WO2022225061A1 - 複合半透膜 - Google Patents

複合半透膜 Download PDF

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Publication number
WO2022225061A1
WO2022225061A1 PCT/JP2022/018638 JP2022018638W WO2022225061A1 WO 2022225061 A1 WO2022225061 A1 WO 2022225061A1 JP 2022018638 W JP2022018638 W JP 2022018638W WO 2022225061 A1 WO2022225061 A1 WO 2022225061A1
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WIPO (PCT)
Prior art keywords
composite semipermeable
semipermeable membrane
membrane
thickness
height
Prior art date
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Ceased
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PCT/JP2022/018638
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English (en)
French (fr)
Japanese (ja)
Inventor
崚輔 岡西
俊介 田林
雄太 天野
崇夫 佐々木
雅樹 東
孝 吉野
宏樹 峰原
宏明 田中
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Toray Industries Inc
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Toray Industries Inc
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Filing date
Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Priority to JP2022525132A priority Critical patent/JP7173407B1/ja
Priority to EP22791832.3A priority patent/EP4327920A4/en
Priority to CN202280030071.9A priority patent/CN117202982B/zh
Priority to KR1020237035604A priority patent/KR102685078B1/ko
Priority to US18/287,786 priority patent/US12161978B2/en
Publication of WO2022225061A1 publication Critical patent/WO2022225061A1/ja
Priority to JP2022175059A priority patent/JP7567890B2/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/06—Surface irregularities
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • 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 composite semipermeable membrane useful for selective separation of liquid mixtures.
  • the composite semipermeable membrane obtained by the present invention can be suitably used, for example, for desalination of seawater and brackish water.
  • Membranes used in membrane separation include microfiltration membranes, ultrafiltration membranes, nanofiltration membranes, and reverse osmosis membranes. It is used to obtain water, to produce industrial ultrapure water, to treat wastewater, and to recover valuables.
  • composite semipermeable membranes having crosslinked polyamide as a separation active layer have been proposed as reverse osmosis membranes and nanofiltration membranes.
  • Methods for producing a composite semipermeable membrane having a crosslinked polyamide as a separation active layer include a method of polymerizing in the presence of an organic additive (Patent Documents 1 and 2) and a method of polymerizing in the presence of a monofunctional acid halide. (Patent Document 3), and a method of polymerizing in the presence of a partially hydrolyzed acid halide (Patent Document 4).
  • the present invention has been made in view of the above, and an object of the present invention is to provide a composite semipermeable membrane that has excellent abrasion resistance and excellent water permeability even during high-pressure operation.
  • a composite semipermeable membrane comprising a support membrane and a separation functional layer provided on the support membrane,
  • the separation function layer includes a thin film, the thin film forms a fold structure including a plurality of protrusions with a height of 10 nm or more,
  • the ratio (T100/T25) of the thickness T25 of the thin film in the region of 0 to 25% of the height of the protrusion and the thickness T100 of the thin film in the region of 50 to 100% of the height of the protrusion is 0
  • a composite semipermeable membrane that is less than 0.95.
  • the ratio of the number of protrusions with a height of 400 nm or more to the number of protrusions with a height of 10 nm or more in the fold structure is 1/20 or more and 1/5 or less.
  • the present invention it is possible to provide a membrane that exhibits excellent water permeability even during high-pressure operation while having excellent abrasion resistance.
  • FIG. 1 is a cross-sectional view of a composite semipermeable membrane according to one embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of the separation functional layer, which is a schematic diagram showing the fold structure.
  • FIG. 3 is an enlarged cross-sectional view of protrusions in a pleated structure.
  • the supporting membrane does not substantially have separation performance for ions and the like, and gives strength to the separation functional layer having substantially separation performance.
  • the size and distribution of the pores of the support membrane are not particularly limited.
  • a support film having a fine pore size of 0.1 nm or more and 100 nm or less on the side where the separation functional layer is formed is preferable.
  • the material used for the support film and its shape are not particularly limited. or a film consisting of only one layer.
  • the base material examples include fabrics whose main component is at least one selected from polyesters and aromatic polyamides.
  • the fabric a long-fiber nonwoven fabric or a short-fiber nonwoven fabric can be preferably used.
  • the thickness of the substrate is preferably in the range of 10 ⁇ m to 200 ⁇ m, more preferably in the range of 30 ⁇ m to 120 ⁇ m.
  • Polysulfone, cellulose acetate, polyvinyl chloride, or a mixture thereof is preferably used for the porous support layer, and it is particularly preferable to use polysulfone, which has high chemical, mechanical, and thermal stability.
  • the thickness of the porous support layer is preferably in the range of 10-200 ⁇ m, more preferably in the range of 20-100 ⁇ m.
  • the thickness of the porous support layer is 10 ⁇ m or more, good pressure resistance can be obtained, and a uniform support membrane without defects can be obtained. , can show good salt removal performance.
  • the thickness of the porous support layer is 200 ⁇ m or less, the amount of unreacted substances remaining during production does not increase, and deterioration of chemical resistance due to a decrease in the amount of permeated water can be prevented.
  • the thickness of the supporting membrane is preferably within the range of 30-300 ⁇ m, more preferably within the range of 50-250 ⁇ m.
  • the morphology of the support film can be observed with a scanning electron microscope, a transmission electron microscope, an interatomic microscope, or the like.
  • the porous support layer is peeled off from the substrate and then cut by freeze fracture to obtain a sample for cross-sectional observation.
  • This sample is preferably thinly coated with platinum or platinum-palladium or ruthenium tetrachloride, more preferably ruthenium tetrachloride, and subjected to a high-resolution field emission scanning electron microscope (UHR-FE-SEM) at an accelerating voltage of 3 to 6 kV. to observe.
  • UHR-FE-SEM high-resolution field emission scanning electron microscope
  • the thickness of the base material, porous support layer, and composite semipermeable membrane can be measured with a digital thickness gauge.
  • the thickness of the separation function layer which will be described later, is much thinner than that of the support membrane
  • the thickness of the composite semipermeable membrane can also be regarded as the thickness of the support membrane. Therefore, the thickness of the porous support layer can be easily calculated by measuring the thickness of the composite semipermeable membrane with a digital thickness gauge and subtracting the thickness of the substrate from the thickness of the composite semipermeable membrane.
  • a digital thickness gauge it is preferable to measure the thickness at 20 points and calculate the average value.
  • the thickness of the base material, porous support layer, and composite semipermeable membrane may be measured with the microscope described above.
  • the thickness of one sample is obtained by measuring the thickness from electron micrographs of the cross section observed at any five points and calculating the average value. It should be noted that the thickness and pore size in this embodiment mean average values.
  • the separation functional layer substantially has the ability to separate ions and the like.
  • the separation functional layer is denoted by reference numeral "4".
  • the thin film 11 forms a fold structure including a plurality of projections as shown in FIG.
  • the separation functional layer preferably contains polyamide as a main component.
  • the polyamide can be formed, for example, by interfacial polycondensation of polyfunctional amines and polyfunctional acid halides.
  • at least one of the polyfunctional amine and the polyfunctional acid halide preferably contains a trifunctional or higher compound.
  • the thickness of the separation functional layer is usually within the range of 0.01 to 1 ⁇ m, preferably within the range of 0.1 to 0.5 ⁇ m, in order to obtain sufficient separation performance and water permeation amount.
  • the polyfunctional amine has at least two primary amino groups and/or secondary amino groups in one molecule, and at least one of the amino groups is a primary amino group.
  • Polyfunctional amines include, for example, phenylenediamine, xylylenediamine, and 1,3,5-triamino in which two amino groups are bonded to a benzene ring in either the ortho-position, meta-position, or para-position.
  • aromatic polyfunctional amines such as benzene, 1,2,4-triaminobenzene, 3,5-diaminobenzoic acid, 3-aminobenzylamine and 4-aminobenzylamine; aliphatic amines such as ethylenediamine and propylenediamine; ,2-diaminocyclohexane, 1,4-diaminocyclohexane, 4-aminopiperidine, 4-aminoethylpiperazine, and other alicyclic polyfunctional amines.
  • aromatic polyfunctional amines having 2 to 4 primary amino groups and/or secondary amino groups in one molecule are preferred in consideration of the selective separation property, permeability, and heat resistance of the membrane.
  • polyfunctional aromatic amines for example, m-phenylenediamine, p-phenylenediamine, 1,3,5-triaminobenzene and the like are preferably used.
  • m-PDA m-phenylenediamine
  • polyfunctional amines may be used alone or in combination of two or more.
  • the above amines may be combined, or the above amine may be combined with an amine having at least two secondary amino groups in one molecule.
  • examples of amines having at least two secondary amino groups in one molecule include piperazine and 1,3-bispiperidylpropane.
  • a polyfunctional acid halide refers to an acid halide having at least two halogenated carbonyl groups in one molecule.
  • trifunctional acid halides include trimesic acid chloride, 1,3,5-cyclohexanetricarboxylic acid trichloride, and 1,2,4-cyclobutanetricarboxylic acid trichloride.
  • biphenyldicarboxylic acid dichloride is, for example, biphenyldicarboxylic acid dichloride, azobenzenedicarboxylic acid dichloride, terephthalic acid chloride, isophthalic acid chloride, aromatic bifunctional acid halides such as naphthalenedicarboxylic acid chloride, adipoyl chloride, aliphatic bifunctional such as sebacoyl chloride Acid halides, alicyclic bifunctional acid halides such as cyclopentanedicarboxylic acid dichloride, cyclohexanedicarboxylic acid dichloride, and tetrahydrofurandicarboxylic acid dichloride can be mentioned.
  • the polyfunctional acid halide is preferably a polyfunctional acid chloride.
  • Preferred are polyfunctional aromatic acid chlorides with ⁇ 4 carbonyl chloride groups.
  • trimesic acid chloride is more preferable from the viewpoint of availability and ease of handling.
  • These polyfunctional acid halides may be used alone or in combination of two or more.
  • the thin film forms a fold structure having a plurality of concave portions and convex portions, and has a plurality of protrusions with a height of 10 nm or more, as shown in FIG.
  • the terms “convex” and “concave” refer to a relatively protruding portion and a concave portion of the thin film.
  • the lower (supporting film side) portion is called a recess.
  • Protrusion refers to the distance from the bottom of a recess to the bottom of the adjacent recess, that is, to the bottom of one protrusion and the recesses on both sides thereof. Further, in this specification, projections refer to projections having a height of 1/5 or more of the 10-point average surface roughness of the thin film.
  • the actual length L of the thin film per 1 ⁇ m length of the support film in the cross-sectional direction perpendicular to the film surface is preferably 3.0 ⁇ m or more.
  • the composite semipermeable membrane can obtain high water permeability.
  • the actual length L of the thin film is more preferably 3.0 to 100 ⁇ m, even more preferably 3.0 to 10 ⁇ m.
  • "a cross-sectional direction perpendicular to the film surface" means a direction perpendicular to the direction perpendicular to the film surface.
  • the actual length L of the thin film can be determined according to a general method for determining the surface area and specific surface area, and the method is not particularly limited.
  • a general method for determining the surface area and specific surface area and the method is not particularly limited.
  • SEM scanning electron microscope
  • FE-SEM transmission type A method using an electron microscope such as an electron microscope (TEM) can be mentioned.
  • TEM electron microscope
  • TEM transmission electron microscope
  • the observation magnification may be appropriately determined according to the film thickness of the separation functional layer, but the thickness of the separation functional layer should be 10 to 100 nm so that the cross-sectional shape of the separation functional layer can be observed and the measurement is not localized. If it is a degree, it is preferable to set the observation magnification to 50,000 to 100,000 times.
  • the actual length of the thin film per 1 ⁇ m length of the support film in the cross-sectional direction perpendicular to the film surface was measured in arbitrary 10 cross sections with a length of 2.0 ⁇ m in the cross-sectional photograph obtained above.
  • the average value is calculated as the actual length L of the thin film in the composite semipermeable membrane.
  • the 10-point average surface roughness of a thin film is obtained by the following method.
  • a cross section perpendicular to the film surface is observed with an electron microscope.
  • the observation magnification is preferably 10,000 to 100,000 times.
  • the obtained cross-sectional image shows the surface of the thin film (indicated by reference numeral "11" in FIG. 2) as a curved line.
  • a roughness curve defined based on ISO4287:1997 is obtained.
  • the average line is a straight line drawn so that the total area of the area surrounded by the average line and the roughness curve is equal above and below the average line.
  • the height of the protrusion is calculated as follows. In a cross section with a length of 2.0 ⁇ m in the direction of the above average line, for protrusions that are one-fifth or more of the above 10-point average surface roughness, the depth of the recesses on both sides of the protrusions (from the reference line to the apex of the recesses The sum of the average d of d1 and d2 and the height h of the protrusion (the distance from the reference line to the top of the protrusion) is calculated as the height Ph of the protrusion.
  • the ratio (N/M) of the number N of protrusions having a height of 200 nm or more existing in ten cross sections is 1/20 or more and 1/2 or less.
  • N/M is 1/20 or more
  • the composite semipermeable membrane has high water permeability.
  • N/M is more preferably 1/10 or more.
  • N/M is 1/2 or less, high water permeability can be obtained while maintaining a high removal rate.
  • N/M is more preferably 1/3 or less.
  • the number of all protrusions present in 10 cross sections means that the number of protrusions included in each cross section is obtained in all 10 cross sections, and the number of protrusions obtained in each cross section is calculated in all 10 cross sections. means total sum.
  • At least one protrusion having a height of 400 nm or more is present in any 10 cross sections having a length of 2.0 ⁇ m in the direction of the mean line.
  • the ratio (N1/M) of the number N1 of protrusions having a height of 400 nm or more present in the ten cross sections to the number M of protrusions having a height of 10 nm or more present in the ten cross sections (N1/M) is 1/20 or more, It is more preferably 1/5 or less.
  • High water permeability can be obtained by having protrusions with a height of 400 nm or more in the above range.
  • the height of the protrusion is preferably 70 nm or more, more preferably 90 nm or more.
  • the height of the projections is preferably 1000 nm or less, more preferably 800 nm or less.
  • the height of the projections is 70 nm or more, a composite semipermeable membrane having sufficient water permeability can be easily obtained.
  • the height of the projections is 1000 nm or less, stable membrane performance can be obtained without crushing the projections even when the composite semipermeable membrane is operated under high pressure.
  • the thickness of the thin film can be measured by TEM.
  • Ultra-thin slice preparation for TEM is as described in the description of the measurement of the actual length L of the thin film.
  • a cross-section of the obtained ultra-thin section is photographed by TEM.
  • the observation magnification may be appropriately determined according to the thickness of the separation functional layer.
  • the obtained cross-sectional photograph can be analyzed with image analysis software.
  • the thickness of the thin film in the upper portion and the thickness of the thin film in the lower portion of the protrusion in the fold structure are obtained as follows. As shown in FIG. 3, the average value d of the depths d1 and d2 from the reference line A to the apex of the concave portion on both sides of the convex portion is calculated. Below the reference line A (supporting film side), the position at the distance d from the reference line A has a height of 0%, and the apex of the convex portion has a height of 100%. The thickness of the thin film in the 50% to 100% thickness area is measured at 10 points. Similar measurements are made for 5 protrusions. An arithmetic mean value is calculated for 50 thin film thickness values in the range of 0 to 25% height.
  • This value is taken as the lower thickness T25 of the thin film in the composite semipermeable membrane.
  • the arithmetic mean value is calculated for the thickness of the thin film in the region of 50% to 100% of the height, and this value is defined as the upper thickness T100 of the thin film.
  • the lower thickness T25 is preferably 13 nm or more and less than 24 nm.
  • T25 is more preferably 14 nm or more, and even more preferably 16 nm or more.
  • T25 is less than 24 nm, sufficient water permeability can be maintained while ensuring a high salt removal rate.
  • T25 is more preferably 23 nm or less, even more preferably 21 nm or less.
  • the ratio (T100/T25) between the upper thickness T100 and the lower thickness T25 is less than 0.95.
  • T100/T25 is preferably 0.92 or less, more preferably 0.90 or less, and even more preferably 0.87 or less.
  • T100/T25 is preferably 0.70 or more, more preferably 0.72 or more, and still more preferably 0.75 or more.
  • Composite semipermeable membranes are generally stacked and used, and for example, a channel material is inserted between the composite semipermeable membranes.
  • T100/T25 satisfies the above range
  • the upper part of the projection becomes relatively thin and flexible compared to the lower part, and the lower part becomes thicker and stronger than the upper part. Even if it rubs against other composite semipermeable membranes, the force field is dispersed in the lower part and damage can be reduced.
  • T100/T25 is less than 0.95 and T25 is preferably 13 nm or more, even if the protrusions of the thin film rub against the channel material or other composite semipermeable membranes during use of the composite semipermeable membrane, Damage to the lower part of the protrusion and collapse of the fold structure can be further suppressed.
  • the step of forming a separation functional layer includes contacting a polyfunctional amine solution and a polyfunctional acid halide solution on a porous support layer to form a polyamide through an interfacial polycondensation reaction. More specifically, the step of forming the separation functional layer includes: (i) contacting the porous support layer with a polyfunctional amine solution; (ii) after (i) above, contacting the porous support layer with an organic solvent solution containing a polyfunctional acid halide to form a polyamide on the porous support layer by interfacial polycondensation.
  • a polyfunctional amine solution includes contacting the porous support layer with a polyfunctional amine solution; (ii) after (i) above, contacting the porous support layer with an organic solvent solution containing a polyfunctional acid halide to form a polyamide on the porous support layer by interfacial polycondensation.
  • the polyfunctional amine solution is an aqueous solution, and the concentration of the polyfunctional amine in this solution is preferably in the range of 0.1 to 20% by weight, preferably in the range of 0.5 to 15% by weight. more preferred. When the concentration of the polyfunctional amine is within this range, a composite semipermeable membrane having sufficient salt removal performance and water permeability can be obtained.
  • the polyfunctional amine aqueous solution may contain surfactants, organic solvents, alkaline compounds, antioxidants, etc. as long as they do not interfere with the reaction between the polyfunctional amine and the polyfunctional acid halide. good.
  • surfactants include compounds having a polyoxyalkylene structure, a fatty acid ester structure, or a hydroxyl group.
  • polyoxyalkylene structures include -(CH 2 CH 2 O) n -, -(CH 2 CH 2 (CH 3 )O) n -, -(CH 2 CH 2 CH 2 O) n -, -(CH 2 CH 2 CH 2 CH 2 O) n -, and the like.
  • Fatty acid ester structures include fatty acids having long chain aliphatic groups. The long-chain aliphatic group may be linear or branched, and fatty acids include stearic acid, oleic acid, lauric acid, palmitic acid and salts thereof.
  • fatty acid esters derived from oils and fats such as beef tallow, palm oil, and coconut oil.
  • Surfactants having a sulfo group include 1-hexanesulfonic acid, 1-octanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, perfluorobutanesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, and octylbenzene. sulfonic acid and the like.
  • Surfactants having a hydroxyl group include ethylene glycol, propylene glycol, 2-propanediol, 1,4-butanediol, glycerin, sorbitol, glucose and sucrose.
  • a surfactant has the effect of improving the wettability of the surface of the porous support layer and reducing the interfacial tension between the aqueous amine solution and the nonpolar solvent.
  • organic solvents include chain amide compounds and cyclic amide compounds.
  • chain amide compounds include N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide and N,N-diethylacetamide.
  • Cyclic amide compounds include, for example, N-methylpyrrolidinone, ⁇ -butyrolactam, and ⁇ -caprolactam.
  • the organic solvent may act as a catalyst for the interfacial polycondensation reaction, and the addition of the organic solvent may improve the efficiency of the interfacial polycondensation reaction.
  • Alkaline compounds include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, carbonates and hydrogen carbonates inorganic compounds such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, and tetramethylammonium hydroxide. and organic compounds such as tetraethylammonium hydroxide.
  • antioxidants examples include phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.
  • Phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol, 2,2′-methylenebis(4-ethyl-6-tert-butylphenol ) and tetrakis-[methylene-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate]methane.
  • Amine antioxidants include phenyl- ⁇ -naphthylamine, ⁇ -naphthylamine, N,N'-di-sec-butyl-p-phenylenediamine, phenothiazine, N,N'-diphenyl-p-phenylenediamine, and the like. be done.
  • sulfur-based antioxidants examples include dilauryl 3,3'-thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, and dimyristyl 3,3'-thiodipropionate.
  • Phosphorus antioxidants include triphenylphosphite, octadecylphosphite and trinonylphenylphosphite.
  • antioxidants include, for example, ascorbic acid or its alkali metal salts, sterically hindered phenol compounds such as dibutylhydroxytoluene and butylhydroxyanisole, isopropyl citrate, dl- ⁇ -tocopherol, nordihydroguaiaretic acid, and gallic acid. and propyl acid.
  • the contact of the polyfunctional amine aqueous solution with the porous support layer is preferably carried out uniformly and continuously on the surface of the porous support layer.
  • a method of applying an aqueous solution of polyfunctional amine to the porous support layer, or a method of immersing the porous support layer in an aqueous solution of polyfunctional amine can be used.
  • the contact time between the porous support layer and the polyfunctional amine aqueous solution is preferably in the range of 1 to 10 minutes, more preferably in the range of 1 to 3 minutes.
  • the support film after contact with the polyfunctional amine aqueous solution is held vertically and the excess aqueous solution is allowed to flow down naturally.
  • a method of forcibly removing the liquid by blowing an air stream of nitrogen or the like from an air nozzle can be used.
  • the film surface can be dried to partially remove water from the aqueous solution.
  • Step (ii) contacts the porous support layer with a polyfunctional acid halide or an organic solvent solution containing the polyfunctional acid halide to form a polyamide on the porous support layer by interfacial polycondensation. is a step.
  • Step (ii) forms a layer of polyfunctional acid halide solution on top of the layer of aqueous amine solution on the porous support layer that had been formed in step (i).
  • Examples of the method of contacting the polyfunctional acid halide solution with the porous support layer include coating or dropping.
  • coating includes other contact methods unless otherwise specified.
  • the concentration of the polyfunctional acid halide in the organic solvent solution is preferably within the range of 0.01 to 10% by weight, more preferably within the range of 0.02 to 2.0% by weight.
  • concentration of the polyfunctional acid halide is 0.01% by weight or more, a sufficient reaction rate can be obtained, and when it is 10% by weight or less, side reactions can be suppressed.
  • the organic solvent is preferably one that is immiscible with water, dissolves the polyfunctional acid halide, does not destroy the support film, and is inert to the polyfunctional amine compound and the polyfunctional acid halide. Anything is fine.
  • Preferred examples of organic solvents include hydrocarbon compounds such as n-hexane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, isodecane and isododecane.
  • the polyfunctional acid halide solution preferably further contains water.
  • the polyfunctional acid halide solution contains water, and the water content in the layer of the polyfunctional acid halide solution has the above gradient, so that the upper thickness and the lower thickness of the thin film in the pleated structure can be changed. can.
  • the abrasion resistance of the composite semipermeable membrane can be improved, and a composite semipermeable membrane having both abrasion resistance and water permeability can be obtained.
  • the method for forming a concentration gradient in the water content of the layer of the polyfunctional acid halide solution is not limited to a specific form.
  • a polyfunctional acid halide solution) may be first applied to the porous support layer, followed by a polyfunctional acid halide solution with a high water content (second polyfunctional acid halide solution).
  • the water content of the first polyfunctional acid halide solution is preferably 500 ppm or less. By setting the water content of the first polyfunctional acid halide solution to 500 ppm or less, the reactivity with amine is improved, and the lower thickness of the thin film can be increased.
  • the water content of the first polyfunctional acid halide solution is more preferably 200 ppm or less, still more preferably 150 ppm or less. Also, the water content of the first polyfunctional acid halide solution is preferably greater than 0 ppm, more preferably 5 ppm or more, and even more preferably 40 ppm or more.
  • the water content of the second polyfunctional acid halide solution is preferably larger than the water content of the first polyfunctional acid halide solution and is 500 ppm or less, more preferably 300 ppm or less, and still more preferably. 150 ppm or less.
  • the water content of the second polyfunctional acid halide solution is larger than that of the first polyfunctional acid halide solution and is preferably 0 ppm or more, more preferably 20 ppm or more, and further. Preferably it is 40 ppm or more.
  • the number of times the polyfunctional acid halide solution is applied to the porous support layer is preferably 2 to 6 times, more preferably 2 times.
  • the polyfunctional acid halide solution more preferably contains a compound represented by the following chemical formula (I) (hereinafter referred to as compound (I)).
  • R 1 and R 2 are each independently an alkyl group having 1 or more carbon atoms.
  • aromatic esters are preferred, and phthalates are particularly preferred.
  • phthalates include dibutyl phthalate, dibutylbenzyl phthalate, diethylhexyl phthalate, diisodecyl phthalate, diisonoyl phthalate, dioctyl phthalate, diisobutyl phthalate, diethyl phthalate, dimethyl phthalate, Diisooctyl phthalate, dipropyl phthalate, dicyclohexyl phthalate, dinonyl phthalate, dibenzyl phthalate, dihexyl phthalate, dibenzyl phthalate, diphenyl phthalate, bis(2-ethylhexyl) phthalate.
  • the organic solvent containing the polyfunctional acid halide from the polyfunctional amine aqueous solution side When the amine diffuses to the side, the presence of the compound (I) moderates the amine concentration gradient, and as a result, the formation time of the protrusions in the separation functional layer is sufficiently long, and the formation of the protrusion structure is facilitated. , both the surface area and thickness of the protrusions are considered to increase.
  • the polyfunctional acid halide solution to which the compound (I) is added further contains water.
  • the concentration gradient from the amine aqueous solution side to the polyfunctional acid halide solution side varies in the film surface direction, and it is thought that the protrusion height and protrusion angle also change.
  • the concentration of compound (I) in the polyfunctional acid halide solution can be changed depending on the type of compound (I) added, but is preferably within the range of 5 ppm to 500 ppm. It is also preferable to add 10 ppm or more of water to the polyfunctional acid halide solution.
  • the polyfunctional acid halide solution contains, as a further additive, a monofunctional acid halide or trimesic acid chloride obtained by hydrolysis of one acid chloride group (hereinafter referred to as monohydrolyzed TMC), or two acid chloride groups. may contain hydrolyzed trimesic acid chloride (hereinafter referred to as dihydrolyzed TMC).
  • monohydrolyzed TMC monofunctional acid halide or trimesic acid chloride obtained by hydrolysis of one acid chloride group
  • dihydrolyzed TMC hydrolyzed trimesic acid chloride
  • Monofunctional acid halides include, for example, benzoyl fluoride, benzoyl chloride, benzoyl bromide, methanoyl fluoride, methanoyl chloride, methanoyl bromide, ethanoyl fluoride, ethanoyl chloride, ethanoyl bromide, propanoyl fluoride propanoyl chloride, propanoyl bromide, propenoyl fluoride, propenoyl chloride, propenoyl bromide, butanoyl fluoride, butanoyl chloride, butanoyl bromide, butenoyl fluoride, butenoyl chloride and butenoyl Mention may be made of at least one compound selected from the group consisting of bromides.
  • the temperature of the film surface immediately after contacting the polyfunctional amine aqueous solution and the polyfunctional acid halide solution is preferably in the range of 25 to 60°C, more preferably in the range of 30 to 50°C. .
  • the temperature of the membrane surface is preferably in the range of 25 to 60°C, more preferably in the range of 30 to 50°C. .
  • the support film may be heated, or a heated organic solvent solution of a polyfunctional acid halide may be brought into contact.
  • the temperature of the film surface immediately after contacting the polyfunctional amine aqueous solution and the polyfunctional acid halide solution can be measured with a non-contact thermometer such as a radiation thermometer.
  • the excess solvent is drained off. do it.
  • a method for draining the liquid for example, a method can be used in which the film is held vertically and excess organic solvent is allowed to naturally flow down to remove.
  • the holding time in the vertical direction is preferably 1 to 5 minutes, more preferably 1 to 3 minutes. When this time is 1 minute or more, a sufficient amount of polyamide can be formed as the separation functional layer, and when it is 5 minutes or less, the organic solvent does not evaporate too much, and the occurrence of film defects can be suppressed. can be done.
  • a support film having a substrate and a porous support layer may be formed by coating a polymer solution on a substrate and then solidifying the polymer, or coating a polymer solution on a substrate such as glass. It may be formed by coating, then solidifying and peeling from the substrate.
  • polysulfone when forming a support membrane using polysulfone, polysulfone is dissolved in N,N-dimethylformamide (hereinafter referred to as DMF) to obtain a polymer solution, and this solution is spread on a substrate to a certain thickness. and wet coagulate it in water. According to this method, it is possible to obtain a porous support layer having fine pores with a diameter of several tens of nanometers or less on most of the surface.
  • DMF N,N-dimethylformamide
  • the composite semipermeable membrane after the separation functional layer is formed is preferably 50 to 150°C, more preferably 70 to 130°C, preferably 1 second to 10 minutes, more preferably Salt removal performance and water permeability can be improved by adding a step of hot water treatment for 1 to 8 minutes.
  • the composite semipermeable membrane is contacted with a compound (A) that reacts with primary amino groups on the separation functional layer after hydrothermal treatment to produce a diazonium salt or a derivative thereof, and then reacted with the compound (A).
  • a compound (A) that reacts with primary amino groups on the separation functional layer after hydrothermal treatment to produce a diazonium salt or a derivative thereof, and then reacted with the compound (A).
  • Examples of the compound (A) that reacts with a primary amino group to form a diazonium salt or derivative thereof include aqueous solutions of nitrous acid and its salts, nitrosyl compounds, and the like. Since an aqueous solution of nitrous acid or a nitrosyl compound tends to generate gas and decompose, it is preferable to sequentially generate nitrous acid by, for example, reacting nitrite with an acidic solution. In general, nitrite reacts with hydrogen ions to produce nitrous acid (HNO 2 ), which can be efficiently produced when the pH of the aqueous solution is preferably 7 or less, more preferably 5 or less, and even more preferably 4 or less. Among them, an aqueous solution of sodium nitrite which is reacted with hydrochloric acid or sulfuric acid in an aqueous solution is particularly preferable because it is easy to handle.
  • the concentration of sodium nitrite is preferably 0.01 to 1% by weight. Range. When sodium nitrite is within the above range, the effect of producing a sufficient diazonium salt or derivative thereof can be obtained, and the solution can be easily handled.
  • the temperature of the compound is preferably 15°C to 45°C. When the temperature of the compound is within the above range, the reaction does not take too long and the nitrous acid does not decompose too quickly and is easy to handle.
  • the contact time between the primary amino group and the compound may be any time during which the diazonium salt and/or derivative thereof is formed. is necessary. Therefore, it is preferable that the concentration of the solution is within 10 minutes, and more preferably within 3 minutes.
  • the method of contacting the primary amino group with the compound is not particularly limited, and a solution of the compound may be applied (coated) or the composite semipermeable membrane may be immersed in a solution of the compound. .
  • a solution of the compound may be applied (coated) or the composite semipermeable membrane may be immersed in a solution of the compound.
  • the solvent for dissolving the compound any solvent may be used as long as the compound is dissolved and the composite semipermeable membrane is not eroded.
  • the solution of the compound may contain surfactants, acidic compounds, alkaline compounds, etc., as long as they do not interfere with the reaction between the primary amino group and the reagent.
  • the composite semipermeable membrane produced by the diazonium salt or its derivative is brought into contact with a water-soluble compound (B) that reacts with the diazonium salt or its derivative.
  • the water-soluble compound (B) that reacts with a diazonium salt or a derivative thereof includes chloride ion, bromide ion, cyanide ion, iodide ion, fluoroboric acid, hypophosphorous acid, sodium hydrogen sulfite, sulfite ion. , aromatic amines, phenols, hydrogen sulfide, thiocyanic acid and the like.
  • the concentration and time for contacting the water-soluble compound (B) that reacts with the diazonium salt or its derivative with the composite semipermeable membrane formed by the diazonium salt or the diazonium salt derivative can be appropriately adjusted to obtain the desired effect.
  • the temperature at which the water-soluble compound (B) that reacts with the diazonium salt or its derivative and the composite semipermeable membrane formed by the diazonium salt or the diazonium salt derivative is brought into contact is preferably 10 to 90°C. Within this temperature range, the reaction proceeds easily, and on the other hand, the decrease in the amount of permeated water due to shrinkage of the polymer does not occur.
  • the composite semipermeable membrane of the present embodiment manufactured in this way includes a raw water channel material such as a plastic net, a permeate water channel material such as tricot, and, if necessary, pressure resistance. It is preferably used as a spiral-type composite semipermeable membrane element by being wound around a cylindrical water collection tube having a large number of holes along with a film for heightening. Furthermore, a composite semipermeable membrane module in which these elements are connected in series or in parallel and housed in a pressure vessel can also be formed.
  • the above composite semipermeable membranes, their elements, and modules can be combined with a pump that supplies raw water to them, a device that preprocesses the raw water, and the like to form a fluid separation device.
  • a separator By using this separator, it is possible to separate raw water into permeated water such as drinking water and concentrated water that has not permeated through the composite semipermeable membrane, thereby obtaining desired water.
  • the operating pressure during permeation is preferably 0.5 MPa or more and 10 MPa or less.
  • the raw water to be treated by the composite semipermeable membrane according to the present embodiment is, for example, a liquid mixture containing 50 mg/L to 100 g/L of salts (Total Dissolved Solids) such as seawater, brackish water, and waste water. is mentioned.
  • salt refers to the total dissolved solids content and is expressed as "mass divided by volume” or "weight ratio". According to the definition, it can be calculated from the weight of the residue after evaporating the solution filtered through a 0.45 ⁇ m filter at a temperature of 39.5 to 40.5 ° C., but more easily converted from the practical salinity (S) .
  • membrane permeation flux (membrane permeation flux) In the test described in the preceding paragraph, the membrane permeation flux (m 3 /m 2 /day) was expressed as the permeation water amount (cubic meter) per day per square meter of the membrane surface of the feed water (evaluation raw water). .
  • Example 1 The support film obtained in Reference Example 1 was immersed in an aqueous solution containing 4% by weight of m-phenylenediamine (m-PDA) for 2 minutes, and slowly lifted vertically. After removing excess aqueous solution from the surface of the support film by blowing nitrogen from an air nozzle, 0.12% by weight of trimesic acid chloride (TMC) in n-decane solution was used as the first and second polyfunctional acid halide solutions. They were applied to the support film in this order. The water contents of the first and second polyfunctional acid halide solutions are shown in Table 1.
  • TMC trimesic acid chloride
  • Examples 2 to 17 A composite semipermeable was prepared in the same manner as in Example 1, except that the presence or absence of dioctyl phthalate and the water content in the first and second polyfunctional acid halide solutions were changed to the concentrations shown in Table 1. A membrane was obtained. The additive concentrations of dioctyl phthalate in the first and second polyfunctional acid halide solutions are shown in Table 1.
  • Comparative Example 6 The same polyester nonwoven fabric as in Reference Example 1 was used as the base material. A first polysulfone solution (14.0 wt % DMF solution) and a second polysulfone solution (17.0 wt % DMF solution) were prepared.
  • the first polysulfone solution and the second polysulfone solution are discharged simultaneously, the first polysulfone solution on the substrate, and the second polysulfone solution on the first polysulfone solution.
  • the first polysulfone solution was cast to a thickness of 180 ⁇ m and the second polysulfone solution was cast to a thickness of 20 ⁇ m, and immediately immersed in pure water and allowed to stand for 5 minutes to prepare a supporting membrane.
  • a 2.8% by weight aqueous solution of m-PDA was applied to the support film obtained above and allowed to stand for 2 minutes, and then nitrogen was blown from an air nozzle to remove excess aqueous solution from the surface of the support film.
  • an n-decane solution containing 0.10% by weight of trimesic acid chloride as a first polyfunctional acid halide solution is applied onto the support film so that the surface is completely wetted, and left to stand for 10 seconds. After that, the membrane was held vertically for 1 minute to drain excess solution from the membrane.
  • the membrane thus obtained was washed with hot water at 90° C. for 2 minutes to obtain a composite semipermeable membrane.
  • the water content of the first polyfunctional acid halide solution is as shown in Table 1.
  • Examples 1-17 had higher water permeability and salt removability after rubbing than Comparative Examples 1-6.
  • the composite semipermeable membrane of the present invention is particularly suitable for desalting seawater and brackish water.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
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  • Separation Using Semi-Permeable Membranes (AREA)
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EP22791832.3A EP4327920A4 (en) 2021-04-22 2022-04-22 COMPOSITE SEMI-PERMEABLE MEMBRANE
CN202280030071.9A CN117202982B (zh) 2021-04-22 2022-04-22 复合半透膜
KR1020237035604A KR102685078B1 (ko) 2021-04-22 2022-04-22 복합 반투막
US18/287,786 US12161978B2 (en) 2021-04-22 2022-04-22 Composite semipermeable membrane
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