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WO2019189548A1 - Procédé de production d'une solution ayant une concentration de soluté réduite - Google Patents

Procédé de production d'une solution ayant une concentration de soluté réduite Download PDF

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Publication number
WO2019189548A1
WO2019189548A1 PCT/JP2019/013522 JP2019013522W WO2019189548A1 WO 2019189548 A1 WO2019189548 A1 WO 2019189548A1 JP 2019013522 W JP2019013522 W JP 2019013522W WO 2019189548 A1 WO2019189548 A1 WO 2019189548A1
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Prior art keywords
solution
forward osmosis
semipermeable membrane
osmosis membrane
acid group
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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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Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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Priority to JP2020509305A priority Critical patent/JPWO2019189548A1/ja
Publication of WO2019189548A1 publication Critical patent/WO2019189548A1/fr
Anticipated expiration legal-status Critical
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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
    • 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 solution processing method using a forward osmosis membrane. More specifically, the present invention relates to a method for producing a solution having a reduced solute concentration by using a forward osmosis membrane and transferring a solvent contained in the low solute concentration solution to the high solute concentration solution.
  • 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 the osmotic pressure generated between solutions having different solute concentrations separated by a forward osmosis membrane as a driving force from the low solute concentration side (for example, fresh water) to the high solute concentration side (for example, seawater). And solvent (eg water) move. 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 present invention in order to move the solvent contained in the low solute concentration solution to the high solute concentration solution through the forward osmosis membrane, it is one aspect to obtain a higher permeation flux of the solvent. In the present invention, reducing the back diffusion of salt is also an aspect.
  • the forward osmosis membrane technology performs treatment using osmotic pressure generated between a low solute concentration solution and a high solute concentration solution, but further studies are underway to apply external pressure.
  • the present invention relates to the following [1] to [5].
  • a solution FS is supplied to a region on one surface side of a forward osmosis membrane including a semipermeable membrane and a porous substrate disposed on at least one surface thereof, and the solution is supplied to a region on the other surface side.
  • a solution DS having a higher solute concentration than FS By supplying a solution DS having a higher solute concentration than FS and moving the solvent contained in the solution FS to the solution DS through the forward osmosis membrane, a method for producing a solution having a reduced solute concentration of the solution DS.
  • the supply pressure P1 of the solution FS and the supply pressure P2 of the solution DS are expressed by the formula: 0.5 kPa ⁇ P1 ⁇ P2 ⁇ 700 kPa How to meet.
  • 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. The method according to any one of [1] to [3].
  • 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 solution FS and the solution DS are both aqueous solutions containing a salt, and the salt concentration of the solution DS is higher than the salt concentration of the solution FS, 2.
  • FIG. 1 is a schematic view for explaining an embodiment of the production method of the present invention.
  • the present invention provides a solution FS in a region (hereinafter also referred to as “first region”) on one surface side of a forward osmosis membrane comprising a semipermeable membrane and a porous substrate disposed on at least one surface thereof.
  • a solution DS having a solute concentration higher than that of the solution FS is supplied to a region on the other surface side (hereinafter also referred to as a “second region”), and the solvent contained in the solution FS is used as the forward osmosis membrane.
  • the supply pressure P1 of the solution FS and the supply pressure P2 of the solution DS are: Formula: 0.5 kPa ⁇ P1-P2 ⁇ 700 kPa
  • the P1-P2 preferably satisfies 1.0 kPa ⁇ P1-P2 ⁇ 200 kPa.
  • a more preferable lower limit value of P1-P2 is 1.5 kPa.
  • a more preferable upper limit value of P1-P2 is 100 kPa, and more preferably 50 kPa.
  • a large permeation flux can be obtained in the forward osmosis method by setting the supply pressure P1 of the solution FS higher than the supply pressure P2 of the solution DS so that the above pressure difference is obtained.
  • a semipermeable membrane showing a high permeation flux tends not to have low salt reverse diffusion.
  • the above-mentioned effect can be obtained by applying a pressure difference, for example, about three orders of magnitude smaller than the pressure applied by the normal reverse osmosis method to the solution.
  • the supply pressures P1 and P2 can be measured with a pressure gauge provided in the flow path. These supply pressures can be adjusted by, for example, a pressure applied by a solution feed pump for each solution and / or an opening adjustment valve for adjusting the flow rate of each solution.
  • the solution FS is also referred to as “feed solution” or abbreviated “FS”
  • the solution DS is also referred to as “draw solution” or abbreviated “DS”.
  • the solute concentration of the solution DS is higher than the solute concentration of the solution FS. According to the production method of the present invention, the solute concentration of the solution DS can be reduced.
  • the liquid temperature of the solution FS and the solution DS is not particularly limited, but is room temperature, for example.
  • the solvent in the solution FS and the solution DS is not particularly limited as long as it is a liquid that passes through the forward osmosis membrane, and examples thereof include water, alcohols, and hydrocarbons, and water is preferable. Therefore, the solution FS and the solution DS are preferably aqueous solutions.
  • the solution FS is not particularly limited and may be any solution that has a relatively low solute concentration and thus lower osmotic pressure than the solution DS.
  • purified water drinkable water, river water, ground water, agricultural water, etc.
  • Examples include fresh water, domestic wastewater, industrial wastewater, mineral water, brackish water, and seawater.
  • the solution DS is not particularly limited as long as the solution DS has a solute concentration relatively higher than that of the solution FS, and thus has a higher osmotic pressure, and the solute is not particularly limited.
  • the solution DS can be prepared using a solute having sufficient solubility.
  • the solute include salts that are readily soluble in water such as sodium chloride, potassium chloride, calcium chloride, sodium sulfate, magnesium sulfate, ammonium chloride, ammonium sulfate, and ammonium carbonate; methanol, ethanol, 1-propanol, 2-propanol, and the like.
  • Alcohols such as ethylene glycol and propylene glycol; ketones such as acetone and methyl ethyl ketone; polymers such as polyethylene oxide and propylene oxide.
  • salts are preferred.
  • the solution DS include, for example, seawater, concentrated seawater produced by reverse osmosis, a fertilizer solution, and a solution produced using a solute having sufficient solubility to achieve high osmotic pressure. .
  • the solution FS and the solution DS are both aqueous solutions containing salts, and the salt concentration of the solution DS is preferably higher than the salt concentration of the solution FS.
  • the method of the present invention is preferably used for, for example, seawater desalination, drainage treatment, treatment of accompanying water in oil and gas drilling, power generation using two liquids having different osmotic pressures, dilution of sugars and fertilizers, etc. Can do.
  • the forward osmosis membrane used in the present invention is preferably accommodated in a container, that is, a forward osmosis membrane module in which the forward osmosis membrane is accommodated in the container is preferably used.
  • the forward osmosis membrane partitions the inside of the container into the first region and the second region described above.
  • the solution FS is supplied from the tank of the solution FS to the first area
  • the solution DS is supplied from the tank of the solution DS to the second area.
  • the solution FS and the solution DS are in contact with both sides of the forward osmosis membrane, and the solvent contained in the solution FS moves through the forward osmosis membrane from the solution FS to the solution DS.
  • the solution DS flowing through the second region is diluted by the moved solvent.
  • the solution FS and the solution DS are supplied to the first region and the second region, respectively, across the forward osmosis membrane, and the supply direction of these solutions may be the same direction or opposite to each other. However, the reverse direction, that is, the cross flow is preferable.
  • FIG. 1 to be described later is an example of a cross flow.
  • the liquid feeding system is configured to flow FS from the FS tank to the first region, the DS tank, the first region, the forward osmosis membrane module having the forward osmosis membrane and the second region, and the first region. with the a flow path FS, a flow path DS for supplying a DS from the tank of the DS in the second region.
  • the liquid feed system may be a circulation passage FS for returning the FS to the tank of the FS from the first region, and a circulation channel DS for returning the DS to the tank of the DS from the second region.
  • the liquid feeding system includes a bypass flow path FS branched from the flow path FS for returning the FS to the FS tank without passing through the forward osmosis membrane module, and a DS tank without passing through the forward osmosis membrane module. for returning to the can and a bypass channel DS branched from the flow channel DS.
  • the liquid feeding system includes a liquid feeding pump for flowing FS in the first area and a liquid feeding pump for flowing DS in the second area.
  • Supply pressures P1 and P2 can be adjusted by a liquid feed pump (hereinafter also referred to as “pump”).
  • the pump can be provided, for example, in the middle of the flow path FS and the flow path DS .
  • the liquid feeding system in the middle of the flow path FS, it can have a degree of opening adjustment valve for adjusting the FS flow to the first region, in the middle of the channel DS, DS to the second region
  • An opening adjustment valve for adjusting the flow rate can be provided.
  • Supply pressures P1 and P2 can be adjusted by the opening adjustment valve.
  • the opening degree adjusting valve can be provided, for example, on a flow path between each pump and the first and second regions.
  • the liquid feeding system in the middle of the bypass passage FS, can have an opening adjustment valve for adjusting the flow rate to return the FS to the tank of the FS, in the middle of the bypass passage DS, DS to the tank of DS It is possible to have an opening degree adjusting valve for adjusting the flow rate of returning the pressure. Supply pressures P1 and P2 can be adjusted by the opening adjustment valve.
  • FIG. 1 shows an embodiment of a liquid feeding system suitably used in the present invention.
  • the FS tank 1 is connected to the forward osmosis membrane module 21 by a flow path 2 such as a pipe, specifically, to the first region inlet, and a pump 3 is provided in the middle of the flow path 2.
  • a flow path 2 such as a pipe, specifically, to the first region inlet, and a pump 3 is provided in the middle of the flow path 2.
  • the forward osmosis membrane module 21 has a forward osmosis membrane 22.
  • the forward osmosis membrane module 21, specifically, the first region outlet is connected to the FS tank 1 by a circulation channel 2-1 such as a pipe. Further, a bypass channel 2-2 for returning FS to the tank 1 is branched from the channel 2 and connected to the circulation channel 2-1.
  • An opening degree adjustment valve B1 for adjusting the FS flow rate to the forward osmosis membrane module 21 is provided on the flow path 2, and the opening degree adjustment valve for adjusting the FS flow rate to the bypass flow path side is provided in the bypass flow path 2-2.
  • a valve B2 is provided.
  • a pressure gauge, various valves, etc. may be arranged in the middle of each flow path.
  • the FS is sent to the forward osmosis membrane module 21 using the pump 3.
  • the setting of the pressurizing force by the pump 3, the opening degree of the opening degree adjusting valve B ⁇ b> 1, and the opening degree of the opening degree adjusting valve B ⁇ b> 2 are appropriately adjusted.
  • the supply pressure P1 and the flow rate can be adjusted to set values.
  • DS can use the same apparatus as the FS liquid feeding method, and can appropriately adjust the supply pressure P2 and the flow rate to set values.
  • the flow rate of FS and DS is 0.6 L / min
  • the supply pressure P1 of FS is 28 kPa
  • the supply pressure P2 of DS is 24 kPa
  • a differential pressure of P1 ⁇ P2 4 kPa is applied.
  • a forward osmosis membrane comprising a semipermeable membrane and a porous substrate disposed on at least one surface thereof is used, but a mesh-like support is provided between the semipermeable membrane and the porous substrate.
  • a forward osmosis membrane further comprising a substrate is preferred.
  • the conventionally well-known container used for a forward osmosis membrane module can be used.
  • the forward osmosis membrane comprises the semipermeable membrane, and preferably the porous substrate disposed on at least one surface thereof, and maintains a high filtration function and a salt rejection while maintaining a high permeation rate. Performance can be realized.
  • the forward osmosis membrane may include the porous substrate on both sides of the semipermeable membrane. If it is this aspect, the intensity
  • the forward osmosis membrane may include 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 semipermeable membrane is not particularly limited, but is preferably a membrane containing a material capable of forming a self-supporting membrane. For this reason, the inventors consider the following hypothesis.
  • the semipermeable membrane used in the present invention is exposed to a certain pressure as described above. For this reason, depending on the material, there is a possibility that deformation and structural change occur at the micro level. Any material that can form a self-supporting film is considered to be a material that can easily exhibit the effects of the present invention because the deformation and the structural change are suppressed. Alternatively, the above-described pressure may cause a fine conversion to a structure preferable for water permeation, and may exhibit the water permeation flux aimed at by the present invention and the effect of suppressing salt reverse diffusion.
  • the semipermeable membrane preferably contains a plurality of types of polymers.
  • hydrophilic groups such as sulfonic acid groups.
  • the semipermeable membrane preferably comprises a protonic acid group-containing aromatic polyether resin.
  • a semipermeable membrane using the aromatic polyether resin as a raw material can be produced as a self-supporting membrane. By laminating this semipermeable membrane and a porous substrate, water permeability is high and salt rejection is high. A forward osmosis membrane can be obtained.
  • the semipermeable membrane is substantially composed of only the protonic acid group-containing aromatic polyether resin, but a small amount of other components (for example, 1% by mass or less, or 0.1% by mass) does not impair the effects of the present invention. (Mass% or less) 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. As described above, even if the supply pressure difference is as low as P1-P2 of 700 kPa or less, a high permeation flux can be obtained with such a film thickness.
  • 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 thickness of the semipermeable membrane does not include the thickness of the porous substrate.
  • the proton acid group-containing aromatic polyether resin preferably includes a structural unit represented by the following formula (1) and a structural unit (2) represented by the following formula (2).
  • 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) can form a semipermeable membrane with high water permeability, or water permeation by pressurization of the present invention. From the viewpoint of the effect of improving the flux, it is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, particularly preferably 0.35 or more; Since a semipermeable membrane that does not gel can be formed, it is preferably 0.9 or less, more preferably 0.7 or less, and even more preferably 0.6 or less.
  • the proton acid group-containing aromatic polyether resin may further contain a structural unit derived from a polyfunctional compound described later.
  • the protonic acid group-containing aromatic polyether resin may be a crosslinked product or a non-crosslinked product.
  • the weight average molecular weight (Mw) of the protonic acid group-containing aromatic polyether resin measured by the following conditions (1) to (6) using a GPC (Gel Permeation Chromatography) method is preferably 70,000 or more. 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 proton acid group equivalent of the proton acid group-containing aromatic polyether resin that is, the mass of the proton acid group-containing aromatic polyether resin per mole of the proton acid group was not dissolved in water or methanol, and swelling was suppressed. Since a semipermeable membrane with a small membrane permeation amount of the electrolyte can be obtained, it is preferably 200 g / mol or more. Further, since a semipermeable membrane having a large water permeation flux and high economic efficiency can be obtained, it is preferably 5000 g / mol or less, more preferably 1000 g / mol or less.
  • the protonic acid group-containing aromatic polyether resin 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 within a range that does not impair the solvent solubility of the protonic acid group-containing aromatic polyether resin.
  • the protonic acid group-containing aromatic polyether resin can have 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 from the viewpoint of preventing a decrease in solvent solubility of the protonic acid group-containing aromatic polyether resin, a decrease in fluidity during film formation of the resin, and a decrease in the elongation rate of the semipermeable membrane.
  • 0 to 8 mol% / total OH equivalent that is, out of the total amount of OH groups (100 mol%) of the monomer of formula (1b), the monomer of formula (2b) and the polyfunctional monomer
  • 0 to 8 mol% is an OH group derived from a polyfunctional monomer.
  • the proton acid group-containing aromatic polyether resin varnish is basically linear in molecular structure, and even if it has a cross-linked structure derived from the polyfunctional compound, the amount thereof is small. Excellent solvent solubility. 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 strength at break and the elongation percentage can be increased, for example, by increasing the molecular weight of the protonic acid group-containing aromatic polyether resin.
  • 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 manufactured as a self-supporting membrane from the protonic acid group-containing aromatic polyether resin.
  • the semipermeable membrane can be easily produced by press molding or extrusion molding the protonic acid group-containing aromatic polyether resin. Further, the proton acid group-containing aromatic polyether resin film may be subjected to stretching treatment or the like.
  • 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 protonic acid group-containing aromatic polyether resin 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 proton acid group-containing aromatic polyether resin film may be formed, and then the film may be contacted with hydrochloric acid, sulfuric acid aqueous solution or the like to replace Na or K of the proton acid group with a hydrogen atom.
  • 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, olefin polymers and polyester resins are preferable, and olefin polymers are 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 mesh-like support substrate only needs to have strength to support the semipermeable membrane and sufficient solvent permeability that does not cause permeation resistance, and the shape is not particularly limited, but a lattice-like object made of yarn or fiber Is preferred.
  • the number of meshes of the mesh-like support substrate is preferably 20 to 300 / inch.
  • the mesh size of the mesh-like support substrate is preferably 40 ⁇ 40 to 6,000 ⁇ 6,000 ( ⁇ m ⁇ ⁇ m).
  • the fiber diameter of the mesh-like support substrate is preferably 20 to 300 ⁇ m.
  • the opening ratio of the mesh-like support substrate is preferably 30 to 90%.
  • the material of the mesh-like support base material is not particularly limited as long as it has the strength to support the semipermeable membrane, and examples thereof include a base material made of resin, metal, glass fiber, ceramic and the like. Among these, a resinous base material that is lightweight and excellent in workability is preferable.
  • the resin examples include polyethylene, polypropylene, polyester, polyamide, and polyimide.
  • a resin-made mesh-like support base material for example, there is a product of Kubota Corporation.
  • the mesh-like support base material and the semipermeable membrane may be bonded together via an adhesive, or the mesh-like support base material and the semipermeable membrane are simply bonded together. It may be fixed by sandwiching the periphery with a frame material just by overlapping. From the viewpoint of handling, it is preferable that the mesh-like support substrate and the semipermeable membrane are bonded together via an adhesive.
  • the adhesive is preferably applied only to the fiber portion so as not to block the opening of the mesh-like support substrate.
  • 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 protonic acid group-containing aromatic polyether resin 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.
  • a mesh-like support substrate When using a mesh-like support substrate, a mesh-like support substrate is provided between the semipermeable membrane and the porous substrate in the production method. When providing a porous substrate on both sides of the semipermeable membrane, a mesh-like support substrate is provided on at least one of the semipermeable membrane and the porous substrate.
  • 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.
  • 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 enters 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 nonwoven fabric (Syntex (registered trademark) PS-) having an air permeability of 300 cm 3 / cm 2 / s, a thickness of 290 ⁇ m, and a material measured by A method (Fragile method) described in JIS L 1096 105, made by Mitsui Chemicals, Inc.
  • the semipermeable membranes 1 to 3 are sandwiched between these non-woven fabrics, and these are integrated to form a forward osmosis membrane A and a semipermeable membrane having the semipermeable membrane 1 A forward osmosis membrane B having 2 and a forward osmosis membrane C having a semipermeable membrane 3 were obtained.
  • FIG. 10 A schematic diagram of the apparatus 10 used for the evaluation is shown in FIG.
  • the apparatus 10 includes an FS tank 1, flow paths 2, 2-1, 2-2, pump 3, DS tank 11, flow paths 12, 12-1, 12-2, pump 13, and forward osmosis membrane module 21, Each valve B1 to B4 is provided.
  • the FS tank 1 and the DS tank 11 are installed on the balances 4 and 14, respectively, and are provided with electric conductivity meters 5 and 15.
  • the FS flowing through the flow channel 2 and the DS flowing through the flow channel 12 are in contact with each other through the forward osmosis membrane 22 (the above-described forward osmosis membranes A to C) having an effective membrane area of 86 ⁇ 40 mm 2 inside the forward osmosis membrane module 21.
  • the forward osmosis membrane 22 Through the forward osmosis membrane 22, a part of the FS moves to the DS, and a part of the salt (NaCl) in the DS moves (backflows) to the FS.
  • the pressure on the FS side is 1 kPa, 5 kPa, or 10 kPa higher than the pressure on the DS side, or the pressure on the FS side is
  • the flow rate was maintained at 0.6 L / min while adjusting the supply pressure of FS and DS so as to be the same as the pressure on the DS side.
  • the weight of the solution and the electrical conductivity of the solution were measured every 1 minute on the FS side and the DS side, respectively.
  • the water permeation flux Jw (LMH: L / (m 2 ⁇ h)) that is the amount of permeated water per unit area of the forward osmosis membrane
  • the unit time Obtain the salt back-diffusion amount Js (gMH: g / (m 2 ⁇ h)), which is the amount of salt movement per unit area of the forward osmosis membrane, and measure in a state where Jw and Js are stable after about 10 minutes. Value.
  • a calibration curve of electrical conductivity and salt concentration was prepared in advance, and the salt concentration was calculated from the electrical conductivity and volume change.
  • the amount of salt transfer from DS to FS per hour was calculated from the amount of change in salt concentration on the FS side, and Js (gMH) was calculated.
  • Table 1 shows the measurement results.

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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

Dans ce procédé, une solution FS est fournie à une région sur un côté de surface d'une membrane d'osmose directe qui est pourvue d'une membrane semi-perméable et d'un matériau de base poreux disposé sur au moins une surface de celle-ci, et une solution DS ayant une concentration en soluté plus élevée que la solution FS est fournie à une région sur l'autre côté de surface de façon à transférer un solvant contenu dans la solution FS dans la solution DS à travers la membrane d'osmose directe, ce qui permet de produire une solution dans laquelle la solution DS a une concentration de soluté réduite, la pression d'alimentation P1 de la solution FS et la pression d'alimentation F2 de la solution DS satisfaisant la formule : 0,5 kPa ≤ P1-P2 ≤ 700 kPa.
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JP2022149644A (ja) * 2021-03-25 2022-10-07 三井化学株式会社 正浸透膜
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US12274984B2 (en) 2021-06-28 2025-04-15 Asahi Kasei Kabushiki Kaisha Evaluation method and evaluation device for forward osmosis membrane module

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