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WO2016121599A1 - Procédé de transport par bateau pour élément de membrane de séparation à spirale - Google Patents

Procédé de transport par bateau pour élément de membrane de séparation à spirale 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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WIPO (PCT)
Prior art keywords
ether
separation membrane
membrane element
skin layer
alcohol
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Ceased
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PCT/JP2016/051583
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English (en)
Japanese (ja)
Inventor
かずさ 松井
伸明 丸岡
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Nitto Denko Corp
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Nitto Denko Corp
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Publication of WO2016121599A1 publication Critical patent/WO2016121599A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/10—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

L'objectif de la présente invention est de fournir un procédé de transport par bateau pour élément de membrane de séparation à spirale ne nécessitant pas de stockage réfrigéré de l'élément de membrane de séparation à spirale lors du transport de l'élément de membrane de séparation à spirale par bateau. La présente invention concerne un procédé de transport par bateau pour élément de membrane de séparation à spirale utilisant une membrane semi-perméable composite comportant une couche active qui contient une résine de polyamide sur un corps formant un support poreux et qui est caractérisé en ce que la couche active subit un traitement consistant à faire passer de l'eau chaude à travers, en ce que la couche active présente un module d'élasticité de 100 MPa comme calculé par des mesures de courbe de force par AFM dans l'eau et en ce que l'élément de membrane de séparation à spirale est transporté dans des conditions de stockage n'impliquant pas de réfrigération.
PCT/JP2016/051583 2015-01-29 2016-01-20 Procédé de transport par bateau pour élément de membrane de séparation à spirale Ceased WO2016121599A1 (fr)

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JP2015-015884 2015-01-29
JP2015015884A JP2016140776A (ja) 2015-01-29 2015-01-29 スパイラル型分離膜エレメントの船輸送方法

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JP7072112B1 (ja) 2021-11-05 2022-05-19 日東電工株式会社 複合半透膜、スパイラル型膜エレメント、水処理システム及び水処理方法

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JPH10165790A (ja) * 1996-12-05 1998-06-23 Nitto Denko Corp 複合逆浸透膜の製造方法
JP2005144211A (ja) * 2003-11-11 2005-06-09 Toray Ind Inc 複合半透膜及びその製造方法ならびに流体分離素子の処理方法
JP2007000790A (ja) * 2005-06-24 2007-01-11 Japan Organo Co Ltd 分離膜の処理・保存方法および装置
WO2012033086A1 (fr) * 2010-09-07 2012-03-15 東レ株式会社 Membrane de séparation, élément de membrane de séparation et procédé de production d'une membrane de séparation
WO2012169529A1 (fr) * 2011-06-09 2012-12-13 旭化成メディカル株式会社 Membrane en fibres creuses destinée au traitement du sang et appareil de traitement du sang de type membrane en fibres creuses

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JPH10165790A (ja) * 1996-12-05 1998-06-23 Nitto Denko Corp 複合逆浸透膜の製造方法
JP2005144211A (ja) * 2003-11-11 2005-06-09 Toray Ind Inc 複合半透膜及びその製造方法ならびに流体分離素子の処理方法
JP2007000790A (ja) * 2005-06-24 2007-01-11 Japan Organo Co Ltd 分離膜の処理・保存方法および装置
WO2012033086A1 (fr) * 2010-09-07 2012-03-15 東レ株式会社 Membrane de séparation, élément de membrane de séparation et procédé de production d'une membrane de séparation
WO2012169529A1 (fr) * 2011-06-09 2012-12-13 旭化成メディカル株式会社 Membrane en fibres creuses destinée au traitement du sang et appareil de traitement du sang de type membrane en fibres creuses

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