることがより好ましく、特に好ましくは１００～１５０℃である。加熱時間は３０秒～１０分程度が好ましく、さらに好ましくは４０秒～７分程度である。 In the present invention, after contacting the amine solution and the organic solution, the excess organic solution on the porous support is removed, and the formed film on the porous support is heated and dried at 70 ° C. or more to form a skin layer. It is preferable to do. By heat-treating the formed film, its mechanical strength, heat resistance, etc. can be increased. 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.
　多孔性支持体上に形成したスキン層の厚みは特に制限されないが、通常０．０５～２μｍ程度であり、好ましくは、０．１～１μｍである。 The thickness of the skin layer formed on the porous support is not particularly limited, but is usually about 0.05 to 2 μm, preferably 0.1 to 1 μm.
　また、複合半透膜の塩阻止性、透水性、及び耐酸化剤性等を向上させるために、従来公知の各種処理を施してもよい。 Moreover, in order to improve the salt blocking property, water permeability, oxidation resistance and the like of the composite semipermeable membrane, various conventionally known treatments may be performed.
　本発明においては、スキン層を多孔性支持体の表面に形成した後、スキン層に温水通水処理を施す。温水通水処理に用いる温水の温度は特に制限されないが、通常４０～６５℃程度であり、好ましくは４０～６０である。温水通水処理の時間は特に制限されないが、１～５時間であることが好ましく、より好ましくは３～５時間である。温水通水処理は、膜状の複合半透膜に対して行ってもよく、複合半透膜をスパイラル状に加工して得られるスパイラル型分離膜エレメントに対して行ってもよい。 In the present invention, after the skin layer is formed on the surface of the porous support, the skin layer is subjected to warm water flow treatment. The temperature of the hot water used for the hot water flow treatment is not particularly limited, but is usually about 40 to 65 ° C., preferably 40 to 60. The time for the hot water flow treatment is not particularly limited, but is preferably 1 to 5 hours, and more preferably 3 to 5 hours. The hot water flow treatment may be performed on a membrane-shaped composite semipermeable membrane, or may be performed on a spiral separation membrane element obtained by processing the composite semipermeable membrane into a spiral shape.
　スパイラル型分離膜エレメントは、例えば、複合半透膜を二つ折りにした間に供給側流路材を配置したものと、透過側流路材とを積み重ね、供給側流体と透過側流体の混合を防ぐ封止部を形成するための接着剤を複合半透膜の周辺部（３辺）に塗布して分離膜ユニットを作製し、この分離膜ユニットの単数または複数を中心管の周囲にスパイラル状に巻きつけて、更に分離膜ユニットの周辺部を封止することによって製造される。 Spiral separation membrane elements, for example, stack a supply-side channel material with a composite semipermeable membrane folded in two and a permeate-side channel material to mix the supply-side fluid and permeate-side fluid. A separation membrane unit is manufactured by applying an adhesive for forming a sealing portion to be prevented to the periphery (three sides) of the composite semipermeable membrane, and one or more separation membrane units are spirally formed around the central tube. And is further manufactured by sealing the periphery of the separation membrane unit.
　前記製造方法により得られるスキン層は、水中ＡＦＭでのフォースカーブ測定により算出される弾性率が１００ＭＰａ以上である。弾性率は１１０ＭＰａ以上であることが好ましく、より好ましくは１３０ＭＰａ以上であり、さらに好ましくは１５０ＭＰａ以上である。 The skin layer obtained by the above manufacturing method has an elastic modulus of 100 MPa or more calculated by a force curve measurement with an underwater AFM. The elastic modulus is preferably 110 MPa or more, more preferably 130 MPa or more, and further preferably 150 MPa or more.
　水中ＡＦＭでのフォースカーブ測定によるスキン層の弾性率の算出は、実施例に記載の方法で行う。 The calculation of the elastic modulus of the skin layer by the force curve measurement with the underwater AFM is performed by the method described in the examples.
　以下に実施例をあげて本発明を説明するが、本発明はこれら実施例によりなんら限定されるものではない。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
　〔評価及び測定方法〕
　（水中ＡＦＭでのフォースカーブ測定によるスキン層の弾性率の算出）
　作製したウェット状態の複合半透膜を２ｃｍ×２ｃｍの大きさに切断したサンプル１を、アサイラムテクノロジー社製の液中測定用固定治具（Closed Fluid Cell）、固定ピン２、及び抑え板３を用いて、図１に示すように、固定治具のガラス板４上に固定した。その後、サンプル１上に超純水５を約１００μｌ滴下した。　
　そして、サンプル１を垂直方向に移動させて、サンプル１のスキン層に、荷重をかけながら球形プローブ６を押し込み、そして引き離した際のカンチレバー７のたわみ又はそり（変位）をレーザー光８の変位としてフォトダイオードで検出してフォースカーブを測定し、装置付属のプログラムを用いて荷重とスキン層変形量に変換した。測定面積９０μｍ×９０μｍの領域を２０×２０分割し、合計４００点でフォースカーブを測定した。そして、荷重３μＮの時のスキン層変形量の平均値を求めた。　
　測定装置及び測定条件は以下のとおりである。　
・測定装置：ＭＦＰ－３Ｄ（アサイラムテクノロジー社製）
・カンチレバー：ばね定数４０Ｎ／ｍ
・球形プローブ：ナノセンサーズ社製、先端曲率半径０．４μｍ、Silicon(100)、ポアソン比０．１７、弾性率１５０ＧＰａ
・測定環境：超純水中
・押し込み速度、引き離し速度：４．０μｍ／ｓ
・最大荷重：３μＮ
・測定ｎ数：４００
　スキン層の弾性率Ｅsample（ＭＰａ）は、下記ヘルツ弾性接触理論式に各数値を代入することにより求められる。　
　ｈ＝〔3/4[{(1－νprobe 2)／Ｅprobe｝＋{(1－νsample 2)／Ｅsample｝］〕2/3Ｆ2/3ｒ-1/3
ｈ：スキン層変形量（平均値）
νprobe：プローブのポアソン比０．１７
νsample：サンプルのポアソン比０．３５（樹脂の代表値として０．３５を採用（固定値））
Ｅprobe：プローブの弾性率１５０ＧＰａ
Ｅsample：サンプルの弾性率（ＭＰａ）
Ｆ：荷重３μＮ
ｒ：プローブの先端曲率半径０．４μｍ [Evaluation and measurement method]
(Calculation of elastic modulus of skin layer by force curve measurement with underwater AFM)
A sample 1 obtained by cutting the prepared composite semipermeable membrane in a wet state into a size of 2 cm × 2 cm is attached to a fixing jig (Closed Fluid Cell), a fixing pin 2 and a holding plate 3 manufactured by Asylum Technology. Using, as shown in FIG. 1, it fixed on the glass plate 4 of a fixing jig. Thereafter, about 100 μl of ultrapure water 5 was dropped on the sample 1.
Then, the sample 1 is moved in the vertical direction, the spherical probe 6 is pushed into the skin layer of the sample 1 while applying a load, and the deflection or warpage (displacement) of the cantilever 7 at the time of separation is defined as the displacement of the laser beam 8. The force curve was measured by detecting with a photodiode, and converted to load and skin layer deformation using the program attached to the device. A region having a measurement area of 90 μm × 90 μm was divided into 20 × 20, and a force curve was measured at a total of 400 points. And the average value of the deformation amount of the skin layer when the load was 3 μN was obtained.
The measurement apparatus and measurement conditions are as follows.
・ Measurement device: MFP-3D (manufactured by Asylum Technology)
・ Cantilever: Spring constant 40N / m
-Spherical probe: manufactured by Nanosensors, radius of curvature of the tip 0.4 μm, Silicon (100), Poisson's ratio 0.17, elastic modulus 150 GPa
・ Measurement environment: Ultra pure water ・ Pushing speed, pulling speed: 4.0 μm / s
・ Maximum load: 3μN
-Measurement n number: 400
The elastic modulus E sample (MPa) of the skin layer is obtained by substituting each numerical value into the following Hertz elastic contact theoretical formula.
h = [3/4 [{(1−ν probe 2 ) / E probe } + {(1−ν sample 2 ) / E sample }]]] 2/3 F 2/3 r −1/3
h: Skin layer deformation (average value)
ν probe : Poisson's ratio of probe 0.17
ν sample : Poisson's ratio of sample 0.35 (adopting 0.35 as a representative value of resin (fixed value))
E probe : Elastic modulus of the probe 150 GPa
E sample : Elastic modulus of the sample (MPa)
F: Load 3 μN
r: Probe tip radius of curvature 0.4 μm
　（透過流束の低下率）
　作製した複合半透膜を所定の形状、サイズに切断したサンプルを平膜評価用のセルにセットする。０．２％のＭｇＳＯ４を含みかつＮａＯＨを用いてｐＨ６．５～７．０に調整した水溶液を２５℃で膜の供給側と透過側に０．９ＭＰａの差圧を与えて膜に接触させる。この操作によって得られた透過水の透過速度を測定し、膜面積１平方メートル当たりの１日の透水量（立方メートル）から透過流束Ｘ（ｍ３／ｍ２・ｄ）を算出した。当該サンプルを４０℃の環境下で７日間保管し、その後、同様の方法で透過流束Ｙを算出した。透過流束の低下率は下記式により算出した。　
　透過流束の低下率（％）＝〔（Ｘ－Ｙ）／Ｘ〕×１００ (Decrease rate of permeation flux)
A sample obtained by cutting the produced composite semipermeable membrane into a predetermined shape and size is set in a flat membrane evaluation cell. An aqueous solution containing 0.2% MgSO 4 and adjusted to pH 6.5 to 7.0 using NaOH is brought into contact with the membrane at 25 ° C. by applying a differential pressure of 0.9 MPa to the supply side and the permeation side of the membrane. . The permeation rate of the permeated water obtained by this operation was measured, and the permeation flux X (m 3 / m 2 · d) was calculated from the daily water permeation amount per cubic meter (cubic meter). The sample was stored in an environment of 40 ° C. for 7 days, and then the permeation flux Y was calculated by the same method. The reduction rate of the permeation flux was calculated by the following formula.
Permeation flux reduction rate (%) = [(XY) / X] × 100
　比較例１
　ピペラジン７水和物３．６重量％、ラウリル硫酸ナトリウム０．１５重量％、カンファースルホン酸６重量％、及び水酸化ナトリウム１．４８重量％を水に溶解させてアミン溶液を調製した。そして、アミン溶液を多孔性支持体の表面に接触させた後、余分なアミン溶液を除去した。その後、多孔性支持体の表面のアミン溶液と、トリメシン酸クロライド０．４２重量％及びｔ－ブタノール０．５重量％をＩＰ１０１６（沸点１０６℃）に溶解させた有機溶液とを接触させた。その後、余分な有機溶液を除去し、１２０℃の熱風乾燥機中で３分間保持して、多孔性支持体上にポリアミド系樹脂を含むスキン層を形成して複合半透膜を作製した。 Comparative Example 1
An amine solution was prepared by dissolving 3.6% by weight of piperazine heptahydrate, 0.15% by weight of sodium lauryl sulfate, 6% by weight of camphorsulfonic acid, and 1.48% by weight of sodium hydroxide in water. And after making an amine solution contact the surface of a porous support body, the excess amine solution was removed. Thereafter, the amine solution on the surface of the porous support was brought into contact with an organic solution in which 0.42% by weight of trimesic acid chloride and 0.5% by weight of t-butanol were dissolved in IP1016 (boiling point 106 ° C.). Then, the excess organic solution was removed, and it hold | maintained for 3 minutes in a 120 degreeC hot air dryer, the skin layer containing a polyamide-type resin was formed on the porous support body, and the composite semipermeable membrane was produced.
　実施例１
　比較例１で作製した複合半透膜に、４０℃の温水を５時間通水して、スキン層に温水通水処理を施した。 Example 1
The composite semipermeable membrane produced in Comparative Example 1 was passed through 40 ° C. warm water for 5 hours, and the skin layer was subjected to warm water passing treatment.
　実施例２
　比較例１で作製した複合半透膜に、５０℃の温水を５時間通水して、スキン層に温水通水処理を施した。 Example 2
The composite semipermeable membrane produced in Comparative Example 1 was passed through warm water at 50 ° C. for 5 hours, and the skin layer was subjected to warm water passing treatment.
　実施例３
　比較例１で作製した複合半透膜に、６０℃の温水を５時間通水して、スキン層に温水通水処理を施した。 Example 3
The composite semipermeable membrane produced in Comparative Example 1 was allowed to pass hot water at 60 ° C. for 5 hours, and the skin layer was subjected to hot water flow treatment.
　実施例４
　比較例１で作製した複合半透膜を用いてスパイラル型分離膜エレメントを作製した。作製したスパイラル型分離膜エレメントに、６０℃の温水を３時間通水して、スキン層に温水通水処理を施した。なお、前記弾性率及び透過流束の測定においては、エレメントから複合半透膜を取り出して測定した。 Example 4
A spiral separation membrane element was produced using the composite semipermeable membrane produced in Comparative Example 1. Hot water at 60 ° C. was passed through the produced spiral separation membrane element for 3 hours, and the skin layer was subjected to hot water passage treatment. In the measurement of the elastic modulus and permeation flux, the composite semipermeable membrane was taken out from the element and measured.
Figure JPOXMLDOC01-appb-T000001
  
 
Figure JPOXMLDOC01-appb-T000001
  
 
　本発明のスパイラル型分離膜エレメントは、超純水の製造、かん水または海水の脱塩などに好適であり、また染色排水や電着塗料排水などの公害発生原因である汚れなどから、その中に含まれる汚染源あるいは有効物質を除去・回収し、排水のクローズ化に寄与することができる。また、食品用途などで有効成分の濃縮、浄水や下水用途等での有害成分の除去などの高度処理に用いることができる。また、油田やシェールガス田などにおける排水処理に用いることができる。 The spiral separation membrane element of the present invention is suitable for the production of ultrapure water, desalination of brackish water or seawater, etc., and from contamination that causes pollution such as dyeing waste water and electrodeposition paint waste water. It can contribute to the closure of wastewater by removing and recovering contained pollution sources or effective substances. Moreover, it can be used for advanced treatments such as concentration of active ingredients in food applications and removal of harmful components in water purification and sewage applications. It can also be used for wastewater treatment in oil fields, shale gas fields, and the like.
１：サンプル
２：固定ピン
３：抑え板
４：固定治具のガラス板
５：超純水
６：球形プローブ
７：カンチレバー
８：レーザー光 1: Sample 2: Fixing pin 3: Holding plate 4: Glass plate of fixing jig 5: Ultrapure water 6: Spherical probe 7: Cantilever 8: Laser light

Claims (4)

  1. 多孔性支持体上にポリアミド系樹脂を含むスキン層を有する複合半透膜を内蔵するスパイラル型分離膜エレメントの船輸送方法において、
    　前記スキン層は、温水通水処理が施されており、
    　前記スキン層は、水中ＡＦＭでのフォースカーブ測定により算出される弾性率が１００ＭＰａ以上であり、
    　前記スパイラル型分離膜エレメントを、冷蔵していない保管状態で輸送することを特徴とするスパイラル型分離膜エレメントの船輸送方法。     In a ship transportation method of a spiral type separation membrane element that incorporates a composite semipermeable membrane having a skin layer containing a polyamide-based resin on a porous support,
    The skin layer has been subjected to warm water flow treatment,
    The skin layer has an elastic modulus calculated by a force curve measurement with an underwater AFM of 100 MPa or more,
    A method for transporting a spiral-type separation membrane element, wherein the spiral-type separation membrane element is transported in a storage state that is not refrigerated.
  2. 前記ポリアミド系樹脂は、ピペラジンとトリメシン酸クロライドとの重合体を含む請求項１記載のスパイラル型分離膜エレメントの船輸送方法。 2. The method of transporting a spiral separation membrane element according to claim 1, wherein the polyamide-based resin contains a polymer of piperazine and trimesic acid chloride.
  3. 前記温水通水処理は、４０～６０℃の温水を用いて１～５時間行われる請求項１又は２記載のスパイラル型分離膜エレメントの船輸送方法。 The method for transporting a spiral separation membrane element according to claim 1 or 2, wherein the hot water flow treatment is performed using hot water of 40 to 60 ° C for 1 to 5 hours.
  4. 前記スキン層は、多官能アミン成分を含むアミン溶液と多官能酸ハライド成分を含む有機溶液とを多孔性支持体上で接触させて界面重合させることにより形成され、前記接触は、エタノール、プロパノール、ブタノール、ブチルアルコール、１－ペンタノール、２－ペンタノール、ｔ－アミルアルコール、イソアミルアルコール、イソブチルアルコール、イソプロピルアルコール、ウンデカノール、２－エチルブタノール、２－エチルヘキサノール、オクタノール、シクロヘキサノール、テトラヒドロフルフリルアルコール、ｔ－ブタノール、ベンジルアルコール、４－メチル－２－ペンタノール、３－メチル－２－ブタノール、ペンチルアルコール、アリルアルコール、アニソール、エチルイソアミルエーテル、エチル－ｔ－ブチルエーテル、エチルベンジルエーテル、クラウンエーテル、クレジルメチルエーテル、ジイソアミルエーテル、ジイソプロピルエーテル、ジグリシジルエーテル、シネオール、ジフェニルエーテル、ジブチルエーテル、ジプロピルエーテル、ジベンジルエーテル、ジメチルエーテル、テトラヒドロピラン、トリオキサン、ジクロロエチルエーテル、ブチルフェニルエーテル、フラン、モノジクロロジエチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジブチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレンクロロヒドリンから選ばれる少なくとも一つの溶解度パラメーターが８～１４（cal／cm3)1/2の物質の存在下で行われる請求項１～３のいずれかに記載のスパイラル型分離膜エレメントの船輸送方法。 The skin layer is formed by bringing an amine solution containing a polyfunctional amine component into contact with an organic solution containing a polyfunctional acid halide component on a porous support and interfacially polymerizing the ethanol, propanol, Butanol, butyl alcohol, 1-pentanol, 2-pentanol, t-amyl alcohol, isoamyl alcohol, isobutyl alcohol, isopropyl alcohol, undecanol, 2-ethylbutanol, 2-ethylhexanol, octanol, cyclohexanol, tetrahydrofurfuryl alcohol , T-butanol, benzyl alcohol, 4-methyl-2-pentanol, 3-methyl-2-butanol, pentyl alcohol, allyl alcohol, anisole, ethyl isoamyl ether, ethyl-t-butyl ether , Ethyl benzyl ether, crown ether, cresyl methyl ether, diisoamyl ether, diisopropyl ether, diglycidyl ether, cineol, diphenyl ether, dibutyl ether, dipropyl ether, dibenzyl ether, dimethyl ether, tetrahydropyran, trioxane, dichloroethyl ether, Butyl phenyl ether, furan, monodichlorodiethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, di Chi glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, lines in the presence of diethylene glycol monobutyl ether, at least one solubility parameter selected from diethylene chlorohydrin is 8 ~ 14 (cal / cm 3 ) 1/2 of a substance The method for transporting a spiral separation membrane element according to any one of claims 1 to 3.
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