WO2019189547A1 - Membrane d'osmose directe et ses utilisations - Google Patents

Membrane d'osmose directe et ses utilisations Download PDF

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Publication number
WO2019189547A1
WO2019189547A1 PCT/JP2019/013521 JP2019013521W WO2019189547A1 WO 2019189547 A1 WO2019189547 A1 WO 2019189547A1 JP 2019013521 W JP2019013521 W JP 2019013521W WO 2019189547 A1 WO2019189547 A1 WO 2019189547A1
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Prior art keywords
forward osmosis
osmosis membrane
resin
structural unit
acid group
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PCT/JP2019/013521
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English (en)
Japanese (ja)
Inventor
田原　修二
丸子　展弘
ホキョン ショーン
シュラブ フンチョー
ジュン ユン キム
スンギル リム
バン ヒュイ トゥラン
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三井化学株式会社
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Priority to JP2020509304A priority Critical patent/JP6944044B2/ja
Publication of WO2019189547A1 publication Critical patent/WO2019189547A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/52—Polyethers
    • B01D71/522—Aromatic polyethers
    • 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
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1213—Laminated layers
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group

Definitions

  • the present invention relates to a forward osmosis membrane and its use.
  • the semipermeable membrane is useful for selectively separating a predetermined component from a liquid mixture or a gas mixture, and is suitably used, for example, for producing high-purity water or separating a specific solute from a solution.
  • the reverse osmosis method which is the mainstream in the past, exposes the reverse osmosis membrane to high pressure. Therefore, as a reverse osmosis membrane, in order to obtain high strength, a porous support (for example, non-woven fabric), a porous polymer layer (for example, polysulfone layer), and a layer that actually functions as a semipermeable membrane (skin layer, separation layer) A composite semipermeable membrane obtained by laminating in this order is the mainstream.
  • a porous support for example, non-woven fabric
  • a porous polymer layer for example, polysulfone layer
  • a layer that actually functions as a semipermeable membrane skin layer, separation layer
  • the forward osmosis method uses a osmotic pressure generated between aqueous solutions of different solute concentrations separated by a forward osmosis membrane as a driving force to drive a high salt concentration draw solution from a low salt concentration feed solution side (for example, fresh water). Water moves to the side (eg seawater). For this reason, there is no need for high pressure application or membrane strength to overcome the osmotic pressure as in the reverse osmosis method, and the advantages such as excellent energy saving and simple configuration of the osmotic membrane can be expected.
  • the forward osmosis membrane having a large water permeation flux from the feed solution tends to increase the amount of salt reverse diffusion from the draw solution. It has also been found that the amount of salt back-diffusion per water permeation flux is not necessarily low. Therefore, it can be said that the conventional forward osmosis membrane has room for further improvement from the viewpoint of achieving both high water permeability and high salt rejection.
  • a semipermeable membrane containing at least two types of protonic acid group-containing aromatic polyether resins having different molar fractions of structural units having protonic acid groups is used.
  • a forward osmosis membrane having a high water permeability and a high salt rejection can be produced, and the present invention has been completed.
  • the present invention relates to the following [1] to [15].
  • a forward osmosis membrane comprising a semipermeable membrane and a porous substrate disposed on at least one surface thereof, wherein the semipermeable membrane has an aromatic polyether resin having a protonic acid group-containing structural unit ( A), wherein the resin (A) has a proton acid group-containing aromatic polyether resin (A1) and a proton acid group having a larger molar fraction of the proton acid group-containing structural unit than the resin (A1).
  • a forward osmosis membrane comprising at least the containing aromatic polyether resin (A2).
  • the resins (A1) and (A2) each have a structural unit (1) represented by the following formula (1) and a structural unit (2) represented by the following formula (2),
  • the molar fraction of the structural unit (1) relative to the total amount of the structural unit (1) and the structural unit (2) is larger than those of the resin (A1).
  • the forward osmosis membrane according to any one of the above.
  • R 1 to R 10 are each independently H, Cl, F, CF 3 or C m H 2m + 1 (m represents an integer of 1 to 10); At least one of R 1 to R 10 is C m H 2m + 1 (m represents an integer of 1 to 10), Two or more of R 1 to R 10 may be present in each aromatic ring, and when two or more C m H 2m + 1 are present in one aromatic ring, each C m H 2m + 1 is They may be the same or different.
  • X 1 to X 5 are each independently H, Cl, F, CF 3 or a protonic acid group, At least one of X 1 to X 5 is a protonic acid group; X 1 to X 5 may each be present in two or more in an aromatic ring, and when two or more protonic acid groups are present in one aromatic ring, each protonic acid group may be the same as or different from each other. It may be.
  • a 1 to A 6 are each independently a direct bond, —CH 2 —, —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, —O— or —CO—.
  • the absolute value of the difference in molar fraction of the structural unit (1) with respect to the total amount of the structural unit (1) and the structural unit (2) is The forward osmosis membrane according to [6] or [7], which is 0.03 to 0.6.
  • the forward osmosis membrane according to any one of [1] to [10], which includes the semipermeable membrane and the porous base material disposed on both surfaces thereof.
  • the porous substrate has an air permeability of 100 to 400 cm 3 / cm 2 / s and a thickness of 50 to 700 ⁇ m as measured by Method A (Fragile method) described in JIS L 1096.
  • Method A Frazier method
  • the forward osmosis membrane according to any one of 1] to [11].
  • a forward osmosis membrane element comprising the forward osmosis membrane according to any one of [1] to [12] and a spacer.
  • a forward osmosis membrane module in which the forward osmosis membrane element according to [13] is accommodated in a container.
  • a forward osmosis membrane having an excellent balance between water permeability and salt rejection specifically, a forward osmosis membrane having high water permeability and a high salt rejection can be provided.
  • FIG. 1 is a schematic diagram of an apparatus used for evaluating the separation performance of a forward osmosis membrane in Examples.
  • the forward osmosis membrane of the present invention comprises a semipermeable membrane and a porous substrate disposed on at least one surface thereof.
  • the semipermeable membrane comprises an aromatic polyether resin (A) having a proton acid group-containing structural unit.
  • the forward osmosis membrane of the present invention includes the semipermeable membrane and the porous substrate disposed on at least one surface thereof, and can achieve a high water permeation flux and a high salt rejection. .
  • the semipermeable membrane includes an aromatic polyether resin (A) having a proton acid group-containing structural unit, and the resin (A) includes a proton acid group-containing aromatic polyether resin (A1) and the resin.
  • the resins (A), (A1) and (A2) are also simply referred to as “resin (A)”, “resin (A1)” and “resin (A2)”, respectively.
  • the protonic acid group means a functional group that easily releases protons or a hydrogen atom substituted with Na or K.
  • Examples thereof include a sulfonic acid group (—SO 3 H), a carboxylic acid group, Acid group (—COOH), phosphonic acid group (—PO 3 H 2 ), alkyl sulfonic acid group (— (CH 2 ) n SO 3 H), alkyl carboxylic acid group (— (CH 2 ) n COOH), alkyl phosphone
  • Examples include an acid group (— (CH 2 ) n PO 3 H 2 ), a hydroxyphenyl group (—C 6 H 4 OH), and those having a terminal hydrogen atom substituted with Na or K.
  • n is an integer of 1 to 10.
  • the molar fraction of the proton acid group-containing structural unit is the following ratio: the number of proton acid group-containing structural units / the total number of structural units constituting the aromatic polyether resin.
  • the structural unit (1) represented by Formula (1) mentioned later is mentioned, for example.
  • the resin (A2) having a large molar fraction of the proton acid group-containing structural units since at least two kinds of aromatic polyether resins having different molar fractions of the proton acid group-containing structural units are used, the resin (A2) having a large molar fraction of the proton acid group-containing structural units. As a result, the water permeability is improved, and the reverse diffusion of the salt can be prevented by the resin (A1) having a small molar fraction of the proton acid group-containing structural unit.
  • both the resin (A1) and the resin (A2) are aromatic polyether resins, it is considered that their dispersion is good. For this reason, it is considered that a dense and multi-stage pseudo continuous layer of (A1) / (A2) units is formed, so that the water permeation characteristics and the effect of suppressing salt reverse diffusion can be efficiently exhibited. It will be.
  • the semipermeable membrane preferably has a concentration of protonic acid groups derived from the resin (A) having a gradient in the thickness direction of the semipermeable membrane.
  • the concentration gradient may be a mode in which the concentration continuously increases or a mode in which the concentration increases stepwise.
  • the semipermeable membrane may be a laminated film having a layer (L1) containing a resin (A1) and a layer (L2) containing a resin (A2).
  • the ratio of the thickness of the layer (L1) to the layer (L2) (the thickness of L1: the thickness of L2) is usually 5:95 to 80:20, preferably 20:80 to 60:40.
  • Such a multilayer structure provides higher water permeation flux and salt rejection.
  • This mode can be said to be a preferable mode from the viewpoint of more reliably speaking the effect of the constitution of the above (A1) / (A2) unit.
  • the concentration gradient of the protonic acid group derived from the resin (A) means that the concentration of the protonic acid group contained in the resin (A) changes in the thickness direction of the semipermeable membrane.
  • the concentration gradient can be confirmed by analyzing the concentration distribution of sulfur atoms in the semipermeable membrane cross section by element mapping.
  • the forward osmosis membrane when used, the forward osmosis membrane is arranged so that the side with the higher proton acid group concentration faces the feed solution side and the side with the lower proton acid group concentration faces the draw solution side in the semipermeable membrane. It is preferable.
  • the forward osmosis membrane in the semipermeable membrane, the forward osmosis membrane is arranged so that the layer (L2) containing the resin (A2) faces the feed solution side and the layer (L1) containing the resin (A1) faces the draw solution side. It is preferable to do. With such an embodiment, a higher water permeation flux and salt rejection can be obtained.
  • the semipermeable membrane is preferably formed from a mixture containing at least a resin (A1) and a resin (A2).
  • the semipermeable membrane has a structure separated into at least two phases corresponding to each of the resin (A1) and the resin (A2). This phase separation structure provides higher water permeation flux and salt rejection.
  • the mass ratio (A1: A2) of the resin (A1) to the resin (A2) is usually 10:90 to 90:10, preferably 30:70 to 70:30.
  • phase separation structure can be confirmed by observation with an electron microscope (TEM or SEM).
  • TEM or SEM electron microscope
  • a sea-island structure, an interpenetrating structure, and the like are conceivable, but an interpenetrating structure is more preferable from the viewpoint of preventing salt reverse diffusion from the draw solution.
  • the resin (A1) having a small molar fraction of the protonic acid group-containing structural unit forms a sea phase
  • the resin (A2) having a large molar fraction forms an island phase.
  • a semipermeable membrane using the aromatic polyether resin (A) as a raw material can be produced as a self-supporting membrane.
  • water permeability is high.
  • a forward osmosis membrane having a high salt rejection can be obtained.
  • the semipermeable membrane is substantially composed only of the aromatic polyether resin (A), but is small in amount so as not to impair the effects of the present invention (for example, 1% by mass or less, or 0.1% by mass). The following may be included.
  • the thickness of the semipermeable membrane is usually 3.0 ⁇ m or less, preferably 0.01 to 3.0 ⁇ m, more preferably 0.01 to 1.5 ⁇ m.
  • a forward osmosis membrane using a semipermeable membrane having a thickness within this range has a sufficient membrane strength and exhibits a sufficiently large water permeation flux for practical use.
  • the thickness of the semipermeable membrane can be controlled by the production conditions of the semipermeable membrane, for example, the temperature and pressure during press molding, the varnish concentration during casting and the coating thickness.
  • the semipermeable membrane preferably has as little unevenness in thickness as possible. Since pressure is applied to the semipermeable membrane during water permeation, stress concentration may occur if there is uneven thickness. For this reason, when it uses as a water separation membrane, the durability as a membrane may fall.
  • the semipermeable membrane comprises an aromatic polyether resin (A) having a proton acid group-containing structural unit.
  • the resin (A) includes at least the resins (A1) and (A2) described above.
  • Resins (A1) and (A2) preferably have a structural unit (1) represented by the following formula (1) and a structural unit (2) represented by the following formula (2), respectively.
  • the molar fraction of the structural unit (1) with respect to the total amount of the structural unit (1) and the structural unit (2) the molar fraction of the resin (A2) is more than the molar fraction of the resin (A1). Is also preferably large.
  • the structural units (1) in these resins (A1) and (A2) may be the same or different, and the structural units (2) in the resins (A1) and (A2) may be the same or different. .
  • i, j, k and l each independently represent 0 or 1;
  • R 1 to R 10 are each independently H, Cl, F, CF 3 or C m H 2m + 1 (m represents an integer of 1 to 10), and C m H 2m + 1 is Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
  • At least one of R 1 to R 10 is C m H 2m + 1 (m represents an integer of 1 to 10).
  • R 1 to R 10 may be present in each aromatic ring, and when two or more C m H 2m + 1 are present in one aromatic ring, each C m H 2m + 1 is They may be the same or different.
  • X 1 to X 5 are each independently H, Cl, F, CF 3 or a protonic acid group.
  • At least one of X 1 to X 5 is a protonic acid group.
  • X 1 to X 5 may each be present in two or more in an aromatic ring, and when two or more protonic acid groups are present in one aromatic ring, each protonic acid group may be the same as or different from each other. It may be.
  • a 1 to A 6 are each independently a direct bond, —CH 2 —, —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, —O— or —CO—, and A 1 At least one of ⁇ A 6 is preferably —CO—.
  • the protonic acid group means a functional group that easily releases protons or a hydrogen atom substituted with Na or K.
  • Examples thereof include a sulfonic acid group (—SO 3 H), a carboxylic acid group, Acid group (—COOH), phosphonic acid group (—PO 3 H 2 ), alkyl sulfonic acid group (— (CH 2 ) n SO 3 H), alkyl carboxylic acid group (— (CH 2 ) n COOH), alkyl phosphone
  • Examples include an acid group (— (CH 2 ) n PO 3 H 2 ), a hydroxyphenyl group (—C 6 H 4 OH), and those having a terminal hydrogen atom substituted with Na or K.
  • n is an integer of 1 to 10.
  • the protonic acid group is preferably —C n ′ H 2n ′ —SO 3 Y (n ′ is an integer of 0 to 10, preferably 0, and Y is H, Na or K).
  • Examples of the structural unit (1) include structural units represented by the following formula (1-1) or the following formula (1-2). In these structures, A 1 is —CO—. Is preferred,
  • Examples of the structural unit (2) include structural units represented by the following formula (2-1) or the following formula (2-2).
  • the molar fraction of the structural unit (1) with respect to the total amount of the structural unit (1) and the structural unit (2) is preferable because a semipermeable membrane with high water permeability can be formed. Is not less than 0.1, more preferably not less than 0.2, and further preferably not less than 0.25; and since it can form a semipermeable membrane having a high salt rejection and not gelling, it is preferably not more than 0.9. More preferably, it is 0.7 or less, and further preferably 0.6 or less.
  • the mole of the resin (A1) is preferably 0.03 to 0.6, more preferably 0.1 to 0.4.
  • the aromatic polyether resin contained in resin (A) is not limited to 2 types.
  • the resin (A) includes three or more aromatic polyether resins having different molar fractions of the structural unit (1), the above definition of the difference in the molar fraction of the structural unit (1) is at least one set of “ What is necessary is just to satisfy
  • the aromatic polyether resin (A) may further contain a structural unit derived from a polyfunctional compound described later.
  • the aromatic polyether resin (A) may be a crosslinked body or a non-crosslinked body.
  • the weight average molecular weight (Mw) measured by the following conditions (1) to (6) using the GPC (Gel Permeation Chromatography) method of the aromatic polyether resin (A) is preferably 70,000 or more. Preferably it is 80,000 or more, More preferably, it is 90,000 or more. When the molecular weight is in the above range, the obtained semipermeable membrane has high mechanical properties and is not easily broken during film formation or use.
  • the weight average molecular weight is preferably 180,000 or less from the viewpoint of gel generation rate.
  • the aromatic polyether resin (A) can be obtained by condensation of a monomer having an aromatic ring according to a conventionally known method (for example, a method described in International Publication No. 2003/33566). For example, the following formulas (1a) and (2a)
  • the resin can be obtained by condensation polymerization with a monomer having a hydroxyl group represented by:
  • Y is a halogen atom, and the meanings of the other symbols are the same as the meanings of the same symbols used in the above formulas (1) and (2).
  • Preferred examples of the halogen atom include fluorine and chlorine.
  • Examples of the monomer represented by the above formula (2b) include: 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) propane, 1,1,1 , 3,3,3-hexafluoro-2,2-bis (4-hydroxyphenyl) propane, 1,4-bis (4-hydroxyphenyl) benzene, ⁇ , ⁇ '-bis (4-hydroxyphenyl) -1 , 4-dimethylbenzene, ⁇ , ⁇ '-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene, ⁇ , ⁇ '-bis (4-hydroxyphenyl) -1,3-diisopropylbenzene, 1,4- Aromatic dihydroxylation of bis
  • a polyfunctional compound may be copolymerized with the monomer.
  • the aromatic polyether resin (A) can take a finely crosslinked structure.
  • Polyfunctional compounds include those having 3 or more hydroxyl groups in one molecule, such as (2,4-dihydroxyphenyl) (4-hydroxyphenyl) methanone, 4- [1- (4-hydroxyphenyl) -1 -Methylethyl] -1,3-benzenediol, 4-[(2,3,5-trimethyl-4-hydroxyphenyl) methyl] -1,3-benzenediol, 4-[(4-hydroxyphenyl) methyl] -1,2,3-benzenetriol, (4-hydroxyphenyl) (2,3,4-trihydroxyphenyl) methanone, 4-[(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2 , 3-Benzenetriol, 4-[(2,3,5-trimethyl-4-hydroxyphenyl) methyl] -1,2,3-benzenetriol, 4,4 ′-[1 , 4-phenylenebis (1-methylethylidene)] bis [benzene-1,2-diol], 5,5
  • copolymerization amounts are preferably from the viewpoint of preventing a decrease in solvent solubility of the aromatic polyether resin (A), a decrease in fluidity during film formation of the resin, and a decrease in elongation rate of the semipermeable membrane.
  • 0 to 8 mol% / total OH equivalent that is, 0 to about 0 to about OH groups (100 mol%) of the monomer of formula (1b), the monomer of formula (2b) and the polyfunctional monomer) 8 mol% is an OH group derived from a polyfunctional monomer.
  • the aromatic polyether resin (A) has a molecular structure that is basically linear, and even if it has a cross-linked structure derived from the polyfunctional compound, the amount thereof is very small. Excellent in properties. Therefore, it can be set as the form of the varnish which melt
  • the solvent examples include, but are not limited to, water, alcohols such as methanol, ethanol, 1-propanol, 2-propanol and butanol, hydrocarbons such as toluene and xylene, and halogenated carbonization such as methyl chloride and methylene chloride.
  • ethers such as dichloroethyl ether, 1,4-dioxane and tetrahydrofuran
  • fatty acid esters such as methyl acetate and ethyl acetate
  • ketones such as acetone and methyl ethyl ketone
  • cellosolve such as 2-methoxyethanol and 2-ethoxyethanol
  • aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and dimethyl carbonate.
  • concentration in a varnish can be selected with the usage method of a varnish, Preferably it is 1 to 80 mass%.
  • the tensile modulus of the semipermeable membrane is preferably 0.8 to 2.0 GPa, more preferably 1.2 to 1.6 GPa.
  • the tensile strength at break of the semipermeable membrane is preferably 40 MPa or more, and the upper limit is, for example, 100 MPa.
  • the elongation percentage of the semipermeable membrane is preferably 40% or more, and the upper limit is, for example, 200%.
  • test piece of length x width x thickness 100 mm x 10 mm x 5 ⁇ m was prepared, pulled at a speed of 50 mm / min using a tensile tester, and the strength when the test piece was cut (ruptured) (test the tensile load value) The value divided by the cross-sectional area of the piece) and the elongation rate are obtained.
  • Elongation rate is calculated by the following formula.
  • Elongation rate (%) 100 ⁇ (L ⁇ L 0 ) / L 0 (L 0 : test piece length before test L: test piece length at break)
  • the tensile elastic modulus is a value obtained by dividing the load at break by the cross-sectional area of the test piece and the strain at break, that is, (L ⁇ L 0 ) / L 0 .
  • the tensile breaking strength and the elongation can be increased by increasing the molecular weight of the aromatic polyether resin (A), for example.
  • Solubility and mass reduction rate The solubility of the semipermeable membrane in dimethyl sulfoxide (hereinafter also referred to as “DMSO”) and water can be evaluated by the following mass reduction rates.
  • the mass reduction rate is preferably less than 2% by mass, more preferably 1.0% by mass or less, and particularly preferably 0.5% by mass or less.
  • the semipermeable membrane is allowed to stand at 150 ° C. for 4 hours in a nitrogen atmosphere and dried, and then weighed.
  • the semipermeable membrane is immersed in DMSO or water and allowed to stand at 25 ° C. for 24 hours.
  • the semipermeable membrane is taken out from DMSO or water, left to stand at 150 ° C. for 4 hours in a nitrogen atmosphere, and then weighed. Based on the mass before and after the immersion of the semipermeable membrane, the mass reduction rate is calculated from the following formula.
  • Mass reduction rate (mass before immersion of semipermeable membrane ⁇ mass after immersion of semipermeable membrane) / mass before immersion of semipermeable membrane ⁇ 100
  • the amount of dissolution can be reduced, for example, by crosslinking the protonic acid group-containing aromatic polyether resin, and therefore the amount of dissolution can be within the above range even if the protonic acid group equivalent is small.
  • the semipermeable membrane can be produced as a self-supporting membrane from the aromatic polyether resin (A) having a proton acid group-containing structural unit.
  • the semipermeable membrane can be easily manufactured by pressing or extruding the aromatic polyether resin (A). Moreover, you may give an extending
  • the semipermeable membrane can also be produced from the above varnish by a casting method. That is, a semipermeable membrane can be obtained by applying the varnish on a support and removing the solvent by volatilization. Further, the semipermeable membrane may be peeled off from the support to form a self-supporting membrane.
  • the semipermeable membrane manufactured by the casting method is sufficiently dried and / or washed with water, an aqueous sulfuric acid solution, hydrochloric acid, or the like.
  • the proton acid group of the aromatic polyether resin (A) used for the production of the semipermeable membrane is a functional group that easily releases protons, wherein a hydrogen atom is substituted with Na or K.
  • the membrane of the aromatic polyether resin (A) may be formed, and then the membrane may be contacted with hydrochloric acid, sulfuric acid aqueous solution or the like to replace Na or K of the protonic acid group with a hydrogen atom.
  • the semipermeable membrane in which the concentration of the protonic acid group described above has a gradient in the thickness direction of the semipermeable membrane, specifically, the laminated membrane forms, for example, a layer (L1) containing a resin (A1), Subsequently, it can be obtained by forming a layer (L2) containing the resin (A2) on the layer (L1), and a layer (L2) containing the resin (A2) is formed. It can also be obtained by forming a layer (L1) containing the resin (A1) on the layer (L2).
  • Each layer can be obtained by, for example, press molding, extrusion molding, or a casting method.
  • the semipermeable membrane formed from the mixture containing at least the resins (A1) and (A2) described above is obtained by, for example, press-molding or extruding a mixed resin containing at least the resin (A1) and the resin (A2). It can also be obtained by applying and drying a varnish containing at least the resin (A1) and the resin (A2).
  • the size of the phase separation structure can be adjusted by the stirring speed of the mixed resin or varnish.
  • the air permeability of the porous substrate is preferably 100 to 400 cm 3 / cm 2 / s. This air permeability is measured as follows based on Method A (Fragile method) described in JIS L 1096.
  • test piece of 20 cm ⁇ 20 cm is attached to the testing machine, the suction fan and the air hole are adjusted so that the inclined barometer has a pressure of 125 Pa, and the pressure indicated by the vertical barometer is measured.
  • the amount of air passing through the test piece is obtained from the measured pressure and the type of air hole using the conversion table attached to the tester.
  • the thickness of the porous substrate is usually 50 to 700 ⁇ m, preferably 80 to 600 ⁇ m, more preferably 100 to 500 ⁇ m.
  • the forward osmosis membrane is preferably a thin porous substrate having such a high air permeability, concentration polarization generated inside the porous substrate when the forward osmosis membrane is used is suppressed, and water It is considered that the fluid resistance at the time of passing through the forward osmosis membrane can be reduced, and as a result, the water permeation flux in the forward osmosis membrane can be increased.
  • the air permeability and thickness of the porous substrate can be controlled by conventional methods.
  • Certain materials constituting the porous substrate include synthetic resins and natural fibers.
  • thermoplastic resin examples include a thermoplastic resin and a thermosetting resin, and a thermoplastic resin is preferable.
  • thermoplastic resin include olefin polymers, polyester resins, polyamide resins, polyvinyl chloride, and (meth) acrylic resins. Among these, an olefin polymer and a polyester resin are preferable, and an olefin polymer is particularly preferable.
  • the olefin polymer is a homopolymer or copolymer of ⁇ -olefin, or a copolymer of ⁇ -olefin and another monomer.
  • the ⁇ -olefin include ⁇ -olefins having 2 to 8 carbon atoms such as ethylene, propylene, and 1-butene.
  • olefin polymers include polypropylene, polyethylene, poly 1-butene, poly 4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, and ethylene-4-methyl-1-pentene.
  • Copolymer polyolefin resin such as propylene / 1-butene copolymer, 4-methyl-1-pentene / 1-decene copolymer, ⁇ -olefin such as ethylene / vinyl alcohol copolymer and other monomers Copolymers are included.
  • polyolefin resin such as propylene / 1-butene copolymer, 4-methyl-1-pentene / 1-decene copolymer, ⁇ -olefin such as ethylene / vinyl alcohol copolymer and other monomers Copolymers are included.
  • polyester resin examples include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.
  • polyamide resin examples include nylon 6 and nylon 66.
  • Natural fibers include plant fibers such as cotton and hemp, and animal fibers such as silk and wool. Of these, cotton and silk are preferable.
  • porous substrate examples include fabric substrates such as woven fabrics, nonwoven fabrics, and knitted fabrics, and foamed sheets, among which fabric substrates are preferred, woven fabrics and nonwoven fabrics are more preferred, and nonwoven fabrics are particularly preferred.
  • Non-woven fabrics include long-fiber non-woven fabrics by the spunbond method, short-fiber non-woven fabrics by the melt blown method, flash-spun non-woven fabrics, spunlace non-woven fabrics, airlaid non-woven fabrics, thermal bond non-woven fabrics, needle punched non-woven fabrics, chemical bond non-woven fabrics, etc. Spunbond nonwoven fabrics and meltblown nonwoven fabrics are preferred. Of these, a spunbonded nonwoven fabric is preferable, and a polyethyleneterephthalate or polypropylene spunbonded nonwoven fabric is particularly preferable.
  • the non-woven fabric may be a core-sheath type or side-by-side type composite fiber in which the constituent fibers are composite fibers made of different resins and different resins are arranged on the outer surface side of the fibers.
  • the composite fibers include polyethylene / polypropylene core-sheath type or side-by-side type composite fibers.
  • the laminated nonwoven fabric may be a laminated nonwoven fabric.
  • laminated nonwoven fabrics include laminated nonwoven fabrics including spunbond nonwoven fabrics and meltblown nonwoven fabrics, which are laminates of spunbond nonwoven fabrics and meltblown nonwoven fabrics (SM), spunbond nonwoven fabrics, meltblown nonwoven fabrics and spunbond nonwoven fabrics. Examples include those stacked in order (SMS).
  • a spunbond nonwoven fabric and a meltblown nonwoven fabric are laminated, and the two are integrally formed.
  • methods of integration include a method in which a spunbond nonwoven fabric and a meltblown nonwoven fabric are stacked and heated and pressurized, a method in which both are bonded by an adhesive such as a hot melt adhesive, a solvent-based adhesive, and the like on a spunbond nonwoven fabric.
  • Examples include a method of depositing fibers by a melt blown method and performing heat fusion.
  • the laminated nonwoven fabric may be a laminated nonwoven fabric in which a porous film having micropores is sandwiched between the nonwoven fabrics.
  • a laminated nonwoven fabric for example, a polypropylene (PP) nonwoven fabric, a porous PP film and a PP nonwoven fabric (SFS) are laminated in this order, a PP nonwoven fabric, a porous PP film, and a rayon PP nonwoven fabric (SFR). ) And the like are stacked in this order.
  • the basis weight of the nonwoven fabric is preferably about 10 to 80 g / m 2 , more preferably about 20 to 40 g / m 2 .
  • the forward osmosis membrane of the present invention may include the porous substrate on both sides of the semipermeable membrane. If it is this aspect, the intensity
  • the forward osmosis membrane of the present invention includes a layer other than the porous substrate on both sides or one side of the semipermeable membrane so as to be in the order of semipermeable membrane / layer other than the porous substrate / porous substrate.
  • a polyamide layer may be included as a layer other than the porous substrate, but the thickness is preferably 100 ⁇ m or less.
  • the forward osmosis membrane can be produced, for example, by producing the semipermeable membrane as a self-supporting membrane and sandwiching the semipermeable membrane between the two porous substrates from both sides thereof.
  • the forward osmosis membrane can be specifically manufactured by the following procedure. For example, a dilute solution of the aromatic polyether resin (A) is applied onto a substrate made of PET or the like so that the thickness after drying becomes a target thickness, and after drying, the formed film is peeled off as a self-supporting film.
  • the self-supporting membrane can be sandwiched between two porous substrates such as a nonwoven fabric to produce a forward osmosis membrane.
  • the area of the forward osmosis membrane is large, in order to maintain the distance between the semipermeable membrane and the porous substrate, the two are bonded with an adhesive so as not to affect the permeation flux. Also good.
  • the forward osmosis membrane can also be produced by producing the semipermeable membrane as a self-supporting membrane and laminating the semipermeable membrane on the porous substrate. At this time, they may be bonded together using an adhesive.
  • the semipermeable membrane described above is first manufactured as a self-supporting membrane, and this is laminated on a porous substrate (nonwoven fabric, etc.) or sandwiched between two porous substrates (nonwoven fabric, etc.)
  • a porous substrate nonwoven fabric, etc.
  • sandwiched between two porous substrates nonwoven fabric, etc.
  • the forward osmosis membrane element of the present invention includes the forward osmosis membrane of the present invention described above and a spacer.
  • the forward osmosis membrane element of the present invention is obtained by using the forward osmosis membrane of the present invention as a forward osmosis membrane in a conventional forward osmosis membrane element including a forward osmosis membrane and a spacer.
  • the spacer a conventionally known spacer used for a forward osmosis membrane element can be used.
  • the forward osmosis membrane module of the present invention comprises the forward osmosis membrane element of the present invention accommodated in a container.
  • the forward osmosis membrane module of the present invention is a conventional osmosis membrane element in which the forward osmosis membrane element is accommodated in a container, and the forward osmosis membrane element of the present invention is used as the forward osmosis membrane element.
  • the conventionally well-known container used for a forward osmosis membrane module can be used as a container.
  • the system of the present invention includes a forward osmosis membrane module of the present invention, and a feed solution (FS) on one side of the forward osmosis membrane of the present invention included in the forward osmosis membrane module, and a feed solution (FS) on the other side of the feed solution. It has a drive pump for flowing a draw solution (DS) having a high solute concentration such as salt, and is configured to be able to move water contained in the feed solution to the draw solution through the forward osmosis membrane.
  • DS draw solution
  • pressure can be applied from the FS side to the DS side.
  • pressure when pressure is applied from the FS side to the DS side, preferably 15 kPa or less, more preferably 12 kPa or less, and even more preferably 10 kPa or less. It may be preferable.
  • Solvent DMSO Dimethyl sulfoxide
  • DMF N, N-dimethylformamide
  • Component of aromatic polyether DFBP 4,4′-difluorobenzophenone
  • DSDFBP 5,5'-carbonylbis (sodium 2-fluorobenzenesulfonate)
  • TMBPF 3,3 ′, 5,5′-Tetramethyl-4,4′-dihydroxydiphenylmethane Test methods for various tests are as follows.
  • HPLC high-performance liquid chromatograph
  • the thickness of the semipermeable membrane was measured. Specifically, when light is incident on a film having a refractive index n at a certain angle ( ⁇ ), the reflected light A from the surface of the film and the reflected light B from the back surface interfere with each other to generate a wavy interference spectrum.
  • the thickness (d) was calculated from the equation (1) by counting the number ( ⁇ m) of peaks (peaks or valleys) of the interference spectrum within a certain wavelength range ( ⁇ 1 to ⁇ 2 ).
  • Resin synthesis example 2 Resin raw materials and solvents were added as follows: DSDFBP 40.1 g (0.095 mol), DFBP 62.2 g (0.284 mol), TMBPF 97.4 g (0.380 mol) and potassium carbonate 65.7 g (0.475 mol), and DMSO 798.4 g and 156.5 g of polymer powder (yield 85%) (resin 2) was obtained in the same manner as in Resin Synthesis Example 1 except that 266.2 g of toluene was used.
  • the structural unit (1): the structural unit (2) 25 mol: 75 mol.
  • Mw 123,000.
  • a resin film is obtained in the same manner as in Production Example 1 except that the resin 1 and the resin 2 are mixed in a mass ratio (resin 1: resin 2) of 7: 3, and this is peeled off from the release sheet.
  • a semipermeable membrane 2 having a thickness of 0.6 ⁇ m was obtained as a self-supporting membrane.
  • a non-woven fabric having an air permeability of 300 cm 3 / cm 2 / s, a thickness of 290 ⁇ m, a basis weight of 25 g / m 2 , and a material of polypropylene as measured by A method (fragile type method) described in JIS L 1096 Tex (registered trademark) PS-105 (made by Mitsui Chemicals, Inc.) was prepared, and the semipermeable membrane obtained in each production example was sandwiched between these nonwoven fabrics, and these were integrated to obtain a forward osmosis membrane. It was. The following evaluation was performed using the obtained forward osmosis membrane.
  • FIG. 10 A schematic diagram of the apparatus 10 used for evaluating the separation performance of the forward osmosis membrane is shown in FIG.
  • the apparatus 10 includes a feed solution tank 1, a flow path 2, a pump 3, a draw solution tank 11, a flow path 12, a pump 13, and an evaluation cell 21.
  • the feed solution tank 1 is installed on the balance 4, and the draw solution tank 11 is provided with an electric conductivity meter 15.
  • 500 g of Milli-Q water having an electric conductivity of 50 ⁇ S / cm or less is stored in the feed solution tank 1 as a feed solution FS (Feed Solution), and the draw solution tank 11 has a draw solution DS.
  • As (Draw Solution) 800 g of 0.2, 0.4, 0.6, or 0.8 mol / L NaCl aqueous solution is stored.
  • the feed solution in the feed solution tank 1 flows through the flow path 2 at a speed of 0.6 L / min by using the pump 3, and the draw solution in the draw solution tank 11 is 0.6 L / min by using the pump 13. It flows through the flow path 12 at a speed.
  • the applied pressure from FS to DS is set to about 0 kPa or about 1 kPa.
  • the feed solution flowing through the flow channel 2 and the draw solution flowing through the flow channel 12 are in contact with each other through the forward osmosis membrane 22 having an effective membrane area of 0.0042 m 2 inside the evaluation cell 21.
  • the water of the feed solution permeates into the draw solution, and a part of the salt (NaCl) in the draw solution diffuses into the feed solution.
  • the semipermeable membranes 1 and 2 had a smaller Js / Jw than the semipermeable membranes c1 and c2, and thus were excellent in the balance between the water permeation flux and the salt rejection.
  • the salt reverse diffusion value is less than or equal to the condition of pressurization from FS to DS compared to the condition of no pressurization. This is considered that the water which permeate
  • the (A1) / (A2) layer may have slightly changed to a suitable structure.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Polyethers (AREA)

Abstract

Cette membrane d'osmose directe est pourvue d'une membrane semi-perméable et d'un matériau de base poreux disposé sur au moins une surface de celle-ci, la membrane semi-perméable contenant une résine polyéther aromatique (A) ayant une unité structurelle contenant un groupe acide protonique, et la résine (A) au moins contient : une résine polyéther aromatique contenant un groupe acide protonique (A1); et une résine polyéther aromatique contenant un groupe acide protonique (A2) ayant une fraction molaire plus élevée de l'unité structurale contenant un groupe acide protonique que la résine (A1).
PCT/JP2019/013521 2018-03-29 2019-03-28 Membrane d'osmose directe et ses utilisations WO2019189547A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
JP7508253B2 (ja) 2020-03-31 2024-07-01 三井化学株式会社 正浸透膜の製造方法
JP7508254B2 (ja) 2020-03-31 2024-07-01 三井化学株式会社 正浸透膜の製造方法

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JP2003335835A (ja) * 2002-05-22 2003-11-28 Mitsui Chemicals Inc スルホン酸基含有樹脂ワニスおよびスルホン酸基含有架橋樹脂
JP2013031836A (ja) * 2011-07-04 2013-02-14 Toyobo Co Ltd ナノろ過用の分離膜
JP2014000533A (ja) * 2012-06-19 2014-01-09 Mitsui Chemicals Inc 微多孔性支持膜用樹脂組成物およびそれを用いた微多孔性支持膜、並びに複合半透膜
WO2016056547A1 (fr) * 2014-10-07 2016-04-14 東洋紡株式会社 Membrane de séparation, élément de membrane de séparation, et module de membrane de séparation
WO2018079733A1 (fr) * 2016-10-27 2018-05-03 三井化学株式会社 Membrane d'osmose directe et ses utilisations

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Publication number Priority date Publication date Assignee Title
JP2003335835A (ja) * 2002-05-22 2003-11-28 Mitsui Chemicals Inc スルホン酸基含有樹脂ワニスおよびスルホン酸基含有架橋樹脂
JP2013031836A (ja) * 2011-07-04 2013-02-14 Toyobo Co Ltd ナノろ過用の分離膜
JP2014000533A (ja) * 2012-06-19 2014-01-09 Mitsui Chemicals Inc 微多孔性支持膜用樹脂組成物およびそれを用いた微多孔性支持膜、並びに複合半透膜
WO2016056547A1 (fr) * 2014-10-07 2016-04-14 東洋紡株式会社 Membrane de séparation, élément de membrane de séparation, et module de membrane de séparation
WO2018079733A1 (fr) * 2016-10-27 2018-05-03 三井化学株式会社 Membrane d'osmose directe et ses utilisations

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7508253B2 (ja) 2020-03-31 2024-07-01 三井化学株式会社 正浸透膜の製造方法
JP7508254B2 (ja) 2020-03-31 2024-07-01 三井化学株式会社 正浸透膜の製造方法

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