Forward osmosis membrane and method for producing same

Abstract

The present invention provides: a forward osmosis membrane which achieves good water permeability, good rejection performance and good resistance against the counter pressure at the same time; and a method for producing a forward osmosis membrane, the method being capable of easily producing the above-described forward osmosis membrane. One embodiment of the present invention provides a forward osmosis membrane which comprises a porous supporting membrane and a separation function layer that is arranged on the porous supporting membrane, wherein: the porous supporting membrane is in contact only with the separation function layer; and the separation function layer is composed of a polyamide layer. With respect to this forward osmosis membrane, if the surface of the separation function layer is measured by X-ray photoelectron spectroscopy, the ratio (O533eV / N ratio) of the relative element concentration obtained by curve fitting centered at 533 eV in the O1s spectrum to the relative element concentration obtained from N1s spectrum is 0.29 to 0.53; and with respect to the IR measurement of the surface of the separation function layer, the ratio (IR1720 / IR1650) of the peak top intensity at 1720 cm-1 to the peak top intensity at 1650 cm-1 is 0.25 or less.

Description

[Technical field]

[0001] The present invention relates to a forward osmosis membrane and a method for producing the same. [Background technology]

[0002] Conventionally, as a membrane separation method for selectively separating a desired substance from a mixture, a method using a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, a forward osmosis membrane, a reverse osmosis membrane, etc. is known. Forward osmosis membranes and reverse osmosis membranes are useful for separating low molecular weight substances such as solvents, and usually have a porous support and a separation functional layer laminated on its surface. In the forward osmosis method, when a raw material liquid and a draw solution having a higher osmotic pressure than the raw material liquid by containing an inducer having an osmotic pressure increasing effect are contacted through a forward osmosis membrane, a solvent (e.g., water) moves from the raw material liquid (dilute solution) to the draw solution (concentrated solution) using the osmotic pressure difference generated on both sides of the separation functional layer as a driving force. That is, the forward osmosis process uses the osmotic pressure difference to move the solvent from the dilute solution side to the concentrated solution side. On the other hand, in the reverse osmosis process, the concentrated solution side is pressurized to move the solvent from the concentrated solution side to the dilute solution side against the osmotic pressure difference.

[0003] When treating an aqueous liquid to be treated using a forward osmosis membrane or a reverse osmosis membrane, the permeability of the membrane may decrease over time due to continuous use, and various methods have been proposed to reduce this decrease in permeability.

[0004] Patent Document 1 describes a forward osmosis membrane having a separating active layer made of a high molecular weight polymer on the surface of a microporous support membrane, in which, when purified water is placed as a raw liquid on the separating active layer side of the forward osmosis membrane and a specific draw solution is placed on the microporous support membrane side, the amount of salt back-diffusion into the raw liquid is a specific value or less and the amount of water permeating into the draw solution is a specific value or more.

[0005] Patent Document 2 describes a polyamide reverse osmosis composite membrane comprising (a) a microporous support, (b) a polyamide layer on the microporous support, and (c) a hydrophilic coating applied onto the polyamide layer, the hydrophilic coating being formed by covalently bonding a hydrophilic compound to the polyamide layer, the hydrophilic compound comprising (i) at least one reactive group covalently bonded directly to the polyamide layer, the at least one reactive group being at least one primary amine and a secondary amine, and (ii) at least one non-terminal hydroxyl group, the hydrophilic coating being characterized in that it provides a membrane surface having an oxygen to nitrogen ratio (O / N) of 1.6 or more as measured by X-ray photoelectron spectroscopy (XPS) and a water contact angle of 40° or less as measured by a goniometer.

[0006] Patent Document 3 describes a composite semipermeable membrane consisting of a support membrane including a substrate and a porous support layer, and a separation functional layer provided on the porous support layer, in which the separation functional layer contains a hydrophilic polymer that is a polymer of a crosslinked polyamide and a monomer having an ethylenically unsaturated group, and in which the ratio of the number of oxygen atoms to the number of nitrogen atoms (O / N ratio) on the surface of the separation functional layer, measured by X-ray photoelectron spectroscopy, is 1.5 or more and 10 or less, and the standard deviation of the ratio is 0.15 or more.

[0007] Non-Patent Document 1 describes a reverse osmosis membrane whose flux has been improved by surface treatment with hydrofluoric acid and fluorosilicic acid. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] International Publication No. 2020 / 241860 [Patent Document 2] JP 2010-012455 A [Patent Document 3] International Publication No. 2018 / 003943 [Non-patent literature]

[0009] [Non-Patent Document 1] Mukherjee et al., Flux enhancement of reverse osmosis membranes by chemical surface modification, Journal of Membrance Science, 97 (1994) 231-249 Summary of the Invention [Problem to be solved by the invention]

[0010] Forward osmosis and reverse osmosis have in common the use of semipermeable membranes, but their operating principles are completely different, so a semipermeable membrane that is useful for one of these methods is not necessarily useful for the other. Forward osmosis has the advantage of being able to simplify the configuration of a membrane separation system compared to reverse osmosis, but according to the study by the present inventors, converting a reverse osmosis membrane into a forward osmosis membrane may cause the following inconveniences. That is, in a reverse osmosis membrane, pressure (more specifically, pressure by liquid) is usually assumed to be applied to the reverse osmosis membrane only on one side of the membrane, so it is sufficient to consider improving the water permeability in order to improve the processing speed, but in a forward osmosis membrane, due to the operating principle of having liquids present on both sides of the membrane, a water permeability improvement method that is effective in a reverse osmosis membrane (for example, hydrophilization treatment and subsequent pressurized operation) does not necessarily bring about a sufficient improvement in water permeability in a forward osmosis membrane. In addition, when a reverse osmosis membrane, which is often constructed to withstand high pressure loads, is converted into a forward osmosis membrane, the diffusibility of the draw solution in the forward osmosis method is hindered, resulting in low water permeability and a high amount of salt back diffusion, which is inconvenient for the forward osmosis membrane.

[0011] In addition, due to the operating principle of forward osmosis membranes, which have liquids on both sides of the membrane, it is necessary to ensure not only water permeability but also blocking properties (i.e., the ability to prevent the outflow of the inducer in the inducer solution into the raw liquid side).

[0012] Furthermore, in a forward osmosis membrane, due to the operating principle of having liquids on both sides of the membrane, not only pressure is applied from the feed liquid side to the draw solution side during normal operation, but also pressure in the opposite direction (back pressure) may occur on the membrane due to improper setting of operating conditions, etc., so resistance to back pressure is also required.

[0013] However, the technology described in Patent Document 1 has room for improvement in terms of compatibility between water permeability, blocking property, and resistance to back pressure. In addition, in the reverse osmosis membranes described in Patent Documents 2 and 3, the water permeability of the reverse osmosis membrane can be improved by a hydrophilic coating, but if this membrane is used as a forward osmosis membrane, the hydrophilic coating will reduce the diffusibility of the draw solution, and therefore the water permeability will be reduced. In addition, there is a concern that the hydrophilic coating will cause elution of coating-derived substances from the membrane. Furthermore, the technology described in Non-Patent Document 1 obtains a reverse osmosis membrane with improved flux by surface treating a membrane composed of a substrate and a porous support membrane with a high concentration of a hydrophilic solvent, but in such a membrane, the interface between the substrate and the porous support membrane is easily peeled off, so that resistance to back pressure becomes a problem when the membrane is converted to a forward osmosis membrane. In addition, when the reverse osmosis membrane described in Non-Patent Document 1 is converted to a forward osmosis membrane, there is also a problem that sufficient water permeability cannot be obtained when trying to improve the flux, because the presence of the substrate prevents the diffusion of the draw solution.

[0014] The present invention aims to solve the above problems and provide a forward osmosis membrane that simultaneously achieves good water permeability, good blocking properties, and good resistance to back pressure, and a method for easily producing such a forward osmosis membrane. [Means for solving the problem]

[0015] This disclosure encompasses the following items. [1] A forward osmosis membrane having a porous support membrane and a separation functional layer disposed on the porous support membrane, The porous support membrane is in contact with only the separation functional layer, The separation functional layer is a polyamide layer, The ratio of the relative element concentration obtained by curve fitting centered at 533 eV in the O1s spectrum to the relative element concentration obtained from the N1s spectrum when the surface of the separation functional layer is measured by X-ray photoelectron spectroscopy (O 533eV / N ratio) is 0.29 to 0.53, In IR measurement of the surface of the separation functional layer, -1 Peak top intensity at 1720cm -1 Peak top intensity ratio (IR 1720 / IR 1650 ) is 0.25 or less. [2] The ratio (O 533eV 2. The forward osmosis membrane according to item 1, wherein the N / A ratio is 0.30 to 0.53. [3] The ratio (O 533eV 3. The forward osmosis membrane according to item 1 or 2, wherein the N / N ratio is 0.35 to 0.51. [4] The forward osmosis membrane according to any one of items 1 to 3, wherein the ratio of the number of oxygen atoms to the number of nitrogen atoms (O / N ratio) when the surface of the separation functional layer is measured by X-ray photoelectron spectroscopy is 1.30 to 1.70. [5] The forward osmosis membrane according to any one of items 1 to 4, wherein the ratio of the number of oxygen atoms to the number of nitrogen atoms (O / N ratio) when the surface of the separation functional layer is measured by X-ray photoelectron spectroscopy is 1.40 to 1.65. [6] The forward osmosis membrane according to any one of items 1 to 5, wherein the porous support membrane is a hollow fiber membrane. [7] The forward osmosis membrane according to item 6, wherein the separation functional layer is disposed on the inner surface of the hollow fiber membrane. [8] The forward osmosis membrane according to any one of items 1 to 7, wherein the porous support membrane contains polysulfone or polyethersulfone as a main component. [9] The forward osmosis membrane according to any one of items 1 to 8, wherein the porous support membrane has an ethanol swelling rate of 1% to 5%.

[10] The forward osmosis membrane according to any one of items 1 to 9, wherein the surface pore size of the surface of the porous support membrane in contact with the separation functional layer is 1 nm to 15 nm.

[11] The forward osmosis membrane according to any one of items 1 to 10, wherein the surface pore size of the surface of the porous support membrane in contact with the separation functional layer is 2.5 nm or more.

[12] The forward osmosis membrane according to any one of items 1 to 11, wherein the surface pore size of the surface of the porous support membrane in contact with the separation functional layer is 11 nm or less.

[13] The forward osmosis membrane according to any one of items 1 to 12, wherein the porous support membrane has a thickness of 50 μm to 400 μm.

[14] The forward osmosis membrane according to any one of items 1 to 13, wherein the separation functional layer has an uneven structure.

[15] The forward osmosis membrane according to any one of items 1 to 14, wherein the separation functional layer has an arithmetic mean height of 60 nm or more.

[16] A method for producing a forward osmosis membrane having a porous support membrane and a separation functional layer disposed on the porous support membrane, comprising: A step of forming a polymer constituting a separation functional layer on a porous support membrane to obtain a composite membrane; A step of subjecting the composite film to a moist heat treatment to obtain a moist heat treated film; contacting the heat-and-moisture treatment film with a hydrophilic organic compound; Including, Purified water was placed as a raw material liquid on the separation functional layer side through the forward osmosis membrane, and a 3.5 mass% sodium chloride aqueous solution was placed as a draw solution on the porous support membrane side. When forward osmosis evaluation was performed while pressurizing the draw solution side to 40 kPa, The amount of water permeating into the draw solution F is 5.0 kg / (m 2 × hr) or more, and The water permeability F (kg / (m 2 × hr) and the amount of salt back-diffusion R (g / (m 2 × hr)) is expressed by the following formula: R ≤ 0.05 × e 0.225×F A method for satisfying the relationship expressed by

[17] The method according to item 16, wherein the porous support membrane is in contact with only the separation functional layer.

[18] The method according to any one of items 16 to 17, wherein the porous support membrane is a hollow fiber membrane.

[19] The method according to item 18, wherein the separation functional layer is disposed on the inner surface of the hollow fiber membrane.

[20] The method according to any one of items 16 to 19, wherein the porous support membrane contains polysulfone or polyethersulfone as a main component.

[21] The method according to any one of items 16 to 20, wherein the separation functional layer is a layer of a crosslinked polyamide obtained by reacting a polyfunctional amine with a polyfunctional acid halide.

[22] The method according to any one of items 16 to 21, wherein the moist heat treatment is carried out in a heated and pressurized moist gas atmosphere.

[23] The method according to any one of items 16 to 22, wherein the moist heat treatment is carried out by contacting the composite membrane with water vapor at 100°C or higher.

[24] The method according to any one of items 16 to 23, wherein the hydrophilic organic compound is an alcohol having 1 to 4 carbon atoms.

[25] The method according to any one of items 16 to 24, wherein the contact is carried out by bringing an aqueous solution containing the hydrophilic organic compound at a concentration of 40 mass % or more into contact with the heat-moisture treatment film.

[26] The method according to any one of items 16 to 25, wherein the contact is performed for 5 minutes or more.

[27] The method according to any one of items 16 to 26, wherein the contacting is carried out by one or more methods selected from the group consisting of immersion, flow through, and filtration.

[28] The method according to any one of items 16 to 27, wherein the ethanol swelling rate of the porous support membrane is 1% to 5%.

[29] The method according to any one of items 16 to 28, wherein the surface pore size of the porous support membrane is 15 nm or less.

[30] The method according to any one of items 16 to 29, wherein the surface pore size of the porous support membrane is 3 nm to 10 nm.

[31] The method according to any one of items 16 to 30, wherein the porous support membrane has a thickness of 50 μm to 400 μm.

[32] The method according to any one of the above items 16 to 31, wherein a salt permeation selectivity R / F, which is a ratio of the salt back-diffusion amount R to the water permeation amount F, is 0.10 g / kg or less.

[33] The method according to any one of the above items 16 to 32, wherein a salt permeation selectivity R / F, which is a ratio of the salt back-diffusion amount R to the water permeation amount F, is 0.07 g / kg or less.

[34] The method according to any one of items 16 to 33, wherein a salt permeation selectivity R / F, which is a ratio of the salt back-diffusion amount R to the water permeation amount F, is 0.035 g / kg or less.

[35] The water permeability F is 8.0 kg / (m 2 35. The method according to any one of items 16 to 34, wherein the running time is 100 s.p.m.×hr or more.

[36] The water permeability F is 10.0 kg / (m 2 36. The method according to any one of items 16 to 35, wherein the running time is 100 s.p.m.×hr or more. Effect of the Invention

[0016] According to one aspect of the present invention, there can be provided a forward osmosis membrane that simultaneously achieves good water permeability, good blocking properties, and good resistance to back pressure, and a method for producing such a forward osmosis membrane that can be easily produced. [Brief description of the drawings]

[0017] [Figure 1] FIG. 1 is a schematic cross-sectional view showing the structure of a hollow fiber membrane module as an example of a forward osmosis membrane module. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] Hereinafter, exemplary embodiments of the present invention (hereinafter also referred to as the present embodiments) will be described, but the present invention is not limited to these embodiments in any way.

[0019] ≪Forward osmosis membrane≫ One aspect of the present invention provides a forward osmosis membrane having a porous support membrane and a separation functional layer disposed on the porous support membrane. In one aspect, the porous support membrane is in contact with only the separation functional layer. In one aspect, the ratio of the relative element concentration obtained by curve fitting centered at 533 eV in the O1s spectrum to the relative element concentration obtained from the N1s spectrum when the surface of the separation functional layer is measured by X-ray photoelectron spectroscopy (O 533eV / N ratio) is 0.29 to 0.53. -1 Peak top intensity at 1720cm -1 Peak top intensity ratio (IR 1720 / IR 1650 ) is less than or equal to 0.25.

[0020] In one embodiment, the surface pore size of the porous support membrane on the surface in contact with the separation functional layer is 1 nm to 15 nm. In one embodiment, the membrane thickness of the porous support membrane is 50 μm to 400 μm. In one embodiment, the separation functional layer has an uneven structure. In one embodiment, the ratio of the number of oxygen atoms to the number of nitrogen atoms (O / N ratio) when the surface of the separation functional layer is measured by X-ray photoelectron spectroscopy is 1.30 to 1.70.

[0021] [Porous support membrane] The porous support membrane plays a role in providing strength to the separation functional layer. The porous support membrane may have a separation performance for particles insoluble in a solvent, but preferably does not have a separation performance for ions dissolved in a solvent. The composition of the porous support membrane is not particularly limited, but it is preferably formed of a resin, and more preferably formed of a thermoplastic resin. Here, the thermoplastic resin means a material that exhibits a property of deforming or flowing when heated by an external force, and in one embodiment is a chain polymer.

[0022] Examples of thermoplastic resins include polysulfone, polyethersulfone, polyketone, polyamide, polyester, cellulose-based polymer, vinyl polymer, polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfone, polyphenylene oxide, etc., and these homopolymers or copolymers can be used alone or in a blend of two or more. These polymers also include those having any functional group in the main chain, side chain, or terminal (i.e., derivatives).

[0023] Specific examples of the thermoplastic resin include the following resins. Cellulosic polymers, such as cellulose acetate, cellulose nitrate, etc.; Examples of vinyl polymers include polyethylene, polypropylene, polyvinyl chloride, chlorinated polyvinyl chloride, polyacrylonitrile, etc.; Each of them can be mentioned.

[0024] Among the above-mentioned examples, it is particularly preferable to use one or more selected from polysulfone, polyacrylonitrile, polyamide, polyester, polyvinyl alcohol, polyphenylene sulfide sulfone, polyphenylene sulfone, polyphenylene sulfide, polyethersulfone, polyvinylidene fluoride, cellulose acetate, polyvinyl chloride, and chlorinated polyvinyl chloride. More preferably, cellulose acetate, polysulfone, polyethersulfone, polyketone, or polyacrylonitrile is used. Polysulfone or polyethersulfone, especially polysulfone, is more preferable because it is chemically, mechanically, and thermally stable, widely available, and easy to mold.

[0025] The porous support membrane may be made of a material containing a thermoplastic resin selected from the above as a main component. "Containing as a main component" means that the porous support membrane contains one or more specific thermoplastic resins in an amount of more than 50 mass%, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, or 95 mass% or more, based on the total mass of the porous support membrane. The porous support membrane may consist only of a thermoplastic resin selected from the above.

[0026] The shape of the porous support membrane is preferably a film (flat membrane), a hollow fiber, or the like, or a chemically or physically modified form thereof. The porous support membrane is more preferably a hollow fiber membrane, since a forward osmosis membrane with a larger membrane area can be stored in a smaller space when modularized.

[0027] In the present disclosure, the membrane area refers to the area of ​​the region where the forward osmosis membrane can come into contact with the raw liquid and exhibit a separation function, that is, the area of ​​the part of the forward osmosis membrane that comes into contact with the raw liquid. More specifically, for example, in the case of a hollow fiber forward osmosis membrane module that supplies the raw liquid to the inside, the membrane area (the inner surface area of ​​the hollow fiber forward osmosis membrane) is defined by the following formula based on the length (also called effective length), inner diameter, and number of hollow fiber forward osmosis membranes excluding the adhesive fixing part in the module. a=c×π×b×n Here, a is the inner surface area of ​​the hollow fiber forward osmosis membrane (m 2 ), b is the length (m) of the hollow fiber forward osmosis membrane excluding the adhesive fixing portion, c is the inner diameter (m) of the hollow fiber forward osmosis membrane, and n is the number of hollow fiber forward osmosis membranes.

[0028] (Surface pore diameter) In the forward osmosis membrane of this embodiment, it is preferable that the surface pore size on the surface of the porous support membrane that is in contact with the separation functional layer is controlled to a specific range. As a result, the separation functional layer is firmly held on the porous support membrane by the anchor effect by partially entering the pores of the porous support membrane, and the advantage that the separation functional layer is difficult to peel off from the porous support membrane even when a back pressure is applied is obtained. In addition, if the surface pore size is too small, the supply balance of the material monomer may be lost when the material monomer of the separation functional layer is polymerized on the porous support membrane to form the separation functional layer. Such a supply balance loss leads to the generation of a separation functional layer that has a low degree of crosslinking and is easily peeled off from the porous support membrane. Furthermore, when the surface pore size is a predetermined value or more, each solution is likely to diffuse through the porous support membrane to the interface between the porous support membrane and the separation functional layer, and the osmotic pressure is easily secured on both sides of the separation functional layer, so that the water permeability as a forward osmosis membrane is improved. Therefore, it is preferable that the surface pore size is a predetermined value or more. On the other hand, when the surface of the porous support membrane that contacts the separation functional layer has a dense structure (i.e., the surface pore size is small), the monomer supply is appropriately slow, and the monomer remaining in the porous support membrane even after the reaction can further react due to an increase in temperature or the passage of time, so that the separation functional layer formed at the interface with the porous support membrane is thin and dense, facilitating the hydrophilization treatment described below during the manufacture of the separation functional layer. In other words, when the wet heat treatment of the present disclosure and further treatment with a hydrophilic organic compound are performed during the manufacture of the separation functional layer, the separation functional layer formed on the porous support membrane with a small surface pore size can retain more hydroxyl groups provided by the hydrophilization treatment due to the contribution of the above structure (in one embodiment, the O / N ratio and O 533eV A forward osmosis membrane having such a separation functional layer can have high water permeability while having high blocking property and high back pressure resistance.

[0029] The surface pore size is preferably 1 nm or more, or 1.5 nm or more, or 2 nm or more, or 2.5 nm or more, or 3 nm or more, or 4 nm or more, or 5 nm or more from the viewpoint of obtaining a good anchor effect and from the viewpoint of obtaining a good effect of hydrophilization of the separation functional layer, and is preferably 15 nm or less, or 13 nm or less, or 12 nm or less, or 11 nm or less, or 10 nm or less, or 9 nm or less, or 8 nm or less. The surface pore size is a value obtained by averaging the circle equivalent diameter (circle equivalent diameter) of the pores included in an arbitrarily selected 1.0 μm × 1.0 μm field of view at a magnification of 50,000 times in a surface observation image of the porous support membrane using a scanning electron microscope (SEM). Since it is preferable that a uniform surface pore size is obtained over the entire porous support membrane, it is preferable to evaluate it as an average value calculated from surface observation images of samples sampled from different parts of the porous support membrane. The surface pore size of a certain porous support membrane is almost the same as the surface pore size of the porous support membrane facing the separation functional layer when the separation functional layer is formed on the porous support membrane, and the surface pore size of the porous support membrane exposed by removing the separation functional layer from the forward osmosis membrane. Therefore, for example, the surface pore size of the porous support membrane exposed by removing the separation functional layer from the forward osmosis membrane can be regarded as the surface pore size of the porous support membrane used in the manufacture of the forward osmosis membrane. As a method for removing the separation functional layer, a known method can be used depending on the chemical structure of the separation functional layer. As an example, when the separation functional layer is made of crosslinked polyamide, it is possible to decompose and remove the separation functional layer by immersing it in an aqueous solution consisting of 2.0 mass% sodium hypochlorite, 2.0 mass% sodium hydroxide, and 0.15 mass% calcium chloride at 60°C or higher for 200 hours or more. If the decomposition is insufficient, the separation functional layer can be decomposed and removed by combining two or more known methods. In the decomposition and removal, a method is adopted that decomposes the separation functional layer and does not affect the porous support membrane and / or the surface pore size of the porous support membrane. Whether or not the surface pore size of the porous support membrane is affected can be determined by observing the surface pore size before and after treatment when only the porous support membrane is treated by the same method as above.When the surface pore size of the porous support membrane changes due to the decomposition and removal method of the separation functional layer, the surface pore size of the porous support membrane facing the separation functional layer can be estimated taking into account that change.

[0030] The surface pore size can be controlled by controlling the composition of the material polymer composition used to form the porous support membrane, the temperature of each solution when forming the porous support membrane by phase separation, the membrane formation environment (e.g., temperature and humidity, membrane formation time, etc.), etc. For example, the surface pore size can be made smaller by increasing the material polymer concentration of the material polymer composition, or the surface pore size can be made larger by decreasing the material polymer concentration.

[0031] (Film thickness) The thickness of the porous support membrane is preferably 50 μm to 400 μm. In a forward osmosis membrane without a substrate, it is desired that the porous support membrane has a sufficient reinforcing effect on the separation functional layer. The membrane thickness is preferably 50 μm or more, or 80 μm or more, or 100 μm or more from the viewpoint of preventing excessive deformation when swollen with a solvent and suppressing salt back diffusion due to damage to the separation functional layer even during repeated use, and is preferably 400 μm or less, or 350 μm or less, or 300 μm or less, or 250 μm or less from the viewpoint of water permeability.

[0032] (Outer and inner diameters of hollow fiber membrane) In one embodiment, when the porous support membrane is a hollow fiber membrane, the outer diameter and inner diameter are not limited, but considering the membrane production stability, ease of handling, membrane area in a module, etc., the outer diameter is preferably 100 μm to 3,000 μm and the inner diameter is 30 μm to 2,500 μm, and the outer diameter is more preferably 200 μm to 1,500 μm and the inner diameter is 50 μm to 1,000 μm. Furthermore, considering both the ability to pass a raw material liquid containing a poorly soluble substance through the hollow portion without any problems and strength, the outer diameter is preferably 500 μm to 1,300 μm and the inner diameter is 200 μm to 1,000 μm. The membrane thickness of the hollow fiber membrane refers to the value obtained by dividing the difference between the outer diameter and the inner diameter of a cross section obtained by cutting the hollow fiber membrane along a plane perpendicular to the membrane surface direction (longitudinal direction) by 2. The inner diameter, outer diameter, and membrane thickness can be measured by observing the cross section of the hollow fiber membrane using an optical microscope or a scanning electron microscope. The porous support membrane obtained by removing the separation functional layer from the forward osmosis membrane may also be observed.

[0033] In the forward osmosis membrane according to one embodiment, the porous support membrane is in contact with only the separation functional layer. In this case, when the forward osmosis membrane is combined with other members to be modularized, the porous support membrane is not prevented from being in contact with members other than the forward osmosis membrane. The porous support membrane has the effect of reinforcing the separation functional layer, and in conventional forward osmosis membranes and reverse osmosis membranes, a good reinforcing effect is obtained by combining the porous support membrane with a substrate. However, when the forward osmosis membrane has a substrate, the forward osmosis membrane may be damaged due to a large difference in the swelling degree with respect to an organic solvent between the substrate and the porous support membrane. For example, when the forward osmosis membrane is brought into contact with an organic solvent, if the porous support membrane swells more than the substrate, the entire forward osmosis membrane is deformed to release the stress applied to the porous support membrane, which may cause defects in the separation functional layer. In addition, peeling or cracks may occur at the interface between the substrate and the porous support membrane due to the difference in the swelling degree between the two. Therefore, in one embodiment, the forward osmosis membrane does not have a substrate.

[0034] In one embodiment, the forward osmosis membrane is composed of a porous support membrane and a separation functional layer. However, "composed of a porous support membrane and a separation functional layer" does not mean that the components of the forward osmosis membrane are strictly limited to the porous support membrane and the separation functional layer, but may contain optional components such as a dispersant, a coating agent, a moisturizing agent, a preservative, etc., in addition to these, as long as the effects of the present invention are not impaired. These optional components may be inorganic compounds or organic compounds.

[0035] The substrate is generally porous, and specific examples thereof include woven fabric, nonwoven fabric, mesh net, and foamed sintered sheet. Examples of the material of the substrate include polyester, polyamide, polyolefin, and mixtures and copolymers thereof. The substrate is generally a porous body having a pore size larger than that of the porous support membrane and the separation functional layer. The substrate may have an average pore size of 0.1 μm to 100 μm as measured using a general porometer such as a macro-nano porometer (manufactured by PIM Co., Ltd.), and / or a basis weight of 20 g / m. 2 ~150g / m 2 and / or the air permeability measured by the Frazier method may be 0.5 cc / (cm 2 ×sec)~30cc / (cm 2 × sec). The substrate generally does not have a separation function for solutes such as ions, but may have a separation function for solids such as particles.

[0036] (Ethanol swelling rate) In one embodiment, the porous support membrane has an ethanol swelling ratio in a specific range. It is believed that the separation functional layer is held on the porous support membrane by the anchor effect by partially entering the pores of the porous support membrane, and when forward osmosis treatment is performed in the presence of an organic solvent, the porous support membrane and the separation functional layer swell with the organic solvent. Such swelling increases the pore size of the porous support membrane, thereby reducing the anchor effect and causing the separation functional layer to peel off from the porous support membrane. Therefore, it is desirable that the porous support membrane is less likely to swell in an organic solvent. On the other hand, it is preferable that the porous support membrane has an ethanol swelling ratio of a certain level or more from the viewpoint of improving the diffusibility of the draw solution in contact with the forward osmosis membrane and from the viewpoint of the hydrophilicity of the membrane to obtain good water permeability. In other words, the swelling ratio with respect to ethanol, which is a hydrophilic organic solvent, is an indicator of both the hydrophilicity of the porous support membrane and its swelling property with respect to the organic solvent. In one embodiment, the ethanol swelling ratio of the porous support membrane is preferably 1% or more, or 1.2% or more, or 1.5% or more, or 1.7% or more, or 2% or more from the viewpoint of obtaining good diffusibility of the draw solution and good water permeability, and is preferably 5% or less, or 4.5% or less, or 4% or less, or 3.5% or less, or 3% or less from the viewpoint of obtaining good blocking properties and back pressure resistance. The ethanol swelling ratio is a value measured in accordance with the description in [Examples] of the present disclosure.

[0037] [Separation functional layer] The separation functional layer essentially performs the function of separating solutes in the forward osmosis membrane. More specifically, it performs the function of separating the solvent in the liquid mixture from the solutes, such as ions, dissolved in the solvent. The composition, thickness, etc. of the separation functional layer are set according to the purpose of use of the forward osmosis membrane. The separation functional layer may be present on one or both sides of the porous support membrane. When the separation functional layer is present on both sides of the porous support membrane, the thickness, separation performance, salt blocking performance, etc. of the separation functional layer on these sides may be the same or different from each other. In addition, the separation functional layers on both sides of the porous support membrane may be continuous or discontinuous via the porous support membrane.

[0038] When separation functional layers are disposed on both sides of the porous support membrane, the "separation functional layer side" in the present disclosure means the side of the layer that rejects the solute with a higher rejection rate in the entire forward osmosis membrane. The following method, for example, can be used to know the side that rejects the solute with a higher rejection rate.

[0039] The amount of salt back-diffusion into the feed solution is evaluated when purified water is placed as the feed solution on one side and the draw solution on the other side through a forward osmosis membrane, and when the arrangement of these solutions is reversed. When comparing these two evaluation results, the feed solution side with the arrangement that results in a smaller amount of salt back-diffusion can be the side that blocks the solute of the draw solution with higher efficiency, that is, the separation functional layer side, and the opposite side can be the support membrane side. In one embodiment, the draw solution is a 3.5% by mass aqueous sodium chloride solution or a 50% by mass aqueous isopropanol solution, particularly a 3.5% by mass aqueous sodium chloride solution.

[0040] Examples of the material of the separation functional layer include one or more materials selected from a polymer, an inorganic substance, an organic-inorganic hybrid compound, and a composition in which a specific inorganic compound or an organic compound is dispersed or dissolved therein. In one embodiment, the separation functional layer includes a nitrogen-containing material. In one embodiment, the surface of the separation functional layer may be hydrophilized. The hydrophilization treatment can be carried out, for example, by contacting the polymer with a hydrophilic organic compound described below.

[0041] In one embodiment, the separation functional layer is composed of a high molecular weight polymer. The separation functional layer composed of a high molecular weight polymer preferentially allows the solvent to permeate and blocks the solute, and has substantial separation performance. Examples of the high molecular weight polymer include polyamide, polyvinyl alcohol / polypiperazine amide, polypiperazine amide, polyimide, sulfonated polyether sulfone, and composite materials composed of two or more of these, and preferably one or more selected from the group consisting of polyamide, polyvinyl alcohol, polypiperazine amide, and polyimide. From the viewpoint of easily forming a defect-free thin film on the porous support membrane, the separation functional layer is a polyamide layer in one embodiment.

[0042] The polyamide layer is a layer containing polyamide as a main component. In the present disclosure, "containing polyamide as a main component" means a separation functional layer in which the mass ratio of polyamide to the total mass of the separation functional layer is 50 mass% or more, or 75 mass% or more, or 95 mass% or more, or 100 mass%. The polyamide layer is preferably formed of a polycondensation product of a polyfunctional amine and a polyfunctional acid halide. More preferably, the polyamide layer is mainly composed of a polyamide formed of a bifunctional amine and a trifunctional acid halide. The formation of the polyamide layer includes forming a polyamide skeleton by performing interfacial polycondensation on the surface of the porous support membrane using an aqueous solution containing a polyfunctional amine and an organic solvent solution containing a polyfunctional acid halide. The organic solvent in the organic solvent solution containing a polyfunctional acid halide is preferably an organic solvent immiscible with water. The method for forming the polyamide layer will be described in detail later.

[0043] (Average thickness of separation functional layer) The average thickness of the separation functional layer is preferably as thin as possible without pinholes. However, in order to maintain mechanical strength and chemical resistance, it is desirable to have an appropriate thickness. Considering the film formation stability, water permeation resistance, etc., the average thickness of the separation functional layer, for example, the average thickness of the separation functional layer (polymer thin film) made of a polymer, is preferably 0.01 μm to 3 μm, more preferably 0.1 μm to 1 μm, and even more preferably 0.1 μm to 0.8 μm.

[0044] The average thickness of the separation functional layer is measured by microscopic observation. Specifically, for example, the separation functional layer is embedded in a resin, and then cut to prepare ultrathin slices. The obtained slices are stained and observed with a transmission electron microscope (TEM) or a scanning electron microscope (SEM). A preferred method for measuring the thickness is to import an image of a cross section of the separation functional layer in the thickness direction taken with a scanning electron microscope into a suitable image processing software and process the image. An example of the image processing software is ImageJ (developed by the National Institutes of Health). The outline of the separation functional layer is extracted from the SEM image imported into ImageJ, and the inside is filled in to calculate the area of ​​the separation functional layer, which can be converted into the average thickness of the separation functional layer in one image using a calibration curve prepared in advance.

[0045] More specifically, the contour of the separation functional layer is extracted by, for example, binarizing the SEM image imported into ImageJ by a known binarization method, preferably the Otsu method, appropriately selected based on the obtained image. The contour at the contact interface between the porous support membrane of the forward osmosis membrane and the separation functional layer is obtained by calculating the average brightness in the horizontal direction from the membrane surface in the entire obtained binarized image, comparing the average brightness from the surface of the separation functional layer toward the porous support membrane side, and the horizontal direction of the part with the highest average brightness is the contact interface between the porous support membrane of the forward osmosis membrane and the separation functional layer, and the straight part can be the contour. In addition, the contour at the surface of the separation functional layer can be a curved line connecting the parts with a contrast difference from the background in the obtained binarized image with a continuous line. The contour in the thickness direction may be both ends of the obtained image. The contour of the separation functional layer can be extracted by connecting these lines.

[0046] The observation magnification of the cross-sectional image is, for example, preferably 5,000 to 30,000 times, more preferably 10,000 times. The width of the cross section (the length in the direction parallel to the interface between the porous support membrane and the separation functional layer) is preferably about 5 to 100 μm, more preferably 5 to 50 μm, even more preferably 5 to 20 μm, and most preferably 13 μm.

[0047] In addition, there may be cases where the contact interface between the porous support membrane and the separation functional layer of the forward osmosis membrane is wavy and cannot be expressed as a straight line, but unless the membrane is intentionally bent for measurement, the contact interface between the porous support membrane and the separation functional layer of the forward osmosis membrane can be unambiguously determined by a similar method.

[0048] (Uneven structure) In one embodiment, the separation functional layer has an uneven structure on the surface (more specifically, the outermost surface, which is the exposed surface). This allows the separation functional layer to follow the shape change of the porous support membrane well even when the porous support membrane swells due to contact with an organic solvent, thereby preventing the performance of the forward osmosis membrane from being reduced due to damage to the separation functional layer. In the present disclosure, the uneven structure means that the outermost surface of the separation functional layer (i.e., the surface not in contact with the porous support membrane) has multiple convex and concave portions, which are present repeatedly. In one embodiment, the uneven structure has an unevenness height of 40 nm or more, which is the arithmetic mean height (Sa). The arithmetic mean height (Sa) means the arithmetic mean height (Sa) defined by ISO 25178 when the surface roughness of the outermost surface of the separation functional layer is measured.

[0049] The arithmetic mean height (Sa) of the uneven structure of the separation functional layer is preferably 60 nm or more, more preferably 100 nm or more, from the viewpoint that the separation functional layer can easily follow the deformation of the porous support membrane when the porous support membrane is deformed. In addition, in practical use, depending on the properties of the liquid passing through the forward osmosis membrane, there is a possibility that a substance that is easily caught in the uneven structure of the separation functional layer and adheres to the membrane surface may be mixed in. In such a case, from the viewpoint of reducing adhesion, the arithmetic mean height (Sa) of the separation functional layer is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less.

[0050] In one embodiment, the uneven structure has a repeating uneven shape in a first direction due to the convex portions extending in a stripe pattern, and the convex portions may have an elongated length in a direction different from the first direction (in one embodiment, approximately perpendicular to the first direction) (i.e., may have a pleated structure).

[0051] The arithmetic mean height (Sa) of the relief structure of the separation functional layer can be analyzed by an atomic force microscope (AFM). Specifically, under conditions in which the forward osmosis membrane does not dry out, the surface of the separation functional layer is exposed as an observation sample, and AFM observation is performed. The measurement conditions are, for example, as follows. Measurement mode: QNM in fluid (measurement in pure water) Field of view size: 3μm square Probe used: OLTESPA For example, under the above-mentioned conditions, the outermost surface of the separation functional layer is scanned to measure the arithmetic mean height (Sa), and the average value of nine samples is suitably evaluated.

[0052] In one embodiment, the method for measuring the concave-convex structure of the separation functional layer is as follows. Under conditions where the membrane does not dry out, the hollow fiber membrane is divided into three equal parts in the longitudinal direction to obtain three samples. Any part of each of the three samples, preferably the part divided into two equal parts in the longitudinal direction, is cut open obliquely to expose the surface of the separation functional layer, and the arithmetic mean height of the separation functional layer in each sample is measured by observing with an atomic force microscope.

[0053] This operation is performed on three forward osmosis membranes or three forward osmosis membranes cut out from one forward osmosis membrane module, and the average of the arithmetic mean heights of the separation functional layers in a total of nine samples can be used as the arithmetic mean height of the forward osmosis membrane.

[0054] When cutting out three forward osmosis membranes from one forward osmosis membrane module, it is preferable to cut them out from three locations in the radial direction of the forward osmosis membrane module: the outer periphery, the middle, and the center. By using such a cutting method, the variation of the entire module can be evaluated.

[0055] In the case of a flat forward osmosis membrane, a method can be adopted in which the membrane is divided into nine parts to obtain nine samples under conditions in which the membrane does not dry out, and the center of each sample is observed using an atomic force microscope.

[0056] The uneven structure can be formed, for example, by controlling the composition of the material monomer composition used to form the separation functional layer, the difference in monomer supply speed depending on the surface pore size of the porous support membrane, etc. For example, in an embodiment in which a material monomer composition is applied to a porous support membrane to form a separation functional layer by interfacial polymerization, if a surfactant is contained in the material monomer composition, the uneven structure is formed by making it easier for the monomer to be continuously supplied to the reaction interface even after the separation functional layer is initially formed. In addition, if the surface pore size of the porous support membrane is within a predetermined range, the uneven structure is easily formed because the uneven structure is easily formed by making it easier to supply the monomer over time while suppressing defects in the separation functional layer that occur initially and making the film thickness of the separation functional layer moderately thin.

[0057] (O / N ratio) The ratio of the number of oxygen atoms to the number of nitrogen atoms (O / N ratio) when the surface (more specifically, the exposed surface) of the separation functional layer is measured by X-ray photoelectron spectroscopy is an index of the proportion of hydrophilic structures on the surface of the separation functional layer. In one embodiment, the nitrogen atoms are derived from the constituent material of the separation functional layer, particularly a polymer. That is, in one embodiment, the separation functional layer contains a nitrogen-containing material. The presence of a hydrophilic structure on the surface of the separation functional layer contributes to improving water permeability, but excessive hydrophilicity also increases the back diffusion of the draw solution in the forward osmosis method, and the osmotic pressure difference through the separation functional layer decreases, thereby decreasing the water permeability. Therefore, it is preferable that the O / N ratio is controlled within a moderate range. In one embodiment, the O / N ratio is 1.30 or more, or 1.35 or more, or 1.40 or more, or 1.45 or more, or 1.50 or more, and in one embodiment, it is 1.70 or less, or 1.65 or less, or 1.60 or less. The O / N ratio in the above range is particularly advantageous in a separation functional layer composed of a polyamide consisting of a bifunctional amine having two or more amino groups in one molecule and a trifunctional carboxylic acid halide having three or more carboxylic acid halide groups in one molecule. The O / N ratio can be controlled by adjusting the constituent materials of the separation functional layer. For example, the composition of the polymer constituting the separation functional layer, the composition of the hydrophilic organic compound used to hydrophilize the polymer, etc. may be adjusted. The O / N ratio can be evaluated based on the method described in the examples below.

[0058] (O 533eV / N ratio) The ratio of the relative elemental concentration of oxygen obtained by curve fitting centered at 533 eV in the O1s spectrum to the relative elemental concentration of nitrogen obtained from the N1s spectrum when the surface (more specifically, the exposed surface) of the separation functional layer is measured by X-ray photoelectron spectroscopy (O 533eV The O / N ratio is an index of the proportion of hydrophilic structures on the surface of the separation functional layer, and in particular, an index of the proportion of water molecules or hydrophilic compounds that are strongly adsorbed on the separation functional layer. 533eV When the O / N ratio is large, the hydrophilicity of the spaces (such as the free volume spaces of the components that make up the separation functional layer) present on or inside the separation functional layer increases, resulting in an increase in the spaces through which solvents (especially water) can highly selectively permeate, improving the water permeability (solvent permeability) of the forward osmosis membrane. On the other hand, for example, in a separation functional layer made of polyamide, when the degree of crosslinking is low, the result can be that the number of uncrosslinked terminal functional groups increases, resulting in a high relative elemental ratio of oxygen atoms. In this case, by using IR measurements, etc., as described below, in combination, the uncrosslinked terminal functional groups of the separation functional layer can be measured based on the O / N ratio or O 533eV Taking into account the effect on the / N ratio, it is possible to more accurately estimate the proportion of water molecules that are firmly adsorbed to the separation functional layer, or the proportion of hydrophilic compounds that are adsorbed by the hydrophilization treatment described below. When the degree of crosslinking in the separation functional layer is low, the disadvantage of a significantly increased amount of salt back diffusion is more likely to be manifested than the advantage of improved water permeability of the forward osmosis membrane, and as a result, the performance of the forward osmosis membrane often deteriorates. This is thought to be because, for example, uncrosslinked low-molecular-weight oligomers exist in the separation functional layer, and when they are desorbed, large holes are formed in the separation functional layer, and these large holes become spaces (defects in the separation functional layer) through which the lead solute can easily back-diffuse.

[0059] In this embodiment, since the separation functional layer has a high degree of crosslinking and is capable of firmly adsorbing and supporting a hydrophilic substance, it is possible to increase the space through which the solvent can highly selectively permeate while forming a space through which the lead solute is less likely to back-diffuse. Therefore, according to this embodiment, a high-performance forward osmosis membrane having high water permeability (solvent permeability) and low salt back-diffusion amount is provided.

[0060] In one embodiment, the nitrogen atoms are derived from the constituent material of the separation functional layer, particularly a high molecular weight polymer. That is, in one embodiment, the separation functional layer contains a nitrogen-containing material. The presence of a hydrophilic structure on the surface of the separation functional layer contributes to improving water permeability, but excessive adsorption of a hydrophilic substance also enhances the back diffusion of the draw solution in the forward osmosis method, and the osmotic pressure difference through the separation functional layer decreases, thereby decreasing water permeability. 533eV It is preferable that the / N ratio is controlled within a suitable range. 533eV In one embodiment, the / N ratio is 0.29 or more, or 0.30 or more, or 0.35 or more, or 0.40 or more, or 0.43 or more, or 0.45 or more, and in one embodiment, 0.53 or less, or 0.51 or less, or 0.48 or less. The above range is particularly advantageous when the separation functional layer is composed of a polyamide consisting of a bifunctional amine having two or more amino groups in one molecule and a trifunctional carboxylic acid halide having three or more carboxylic acid halide groups in one molecule. 533eV The O / N ratio can be controlled by adjusting the constituent materials of the separation functional layer. For example, the composition of the polymer constituting the separation functional layer, the composition of the hydrophilic organic compound used to hydrophilize the polymer, etc. may be adjusted. 533eV The / N ratio can be evaluated based on the method described in the Examples below.

[0061] (IR 1720 / IR 1650 ) In one embodiment, the surface of the separation functional layer is measured by IR at 1650 cm -1 Peak top intensity at 1720cm -1 Peak top intensity ratio IR 1720 / IR 1650is 0.25 or less, or 0.20 or less. 533eV In order to more accurately estimate the ratio of water molecules that are strongly adsorbed on the separation functional layer or the ratio of hydrophilic compounds that are adsorbed by hydrophilization treatment in the O / N ratio, IR measurement can be used as an example. In one embodiment, in a separation functional layer made of polyamide, one of the uncrosslinked functional group ends is carboxylic acid (COOH). In this case, the relative element concentration ratio of oxygen element is influenced by the uncrosslinked end. When this influence is large, the O / N ratio and O 533eV The / N ratio is expected to be large. In addition, in a separation functional layer with many uncrosslinked ends, the degree of crosslinking is low, so the blocking ability is low, and as a result, the performance as a forward osmosis membrane may be poor. Generally, in the IR spectrum, the C=O stretching vibration of carboxylic acid is 1720 cm -1 The amide I band, which contains the C=O stretching vibration of the amide bond, is observed around 1650 cm -1 Since it is observed near the amide intensity ratio (IR 1720 / IR 1650 ) is a measure of the degree of crosslinking in polyamides. Considering that the spectrum of carboxylic acids falls on the tail of the spectrum of amides, IR 1720 / IR 1650 It is advantageous that the O / N ratio or O is 0.25 or less, or 0.20 or less. 533eV The effect of carboxylic acid on the O / N ratio was small, and the O / N ratio or O 533eV The / N ratio is considered to more accurately represent the proportion of water molecules firmly adsorbed on the separation functional layer or the proportion of hydrophilic compounds adsorbed by hydrophilization treatment. 1720 / IR 1650 With the O / N ratio and / or O 533eV A ratio of IR / N indicates that the separation functional layer has a high degree of crosslinking and is capable of firmly adsorbing and supporting a hydrophilic substance. 1720 / IR 1650can be evaluated based on the method described in the Examples below. The baseline for calculating the peak intensity ratio by IR measurement is set as follows: -1 If the absorbance at 1800 cm is low and stable, -1 On the other hand, the absorbance at 1800cm -1 If the absorbance of is high or unstable, 1800 to 2500 cm -1 In addition, when a separation functional layer other than a polyamide layer is used, the proportion of water molecules firmly adsorbed to the separation functional layer or hydrophilic compounds adsorbed by hydrophilization treatment can be estimated in the same manner by comparing the crosslinked functional groups with the uncrosslinked functional groups by any known method.

[0062] [Characteristics of forward osmosis membrane] (shape) The forward osmosis membrane of this embodiment may be a hollow fiber membrane, a flat membrane, etc., but is preferably a hollow fiber membrane. The hollow fiber membrane is advantageous in that it can accommodate a larger membrane area in a smaller space when modularized, and that it is easy to form the separation functional layer without defects. From the viewpoint of preventing physical damage to the separation functional layer, it is more preferable to arrange the separation functional layer on the inner surface of the hollow fiber membrane.

[0063] (Water permeability and salt back-diffusion) The forward osmosis membrane of this embodiment has both high water permeability (i.e., high water permeability F) and high rejection (i.e., low salt back-diffusion amount R). The water permeability F and salt back-diffusion amount R are evaluated by performing forward osmosis treatment using purified water as the feed solution and a 3.5% by mass sodium chloride aqueous solution as the draw solution, with each solution at 25°C.

[0064] Here, the water permeability F may vary significantly depending on whether the raw material liquid and the draw solution are placed on the separating functional layer side or the support membrane side of the present disclosure, respectively. In this embodiment, when the forward osmosis membrane is put into practical use, in order to reduce the risk of contamination of the membrane, it is desirable to place the raw material solution on the separation functional layer side and the draw solution on the support membrane side. When evaluating the water permeability and salt back diffusion amount of the forward osmosis membrane, it is desirable to place the raw material solution on the separation functional layer side and the draw solution on the support membrane side, so as to reflect the performance in practical use.

[0065] The salt back diffusion amount R (RSF) of a forward osmosis membrane means the amount of solute that moves from the draw solution to the raw liquid when the feed liquid is placed on the separation functional layer side of the forward osmosis membrane and the draw solution with a higher osmotic pressure is placed on the support membrane side. The salt back diffusion amount R is defined by the following formula (1). R = G / (M×H) (1) where G is the amount of solute transferred (g) and M is the effective surface area of ​​the forward osmosis membrane (m 2 ) and H is time (hr).

[0066] The lower the salt back-diffusion amount R of the forward osmosis membrane of this embodiment, the more preferable. The larger the salt back-diffusion amount, the greater the amount of solutes in the draw solution that are mixed into the feed solution; the greater the amount of solutes in the feed solution that are mixed into the draw solution; the purity of the feed solution concentrate decreases, causing a loss of component balance; the draw solution becomes contaminated; the draw solution becomes less rich in components over time; and the like. In one aspect, the salt back-diffusion amount R of the forward osmosis membrane of this embodiment is 2.0 g / (m 2 ×hr), and preferably 1.2 g / (m 2 ×hr), and more preferably 0.80 g / (m 2 ×hr) or less, and more preferably 0.40 g / (m 2 ×hr), and particularly preferably 0.30 g / (m 2 × hr) or less. The salt back diffusion amount R of the forward osmosis membrane of this embodiment is 0.001 g / (m 2 × hr) or more, the advantageous effects expected by the present invention are manifested.

[0067] The water permeability F (Flux) of a forward osmosis membrane means the amount of water that moves from the raw material solution to the draw solution when the raw material solution is placed on the separation functional layer side of the forward osmosis membrane and the draw solution having a higher osmotic pressure is placed on the support membrane side. The water permeability F of a forward osmosis membrane is defined by the following formula (2). F = L / (M × H) (2) where L is the amount of water that has permeated (kg) and M is the effective surface area of ​​the forward osmosis membrane (m 2 ) and H is time (hr).

[0068] The forward osmosis membrane of the present embodiment has a higher water permeability F, which is preferable. In order to achieve highly efficient solvent transfer, the forward osmosis membrane has a water permeability F of preferably 3.0 kg / (m 2 ×hr) or more, or 5.0 kg / (m 2 ×hr) or more, or 7.0 kg / (m 2 ×hr) or more, or 8.0 kg / (m 2 ×hr) or more, or 9.0 kg / (m 2 ×hr) or more, or 10.0 kg / (m 2 On the other hand, if the water permeability is excessively large, the amount of back-diffusion of salts may become large. Therefore, the water permeability F of the forward osmosis membrane is set to 50 kg / (m 2 × hr) or less.

[0069] In this embodiment, the salt permeation selectivity R / F (RSF / Flux: unit g / kg), which is defined as the salt back diffusion amount R divided by the water permeation amount F, is an index that represents the selectivity between solvent permeation and salt permeation, i.e., the overall performance of the forward osmosis membrane. The lower this value, the more difficult it is for salt to permeate and the easier it is for solvent to permeate. Therefore, the lower this value, the more preferable. In conventional general forward osmosis membranes, when the salt back diffusion amount is low, the water permeation amount is often significantly reduced, and as a result, the R / F value is often large. From the viewpoint of practicality of concentrating the raw material liquid and highly efficient solvent transfer, the R / F value of the forward osmosis membrane of this embodiment is preferably 0.20 g / kg or less, or 0.15 g / kg or less, or 0.10 g / kg or less, or 0.08 g / kg or less, or 0.07 g / kg or less, or 0.06 g / kg or less, or 0.05 g / kg or less, or 0.04 g / kg or less, or 0.035 g / kg or less in the initial state (standard). The R / F value is ideally 0 g / kg, but from the viewpoint of ease of manufacturing the forward osmosis membrane, it may be, for example, 0.0001 g / kg or more.

[0070] <Manufacturing method of forward osmosis membrane> One aspect of the present invention provides a method for producing a forward osmosis membrane. In one aspect, the forward osmosis membrane may be the forward osmosis membrane of the present embodiment described above. In one aspect, the method includes: A step of forming a polymer constituting a separation functional layer on a porous support membrane to obtain a composite membrane; A step of subjecting the composite film to a moist heat treatment to obtain a moist heat treated film; and contacting the heat-moisture treated film with a hydrophilic organic compound.

[0071] The forward osmosis membrane obtained by the method of the present embodiment has a unique feature of achieving both low salt permeation selectivity and high water permeation rate under back pressure. In one embodiment, purified water is placed as a raw material solution on the separation functional layer side of the forward osmosis membrane, and a 3.5 mass% aqueous sodium chloride solution is placed as a draw solution on the porous support membrane side. When forward osmosis evaluation is performed at 25°C while applying a pressure of 40 kPa (i.e., applying a back pressure) with the draw solution side as the positive side, the water permeation rate F into the draw solution is 5.0 kg / (m 2× hr) or more, and the water permeability F (kg / (m 2 × hr) and the amount of salt back-diffusion R (g / (m 2 × hr) is expressed by the following formula: R≦0.05×e 0.225×F In one embodiment, in the forward osmosis evaluation, the amount of water permeated into the draw solution F (kg / (m 2 × hr)) to the amount of salt back-diffusion R (g / (m 2 The salt permeability R / F into the feed solution, which is the ratio of the water permeability R / F to the feed solution, is 0.10 g / kg or less, and the water permeability F into the draw solution is 5.0 kg / (m 2 ×hr) or more.

[0072] The forward osmosis membrane satisfies the above formula: R≦0.05×e 0.225×F The satisfaction of the relationship expressed by the formula (1) is an indicator that the forward osmosis membrane has excellent salt permeation selectivity and resistance to back pressure. 0.225×F Subtract the value of R from the value of g / (m 2 In one embodiment, the value expressed in units of 0 g / (m × hr) is 0 g / (m 2 ×hr) or more, or 0.01g / (m 2 ×hr) or more, or 0.05g / (m 2 ×hr), or 0.1g / (m 2 ×hr) or more, or 0.2g / (m 2 ×hr) or more, and in one embodiment, from the viewpoint of ease of production of the forward osmosis membrane, 2 ×hr) or less, or 10.0g / (m 2 ×hr) or less, or 5.0g / (m 2 ×hr) or less, or 1.0g / (m 2 ×hr).

[0073] From the viewpoint of good overall performance under back pressure of the forward osmosis membrane, in one embodiment, the R / F ratio is 0.10 g / kg or less, or 0.09 g / kg or less, or 0.08 g / kg or less, or 0.07 g / kg or less, or 0.06 g / kg or less, or 0.05 g / kg or less, or 0.04 g / kg or less, or 0.035 g / kg or less, or 0.03 g / kg or less. The smaller the R / F ratio, the more preferable it is, but from the viewpoint of ease of production of the forward osmosis membrane, in one embodiment, it may be 0.0001 g / kg or more, or 0.0002 g / kg or more, or 0.0005 g / kg or more.

[0074] From the viewpoint of good water permeability under the back pressure of the forward osmosis membrane, the water permeability F is, in one embodiment, 5.0 kg / (m 2 ×hr) or more, or 6.0 kg / (m 2 ×hr) or more, or 7.0 kg / (m 2 ×hr) or more, or 8.0 kg / (m 2 ×hr) or more, or 9.0 kg / (m 2 ×hr) or more, or 10.0 kg / (m 2 ×hr) or more. The higher the water permeability, the more preferable. From the viewpoint of maintaining good blocking properties and back pressure resistance, in one embodiment, the water permeability is 50.0 kg / (m 2 ×hr) or less, or 25.0 kg / (m 2 ×hr) or less, or 20.0 kg / (m 2 × hr) or less.

[0075] Each step of the method of this embodiment will now be described.

[0076] <Step of forming a separation functional layer on a porous support membrane to obtain a composite membrane> In this step, a polymer constituting a separation functional layer is formed on a porous support membrane to obtain a composite membrane. Examples of the porous support membrane, a hollow fiber membrane and a flat membrane, can be produced, for example, by the following procedure.

[0077] [Manufacturing of hollow fiber membranes] When the porous support membrane is a hollow fiber membrane, the hollow fiber membrane can be manufactured by a known dry / wet membrane-forming method, melt membrane-forming method, wet membrane-forming method, etc., using a material selected from the above-mentioned thermoplastic resins. Among these, a dry / wet spinning method is preferably used, in which a spinning dope in which a resin (polymer) is dissolved in a solvent and an internal coagulation liquid are discharged from a double tubular nozzle (spinneret), run through the air, and then coagulated in a coagulation bath containing an external coagulation liquid to form a hollow fiber membrane. The obtained hollow fiber may be wound on a winding machine and cut to a predetermined length.

[0078] (Spinning solution) In this method, aprotic polar organic solvents such as N-methyl-2-pyrrolidone, dimethylacetamide, and dimethylformamide are preferably used as the solvent (good solvent) of the spinning dope. The spinning dope may contain a non-solvent for the resin. As the non-solvent in the spinning dope, glycols such as polyethylene glycol and polypropylene glycol, electrolytes, polyvinylpyrrolidone, and the like can be used. Among these, glycols are preferred because of their spinnability and the quality of the resulting membrane.

[0079] The ratio of solvent / non-solvent is preferably set so that the mass ratio of non-solvent / (solvent+non-solvent) is within the range of 50-90% of the mass ratio at the miscibility limit. The miscibility limit is the point at which the polymer solution cannot become a homogeneous solution and undergoes phase separation. Since the miscibility limit is generally a function of temperature, the content ratio of the non-solvent needs to be set based on the miscibility limit at the spinning temperature.

[0080] If the mass ratio of non-solvent / (solvent+non-solvent) is less than 50% of the mass ratio at the compatibility limit, the viscosity of the spinning dope may be too low, resulting in poor spinnability, whereas if this value exceeds 90%, the controllability of the cross-sectional shape of the hollow fiber support membrane may be poor. For the same reason, the temperature of the spinning solution during formation of the hollow fiber porous support membrane is preferably 30 to 80°C, and more preferably 35 to 60°C.

[0081] The polymer concentration in the spinning dope is preferably 10 to 30% by mass, more preferably 15 to 25% by mass. The polymer concentration in the spinning dope is particularly related to the strength of the hollow fiber support membrane to be obtained. When the polymer concentration in the spinning dope is in the above range, a hollow fiber support membrane having excellent membrane strength can be obtained. When preparing the spinning dope, the spinning dope may be stirred at a predetermined temperature for 24 hours or more and then degassed under reduced pressure.

[0082] (Internal coagulation liquid) When forming a hollow fiber-shaped porous support membrane, for example, as described above, a double spinneret is used, with the spinning dope being discharged from the outer annular port and the internal coagulation liquid being discharged from the inner port. As the internal coagulation liquid, for example, an aqueous solution containing water as a main component and one or more additives selected from alcohols (monoalcohols, glycols, and glycerin) and amide solvents can be used.

[0083] Examples of monoalcohols include methanol, ethanol, and isopropyl alcohol. Examples of glycols include ethylene glycols such as triethylene glycol and tetraethylene glycol. Examples of amide solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide.

[0084] By including such an additive in the internal coagulation liquid, the rate of coagulation can be controlled, and a porous support membrane with a desired structure can be easily obtained. For example, when the internal coagulation liquid includes an additive, the coagulation is slowed down, and the pore size of the surface can be made coarse. On the other hand, if the amount of additive in the internal coagulation liquid is too large, the spinning stability may be deteriorated, or the surface pore size may become coarse, making it difficult to form a separation functional layer.

[0085] As the internal coagulation liquid, it is preferable to use water or a mixture of water and a small amount of additives from the viewpoint of spinning stability and variability of membrane performance. When the internal coagulation liquid contains glycols as additives, the content is preferably 60% by mass or less, more preferably 40% by mass or less, even more preferably 20% by mass or less, particularly preferably 10% by mass or less, and most preferably 5% by mass or less. If this value exceeds 60% by mass, it becomes difficult to maintain a balance in the pore sizes of the inner and outer surfaces of the obtained hollow fiber membrane, and the pores on the inner surface in particular tend to become coarse.

[0086] As the internal coagulation liquid, water is preferably used. The internal coagulation liquid is preferably adjusted to an appropriate temperature before being subjected to spinning. The temperature of the internal coagulation liquid is preferably not too high from the viewpoint of making the structure near the inner surface of the hollow fiber membrane uniform, and is preferably not too low from the viewpoint of preventing the structure on the inner surface side of the hollow fiber membrane from becoming too dense, allowing the monomer supply to proceed well during the formation of the separation functional layer, and obtaining good water permeability of the forward osmosis membrane. From the above viewpoint, the temperature of the internal coagulation liquid is preferably 5 to 55°C, or 10 to 40°C, or 15 to 35°C.

[0087] (external coagulation liquid) The external coagulation liquid used as the coagulation bath may contain one or more additional components selected from water, the non-solvents exemplified as additives to the internal coagulation liquid, and organic solvents, etc. The external coagulation liquid may be a liquid having the same composition as the internal coagulation liquid, or a liquid having a different composition.

[0088] As the external coagulation liquid, it is preferable to use water or a mixture of water and the non-solvent exemplified above as an additive to the internal coagulation liquid. When a mixture of water and an additive selected from alcohols (monoalcohols and glycols such as ethylene glycol) and amide solvents is used as the external coagulation liquid, the amount of the additive added is preferably 40 mass% or less, more preferably 30 mass% or less, even more preferably 15 mass% or less, and particularly preferably 5 mass% or less, based on the total mass of the external coagulation liquid. The external coagulation liquid is most preferably water. If the amount of additive in the external coagulation liquid is excessive, coagulation on the outer surface side of the hollow fiber support membrane may be delayed, resulting in an uneven membrane shape.

[0089] The temperature of the coagulation bath is preferably 10 to 60°C, more preferably 20 to 50°C, and even more preferably 25 to 40°C. When the temperature of the coagulation bath is high, the structure of the obtained hollow fiber support membrane tends to be sparse, and the water permeability of the hollow fiber support membrane tends to be high, and accordingly, the water permeability when made into a forward osmosis membrane tends to be high. When the temperature of the coagulation bath is too high, the pore size of the surface tends to be large, which may cause defects when passing a chemical solution in the subsequent formation of a separation functional layer, and the amount of salt back diffusion of the obtained forward osmosis membrane may be large. On the other hand, when the temperature of the coagulation bath is low, the structure of the support membrane tends to be dense, and the water permeability of the hollow fiber support membrane and the forward osmosis membrane may be low. The lower the temperature of the coagulation bath, the higher the spinning stability and the more uniform the structure of the obtained hollow fiber membrane.

[0090] [Flat membrane manufacturing] A flat porous support membrane can be produced, for example, by the following method using the resin solution exemplified as one used in the production of the hollow fiber support membrane. For example, the resin solution is applied to a glass substrate, and the substrate is coagulated by immersion in a coagulation liquid having the same composition as the external coagulation liquid. The coagulated support membrane can then be peeled off from the glass substrate, or the resin solution is cast on a nonwoven fabric substrate and coagulated by immersion in the coagulation liquid. The membrane forming conditions, such as the composition of the resin solution and the composition of the coagulation liquid, can be appropriately set by a person skilled in the art with reference to known techniques and the above-mentioned method for producing the hollow fiber support membrane.

[0091] [Formation of polymers] A composite membrane can be obtained by forming a polymer constituting a separation functional layer on the porous support membrane obtained as described above. In one aspect, the separation functional layer is a layer of crosslinked polyamide obtained by reacting a polyfunctional amine with a polyfunctional acid halide (e.g., a polyfunctional acid chloride). The crosslinked polyamide can be formed by performing interfacial polycondensation on the surface of the porous support membrane using an aqueous solution containing a polyfunctional amine and an organic solvent solution containing a polyfunctional acid halide. In this embodiment, a preferred method for forming a polymer is, for example, a method in which a first solution containing one of a polyfunctional amine and a polyfunctional acid halide and a second solution containing the other are passed through the support membrane in sequence. An aspect in which both a polyfunctional amine and a polyfunctional acid halide are contained in one solution is not preferred. In this embodiment, for example, the first solution may contain a polyfunctional amine, and the second solution may contain a polyfunctional acid halide.

[0092] (Polyfunctional amine) In one embodiment, the polyfunctional amine is an amine having at least two or more primary amino groups and at least one of secondary amino groups in one molecule, and at least one of the amino groups is a primary amino group. For example, aromatic polyfunctional amines such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, o-xylylenediamine, m-xylylenediamine, p-xylylenediamine, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 3,5-diaminobenzoic acid, 3-aminobenzylamine, and 4-aminobenzylamine; aliphatic amines such as ethylenediamine and propylenediamine; and alicyclic polyfunctional amines such as 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 4-aminopiperidine, and 4-aminoethylpiperazine. Among them, considering separation performance, water permeation resistance, and heat resistance, aromatic polyfunctional amines having at least two to four primary amino groups and at least one of secondary amino groups in one molecule are preferable. As such polyfunctional aromatic amines, m-phenylenediamine, p-phenylenediamine, or 1,3,5-triaminobenzene are preferably used. In particular, m-phenylenediamine is more preferably used because of its availability and ease of handling. These polyfunctional amines can be used alone or as a mixture of two or more kinds. When mixing two or more kinds of polyfunctional amines, the above amines may be combined with each other, or the above amines may be combined with an amine having at least two secondary amino groups in one molecule. Examples of amines having at least two secondary amino groups in one molecule include piperazine and 1,3-bispiperidylpropane.

[0093] (Polyfunctional acid halides) A polyfunctional acid halide is an acid halide having at least two halocarbonyl groups in one molecule. For example, Examples of trifunctional acid halides include trimesic acid chloride, 1,3,5-cyclohexanetricarboxylic acid trichloride, and 1,2,4-cyclobutanetricarboxylic acid trichloride. Examples of the bifunctional acid halides include aromatic bifunctional acid halides such as biphenyldicarboxylic acid dichloride, azobenzenedicarboxylic acid dichloride, terephthalic acid chloride, isophthalic acid chloride, and naphthalenedicarboxylic acid chloride; aliphatic bifunctional acid halides such as adipoyl chloride and sebacoyl chloride; and alicyclic bifunctional acid halides such as cyclopentanedicarboxylic acid dichloride, cyclohexanedicarboxylic acid dichloride, and tetrahydrofurandicarboxylic acid dichloride.

[0094] Considering the reactivity with the polyfunctional amine, the polyfunctional acid halide is preferably a polyfunctional acid chloride. Also, considering the separation performance and heat resistance of the resulting forward osmosis membrane, the polyfunctional acid chloride is more preferably a polyfunctional aromatic acid chloride having 2 to 4 carbonyl chloride groups in one molecule. In particular, from the viewpoints of availability and ease of handling, it is preferable to use trimesic acid chloride. These polyfunctional acid halides can be used alone or in combination of two or more kinds.

[0095] (Solvent and monomer solution concentration) The polyfunctional amine and the polyfunctional acid halide are dissolved in a suitable solvent, and are subjected to interfacial polycondensation as the first solution or the second solution. The solvents for the first and second solutions are preferably those which dissolve the monomers contained therein, and which, when the two solutions come into contact, do not dissolve in each other, form a liquid-liquid interface, and do not destroy the support film. In addition, those which are inactive to the polyfunctional amine compound and the polyfunctional acid halide are more preferable. Examples of such solvents include the following solvents.

[0096] The solvent for the polyfunctional amine may be one or more selected from water, alcohol, etc. The solvent for the polyfunctional acid halide may be one or more selected from hydrocarbon solvents such as n-hexane, cyclohexane, n-heptane, n-octane, n-nonane, and n-decane.

[0097] By selecting the above-mentioned solvents as the solvents for the polyfunctional amine and the polyfunctional acid halide, the polyfunctional amine solution and the polyfunctional acid halide solution become immiscible, and the interfacial polycondensation reaction proceeds, resulting in a thin film of a polymer (polyamide). The composition and concentration of each solution should be set according to the type of monomer, the distribution coefficient to the solvent, etc., and are not particularly limited, and can be appropriately set according to the desired separation function.

[0098] For example, in the case of interfacial polycondensation using an aqueous m-phenylenediamine solution as the polyfunctional amine solution and an n-hexane solution of trimesoyl chloride as the polyfunctional acid halide solution, the appropriate monomer concentrations are as follows: The concentration of m-phenylenediamine is preferably 0.1 to 10% by mass, more preferably 0.5 to 5.0% by mass, and particularly preferably 1.0 to 3.0% by mass. The concentration of trimesoyl chloride is preferably 0.01 to 10% by mass, more preferably 0.04 to 2.0% by mass. If the concentration of these solutions is too low, the formation of the separation functional layer by interfacial polycondensation is incomplete and defects are likely to occur, leading to a decrease in separation performance when used as a forward osmosis membrane. Conversely, if the concentration of these solutions is too high, the formed polyamide separation functional layer becomes too thick, resulting in a decrease in water permeability, and the amount of residual unreacted material in the separation functional layer increases, which may adversely affect the performance as a forward osmosis membrane.

[0099] (Polymerization additives) The polyfunctional amine solution or polyfunctional acid halide solution may contain additives such as surfactants, organic solvents (excluding the organic solvent in the polyfunctional acid halide solution), organic acid salts, basic compounds, and antioxidants, as long as they do not significantly interfere with the reaction between the polyfunctional amine and the polyfunctional acid halide.

[0100] The surfactant has the effect of improving the wettability of the porous support membrane surface and reducing the interfacial tension between the amine solution and the non-polar solvent. The organic solvent may act as a catalyst for the interfacial polycondensation reaction, so the addition of the organic solvent may make the interfacial polycondensation reaction more efficient. The organic acid salts can change the wettability of the porous support membrane surface, which may improve the membrane formability and the separation performance when used as a forward osmosis membrane. The basic compound can remove the hydrogen halide produced by polymerization, which may promote polymerization.

[0101] Examples of the polymerization additives include surfactants such as sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and sodium lauryl sulfate; organic solvents such as ethanol, isopropanol, N,N-dimethylformamide, and ε-caprolactam; organic acid salts consisting of a mixture of an amine such as triethylamine and an organic acid such as camphorsulfonic acid; basic compounds such as sodium hydroxide, trisodium phosphate, and triethylamine; phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and acylation catalysts.

[0102] <Step of subjecting the composite film to a wet heat treatment to obtain a wet heat treated film> In this step, the composite membrane obtained in the above step is subjected to a wet heat treatment, thereby crosslinking the polymer constituting the separation functional layer. In the present disclosure, the wet heat treatment means a treatment in which the composite membrane is brought into contact with a water-containing medium at a temperature of 50°C or higher. The wet heat treatment has the effect of arranging the higher-order structure of the separation functional layer and / or improving the crosslink density, and therefore improves the physical strength and solvent resistance of the separation functional layer. The improvement in the physical strength and / or solvent resistance of the separation functional layer also contributes to preventing the separation functional layer from peeling off from the porous support membrane when a counter pressure is applied. In order to receive this effect more significantly, the temperature of the water-containing medium is more preferably 70°C or higher, and even more preferably 85°C or higher.

[0103] In addition, when the heat treatment is performed in a dry state, the composite membrane may be excessively dried, and in particular, the pores of the porous support membrane may shrink, causing deformation of the porous support membrane. When the pores of the porous support membrane shrink, the water permeability of the resulting forward osmosis membrane may decrease. In addition, when the porous support membrane is deformed, deformation of the separation functional layer may be induced, and the salt blocking performance of the separation functional layer may decrease. Heat treatment in a dry state may cause problems such as uneven or insufficient heating of the forward osmosis membrane, and a decrease in the mobility of the separation functional layer caused by an insufficient wet state, and therefore an insufficient increase in the degree of crosslinking. From the above viewpoint, it is preferable that the heat treatment in a dry state is performed for a short time (for example, within 15 minutes), and it is more preferable that it is not performed.

[0104] Examples of the method of the moist heat treatment include permeation of a moist gas (e.g., water vapor, nitrogen or air containing moisture, etc.) heated through a heat source, exposure to a moist gas, permeation of a heated water-containing medium (e.g., hot water), etc. Only one type of heat treatment may be performed, or two or more types of heat treatments may be combined, or the same treatment may be repeated multiple times. Here, "permeation" refers to a treatment in which a fluid is supplied to the composite membrane to bring the separation functional layer and the porous support membrane into contact with the fluid. A preferred method of permeation is a method in which a liquid is supplied from one or both sides of the composite membrane to circulate the fluid on both surfaces and inside the composite membrane (including the pores of the porous support membrane).

[0105] For example, in the method of supplying hot water, a method of circulating hot water at, for example, 50°C to 100°C, preferably 70°C to 95°C, at least on the separation functional layer side of the composite membrane is preferred from the viewpoint of heat transfer efficiency. According to this method, heat is uniformly transferred to the separation functional layer, and residual monomers, etc. in the porous support membrane are washed away, making it difficult for unintended reactions to occur. The flow time of the hot water is preferably 5 minutes or more in order to allow crosslinking reactions, etc. to proceed favorably. On the other hand, if the flow time exceeds 2 hours, the degree of improvement in the effect of supplying hot water according to the supply time is small, so the flow time is preferably 2 hours or less.

[0106] In one embodiment, the wet heat treatment is carried out in a heated and pressurized wet gas atmosphere. The temperature of the heated and pressurized wet gas may be, for example, more than 100°C and not more than 160°C, or more than 100°C and not more than 140°C. The pressure of the heated and pressurized wet gas may be, for example, 102 kPaA to 620 kPaA, or 140 kPaA to 360 kPaA, or 190 kPaA to 320 kPaA in absolute pressure. By contacting the composite membrane with the heated and pressurized wet gas, the polymer can be efficiently crosslinked while suppressing damage to the porous support membrane.

[0107] In one embodiment, the moist heat treatment is carried out by contacting the composite film with water vapor at 100° C. or higher. The temperature of the water vapor may be, for example, 100° C. or higher and 160° C. or lower, or 100° C. or higher and 140° C. or lower.

[0108] The contact time of the above-mentioned heated and pressurized wet gas or water vapor with the composite membrane is preferably 1 minute or more in terms of the favorable progress of the crosslinking reaction, whereas if the contact time exceeds 4 hours, the degree of improvement in the effect is small even if the contact time is extended, so the contact time is preferably 4 hours or less.

[0109] By the above-mentioned examples of the heat-moisture treatment, a heat-moisture treated film can be obtained.

[0110] [Step of contacting the heat-moisture treated film with a hydrophilic organic compound] In this step, the hydrophilic organic compound is brought into contact with the above-mentioned moist heat treatment membrane. This forms a separation functional layer whose surface and interior are hydrophilized. Such a separation functional layer is advantageous for improving the water permeability of the forward osmosis membrane.

[0111] Examples of hydrophilic organic compounds include alcohols, carboxylic acids, esters, ketones, nitriles, ethers, and amides. The alcohol may contain glycol and / or glycerin, and is preferably an alcohol having 1 to 4 carbon atoms, more preferably one or more selected from the group consisting of methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, sec-butanol, and tert-butanol, in that it has a good hydrophilic effect and is unlikely to damage the porous support membrane and the separation functional layer. Examples of carboxylic acids include acetic acid and oxalic acid; esters include methyl acetate and ethyl acetate; ketones include acetone; nitriles include acetonitrile; ethers include tetrahydrofuran and 1,4-dioxane; and amides include dimethylformamide and N-methylpyrrolidone. It is preferable to use these hydrophilic organic compounds in a composition that does not significantly damage the forward osmosis membrane.

[0112] Examples of the method of contacting the hydrophilic organic compound with the heat-moisture treatment membrane include a method of contacting the heat-moisture treatment membrane with an aqueous solution containing the hydrophilic organic compound at, for example, 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more. Examples of the contact method include a method of immersing the heat-moisture treatment membrane in the aqueous solution, a method of passing the aqueous solution through the heat-moisture treatment membrane, and a combination of one or more of the methods of filtering the aqueous solution through the heat-moisture treatment membrane. The contact time is preferably 5 minutes or more from the viewpoint of obtaining a good hydrophilization effect, and is preferably 300 minutes or less from the viewpoint of process efficiency.

[0113] In one embodiment, it is preferable to perform the above-mentioned hydrophilization on a composite membrane in which the degree of crosslinking of the separation functional layer has been further increased by a wet heat treatment. In this case, defects (i.e., defects that increase salt back diffusion) due to oligomer detachment from the separation functional layer or excessive swelling of the separation functional layer caused by the hydrophilization treatment are unlikely to occur, while the effect of improving water permeability is enhanced, so that a forward osmosis membrane having high water permeability and low salt back diffusion amount can be produced.

[0114] <Forward osmosis membrane module> A forward osmosis membrane module may be constructed by storing a plurality of forward osmosis membranes in the housing in this embodiment. The shape of the forward osmosis membrane module is not particularly limited, but typically, a section in which liquid contacts only one surface side of the membrane (e.g., the inner surface side of the hollow fiber membrane) and a section in which liquid contacts only the other surface side of the membrane (e.g., the outer surface side of the hollow fiber membrane) are separated. For example, the separation may be achieved by fixing the membrane to the module housing with an adhesive resin. For example, a urethane-based or epoxy-based adhesive may be used as the adhesive resin. The size of the housing is not particularly limited, but may be, for example, a cylindrical housing having a diameter of 10 to 500 mm and a length of 20 to 10,000 mm.

[0115] FIG. 1 is a schematic cross-sectional view showing the structure of a hollow fiber membrane module as an example of a forward osmosis membrane module. The hollow fiber membrane module (1) shown in FIG. 1 has a structure in which a fiber bundle consisting of a plurality of hollow fiber membranes (4) is packed in a cylindrical housing, and both ends of the hollow fiber bundle are fixed to the cylinder with adhesive fixing parts (5, 6). The housing has outer conduits (2, 3) on its side and is sealed by headers (7, 8). Here, the adhesive fixing parts (5, 6) are each solidified so as not to block the hollow part of the hollow fiber membrane (4). The headers (7, 8) each have inner conduits (9, 10) that communicate with the inside (hollow part) of the hollow fiber membrane (4) but do not communicate with the outside. These inner conduits (9, 10) allow liquid to be introduced into or removed from the inside of the hollow fiber membrane (4). The outer conduits (2, 3) each communicate with the outside of the hollow fiber membrane (4) but do not communicate with the inside. This hollow fiber membrane module (1) is so structured that the liquid flowing inside and the liquid flowing outside are in contact only via the hollow fiber membranes (4).

[0116] <Substances that come into contact with the forward osmosis membrane> [Organic solvents and organic compounds] In this embodiment, the organic solvent that the forward osmosis membrane comes into contact with during use (i.e., the organic solvent that the feed solution or the draw solution may contain) may be any substance that does not instantly dissolve the forward osmosis membrane. The phrase "instantly dissolving the forward osmosis membrane" refers to the forward osmosis membrane losing its original shape within one hour when it is brought into contact with an organic solvent. The organic solvent may be a general organic solvent used in industry and research. Examples of the organic solvent include lower alcohols such as methanol, ethanol, 1-propanol, and 2-propanol; nitriles such as acetonitrile; higher alcohols having 6 or more carbon atoms; glycols such as ethylene glycol and propylene glycol; hydrocarbons such as pentane, hexane, decane, undecane, and cyclooctane; mixtures of two or more of these; and mixtures of these with water. Examples of organic solvents which are contained in large amounts in foods and pharmaceuticals and for which it is preferable that a forward osmosis membrane has durability include alcohols (monoalcohols, glycols, etc.) and nitriles.

[0117] Examples of organic compounds include carboxylic acids such as acetic acid, acrylic acid, propionic acid, formic acid, lactic acid, oxalic acid, tartaric acid, and benzoic acid; organic acids such as sulfonic acid, sulfinic acid, habituric acid, uric acid, phenol, enol, diketone type compounds, thiophenol, imide, oxime, aromatic sulfonamide, primary nitro compounds, and secondary nitro compounds; aromatic hydrocarbons such as benzene, toluene, and xylene; mineral oils; ketones such as acetone and methyl isobutyl ketone; aldehydes such as acetaldehyde; ethers such as dioxane and tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone; nitrogen-containing organic compounds such as pyridine; esters such as acetates and acrylic esters; and organic compounds for industrial and research use such as dimethyl sulfoxide, sugars, fertilizers, and enzymes. When these organic compounds are contained in the above-mentioned organic solvents or the like to the extent that they do not instantly dissolve the forward osmosis membrane and come into contact with the forward osmosis membrane of the present embodiment, the durability of the forward osmosis membrane may become a problem.

[0118] [Inducing solution] The draw solution is a solution that exhibits a higher osmotic pressure than the feed solution and has the function of moving the solvent from the feed solution through the forward osmosis membrane. This draw solution exhibits a high osmotic pressure by containing a high concentration of the draw solute. Examples of the derived solute include alkali metal salts, alkaline earth metal salts, ammonium salts, sugars, monoalcohols, glycols, water-soluble polymers, etc. Specific examples of these include: As alkali metal salts, for example, sodium chloride, potassium chloride, sodium sulfate, sodium thiosulfate, sodium sulfite, etc.; Alkaline earth metal salts, for example, magnesium chloride, calcium chloride, magnesium sulfate, etc.; Ammonium salts, for example, ammonium chloride, ammonium sulfate, ammonium carbonate, etc.; Examples of sugars include common sugars such as sucrose, fructose, and glucose, as well as special sugars such as oligosaccharides and rare sugars; As monoalcohols, for example, methanol, ethanol, 1-propanol, 2-propanol, etc.; Glycols, for example, ethylene glycol, propylene glycol, etc.; Examples of water-soluble polymers include polyethylene oxide, polypropylene oxide, and copolymers of ethylene oxide and propylene oxide; Each of them can be mentioned. EXAMPLES

[0119] The following examples further illustrate exemplary embodiments of the present invention, but the present invention is not limited to these examples.

[0120] Evaluation method [Surface pore diameter] For the hollow fiber forward osmosis membranes, one forward osmosis membrane was taken from each of three locations in the radial direction of the forward osmosis membrane module: the outer periphery, the middle, and the center (a total of three membranes), and each was cut into three equal parts in the longitudinal direction to obtain nine samples. For the flat forward osmosis membrane, each side of the forward osmosis membrane was divided into 9 parts so as to divide it into 3 equal parts, and 9 samples were obtained. In both the hollow fiber forward osmosis membrane and the flat membrane forward osmosis membrane, the measured value was calculated as the average value of nine samples.

[0121] Surface images of each sample were obtained as follows. Each sample was immersed in an aqueous solution of 2.0% by mass sodium hypochlorite, 2.0% by mass sodium hydroxide, and 0.15% by mass calcium chloride at 60°C for 200 hours. The fibers were then thoroughly washed with pure water to obtain a support membrane sample from which the separation functional layer had been removed. In the case of hollow fiber samples that had a separation functional layer on the inner surface, each sample was cut open at an angle in the center to expose the porous support membrane surface. The surface of the obtained sample that had been in contact with the separation functional layer was observed with a scanning electron microscope. The sample was immersed in pure water in a dedicated glass container, frozen with liquid nitrogen, and then dried by freeze-drying. In addition, a thin coating of osmium was applied to prepare an observation sample. The observation sample was photographed under the following conditions using a scanning electron microscope (S-4800, Hitachi High-Tech Corporation). Accelerating voltage: 1.0 kV Emission current: 10μA Probe current:Normal Detector:Upper Magnification: 50,000x Number of pixels: 1280 x 960 Working distance: 5.0mm The number average of the circle equivalent diameters of the holes included in the field of view of 1.0 μm × 1.0 μm arbitrarily selected on the surface image was taken as the value of the surface pore diameter. Specifically, this was done using image processing software (ImageJ; developed by the National Institutes of Health, USA). The surface image was imported into the image processing software, binarized by the Otsu method, and the area of ​​the surface pores was calculated. The obtained area value was converted into the total pore area in one image using a calibration curve prepared in advance. Furthermore, the number of pores was counted, and the total pore area was divided by the total number of pores to calculate the area per pore, and the equivalent circle was obtained, and the diameter was calculated to obtain the pore diameter per pore, which was taken as the average surface pore diameter in one image.

[0122] [Support membrane dimensions] As dimensions of the support membrane, the inner diameter, outer diameter, and membrane thickness were measured for the hollow fiber support membrane, and the membrane thickness was measured for the flat membrane support membrane. In the case of hollow fiber support membranes, the measurements were made using optical microscope photographs (cross-sectional images) of the cross sections obtained by cutting the membrane along a plane perpendicular to the membrane surface direction (longitudinal direction). The outer and inner diameters of the cross-sectional images were measured using a scale. The membrane thickness was calculated by dividing the difference between the outer and inner diameters by 2. The outer and inner diameters referred to here are the outer and inner diameters of the hollow fiber, respectively. In the case of a flat support membrane, the thickness was measured using an optical microscope photograph (cross-sectional image) of a cross section obtained by cutting the membrane in a plane perpendicular to the membrane surface direction. The membrane thickness of this cross-sectional image was measured using a scale. In this example, the inner diameter, outer diameter, and membrane thickness of the support membrane were measured after the membrane was made into a forward osmosis membrane. It was confirmed that the measurements were the same within the margin of error even when the membrane was measured alone.

[0123] [With or without uneven structure] The presence or absence of an uneven structure was evaluated by performing atomic force microscopy (AFM) analysis on nine samples obtained from the forward osmosis membrane and calculating the arithmetic mean height (Sa) defined in ISO 25178.

[0124] For the hollow fiber forward osmosis membrane, one forward osmosis membrane was taken out from each of three locations in the radial direction of the forward osmosis membrane module (three in total) under conditions where the forward osmosis membrane did not dry out, and each was cut into three equal parts in the longitudinal direction to obtain nine samples. Furthermore, the surface of the separation functional layer was exposed, and the outermost surface of the separation functional layer was scanned under the following conditions to determine the arithmetic mean height (Sa).

[0125] For the flat forward osmosis membrane, the forward osmosis membrane was not dried, and each side of the membrane was divided into 9 parts so as to divide it into 3 equal parts, to obtain 9 samples. Furthermore, the outermost surface of the separation functional layer was scanned under the following conditions to obtain the arithmetic mean height (Sa).

[0126] In both the hollow fiber forward osmosis membrane and the flat membrane forward osmosis membrane, the measured value was calculated as the average value of nine samples. Measurement mode: QNM in fluid (measurement in pure water) Field of view size: 3μm square Probe used: OLTESPA

[0127] When the arithmetic mean height (Sa) calculated as the average value of nine samples was 40 nm or more, the separation functional layer was deemed to have a concave-convex structure, and when this arithmetic mean height (Sa) was less than 40 nm, the separation functional layer was deemed not to have a concave-convex structure.

[0128] [O / N ratio] The surface of the separation functional layer of the forward osmosis membrane was measured using an X-ray photoelectron spectrometer. In the case of hollow fiber forward osmosis membranes, five forward osmosis membranes were taken from near the radial center of the forward osmosis membrane module, and further divided into five equal parts lengthwise to obtain a total of 25 samples. Then, a piece 3 mm long was cut from near the longitudinal center of each sample to be used as an XPS measurement sample. Each sample was immersed in pure water and frozen with liquid nitrogen, and then dried by freeze-drying. Furthermore, the hollow fiber was cut open along the longitudinal direction to expose the separation functional layer, and one piece was used as an XPS measurement sample. In the case of a flat forward osmosis membrane, the flat membrane was immersed in pure water and frozen with liquid nitrogen, then dried by freeze-drying, and each side of the forward osmosis membrane was divided into 25 equal parts to obtain 25 samples. The center of each sample was then cut into 3 mm squares to prepare XPS measurement samples. In both the hollow fiber forward osmosis membrane and the flat forward osmosis membrane, the measured value was calculated as the average value of 25 samples. The measurement was performed by the XPS measurement method described later, and the element composition ratio of the surface of the separation functional layer at 25 points was measured, and the average value of the O / N ratio was calculated.

[0129] [O 533eV / N ratio] The surface of the separation functional layer of the forward osmosis membrane was measured using an X-ray photoelectron spectroscopy analyzer. The measurement sample was prepared using the same procedure as the above XPS measurement sample. In both the hollow fiber forward osmosis membrane and the flat forward osmosis membrane, the measured value was calculated as the average value of 25 samples. The element composition ratio of the separation functional layer surface at 25 arbitrary points was measured at a photoelectron detection angle of 45 degrees, and the average O / N ratio was calculated. The above XPS measurement sample was held in a sample holder with double-sided tape, and the separation functional layer side was measured. In addition, the measurement point was identified using the SXI (Scanning X-ray Image) function attached to the device.

[0130] [XPS measurement conditions] Equipment used: ULVAC-Fi Versa probe II Excitation source: mono.AIKα 20kV×5mA 100W Analysis size: 100μmφ×1.4mm During data acquisition, an X-ray beam with a diameter of approximately 100 μm was vibrated parallel to the fiber axis with a width of 1.4 mm. Photoelectron extraction angle: 45° Capture Area Survey scan: 0~1,100eV Narrow scan:C1s, O1s, N1s, S2p, Si2p Pass Energy Survey scan: 117.4eV Narrow scan: 46.95eV Energy step Survey scan: 1eV Narrow scan: 0.1eV Charge neutralization: Normal conditions for both electron gun and Ar+ ion gun

[0131] [Data Processing] Quantitative analysis and curve fitting of O1s spectra were performed using the data processing function of the software provided with the instrument (MultiPak 9.6.0.15).

[0132] [Quantitative analysis] From the area intensities of C1s, O1s, N1s, S2p, and Si2p obtained, the relative element concentration of each element was calculated using the following formula. C j (%) = 100×(I j / RSF j ) / Σ(I j / RSF j ) Here, the parameters are as follows: C j :Relative element concentration (atomic%) I j : Area intensity of C1s, O1s, N1s, S2p, and Si2p spectra (unit: cps eV) RSF j : Corrected relative sensitivity coefficients for C1s, O1s, N1s, S2p, and Si2p (values ​​below) C1s:14.496 O1s:34.046 N1s:23.107 S2p:74.406 Si2p:39.979

[0133] [Curve fitting of O1s spectrum] The O concentration obtained by the quantitative analysis was separated into a 531 eV component (O=C double bond) and a 533 eV component (derived from adsorbed water and hydroxyl groups) according to the following procedures and constraints. (1) The energy values ​​were corrected for charging based on the benzene ring component (284.6 eV) of the C1s spectrum. (2) Curve fitting of the O1s spectrum was performed under the following constraints: The background is a straight line from around 528 eV to around 538 eV. The number of components is two: 531 eV component and 533 eV component. The peak position of the 531 eV component is fixed at 531.2 eV. The full width at half maximum (FWHM) of the 531 eV component and the 533 eV component are assumed to be equal.

[0134] [IR 1720 / IR 1650 ] The surface of the separation functional layer of the forward osmosis membrane was measured using an FT-IR device. In the case of hollow fiber forward osmosis membranes, five forward osmosis membranes were taken from near the center in the radial direction of the forward osmosis membrane module, and further divided into five equal parts in the length direction to obtain a total of 25 samples. Then, each sample was cut out to a length of 10 mm from near the center in the length direction. These were immersed in pure water and frozen with liquid nitrogen, then dried by freeze-drying, and both ends of each sample were fixed on a glass plate with double-sided tape and cut open along the length direction of the hollow fiber to expose the separation functional layer. Furthermore, each sample was cut out to a length of 5 mm from near the center in the length direction to be used as an IR measurement sample. In the case of a flat forward osmosis membrane, the flat membrane was immersed in pure water and frozen with liquid nitrogen, then dried by freeze-drying, and each side of the forward osmosis membrane was divided into 25 equal parts to obtain 25 samples. The center of each sample was then cut into 5 mm squares to prepare IR measurement samples. Each IR measurement sample was attached to a slide glass with double-sided tape, and the surface of the separation functional layer was measured.

[0135] <IR measurement conditions> Equipment used: FT-IR device BRUKER LUMOS Measurement method: Attenuated total reflection (ATR) ATR crystal: Germanium Wavenumber resolution: 4cm -1 Number of times accumulated: 64 Detector: MCT detector Aperture size: 124μm x 124μm Crystal pressing pressure: low or medium Measurement wave number range: 450~4000cm -1

[0136] 《Peak intensity ratio calculation》 1650cm due to the C=O stretching vibration of the amide bond (amide I) -1 Peak absorbance Abs (h1650), 1720 cm due to the C=O stretching vibration of carboxylic acid -1 The peak absorbance Abs (h1720) was measured. The absorbance was low and stable at 1800 cm -1 The absorbance (baseline) was taken as Abs (h1800) and substituted into the following formula to calculate the IR peak intensity ratio.

[0137]

number

[0138] [Ethanol swelling rate] The ethanol swelling ratio of the forward osmosis membrane was measured. For the hollow fiber membrane, a piece was cut out so that the longitudinal direction was about 100 mm, and the length was measured. For the flat membrane, a piece was cut out so that the longitudinal direction was about 100 mm and the lateral direction was 10 mm, and the longitudinal length was measured. These forward osmosis membranes were immersed in 99.5% pure ethanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) at 25°C for 48 hours. The length of the membrane after immersion in ethanol was measured, and the swelling degree was calculated by the following formula: Ethanol swelling rate (%) = {(length of film after immersion / length of film before immersion)-1} x 100 When the forward osmosis membrane was deformed, such as waving, after immersion in ethanol, the membrane was held down by hand within a range in which the membrane was not deformed excessively, and the length was measured. In addition, in all of the forward osmosis membranes of the following Examples and Comparative Examples, after immersion in ethanol at 25° C. for 48 hours, the forward osmosis membranes were not completely dissolved.

[0139] [Water permeability under back pressure F and salt back diffusion rate R] The forward osmosis membrane's water permeability F and salt back diffusion rate R were evaluated by using purified water as the raw material solution and a 3.5% by mass aqueous sodium chloride solution as the draw solution, placing the raw material solution on the separation functional layer side of the forward osmosis membrane and the draw solution on the porous support membrane side, and applying a pressure of 40 kPa with the draw solution side as the positive side for 60 minutes. The hollow fiber forward osmosis membrane was evaluated under the following conditions. The flat membrane-type forward osmosis membrane was evaluated under the same temperature conditions and with the membrane surface linear velocity set to be the same. The draw solution concentration during the evaluation was maintained constant by dripping a saturated aqueous sodium chloride solution. Raw material liquid temperature: 25℃ Induction solution temperature: 25℃ Linear speed of the film surface of the raw material liquid: 3.0 cm / sec Linear velocity of the membrane surface of the draw solution: 3.0 cm / sec

[0140] [Example 1] (Preparation of hollow fiber porous support membrane) A uniform polymer solution consisting of 19% by mass of polysulfone (Udel-P3500, manufactured by Solvay Specialty polymers), 61% by mass of N-methyl-2-pyrrolidone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 20% by mass of tetraethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared as a spinning dope. The dope was filled into a wet hollow fiber spinning machine equipped with a double spinneret. The dope at 40°C and an internal coagulation liquid (water) at 25°C were discharged from the double spinneret, and the spinneret was run for 250 mm in air with a relative humidity of 98% and a temperature controlled at 25°C. The spinneret was then coagulated in a coagulation bath (external coagulation liquid) filled with water at 30°C, and the spinneret was wound up at a tension of 25 g using a free roll as a turn roll to obtain a hollow fiber support membrane. The obtained hollow fiber support membrane had an outer diameter of 1.02 mm, an inner diameter of 0.62 mm, and a membrane thickness of 0.20 mm.

[0141] (Fabrication of supported membrane module) 130 pieces of the above hollow fiber support membrane cut to a length of 120 mm were packed into a cylindrical plastic housing with a diameter of 20 mm and a length of 80 mm, and both ends were fixed with an adhesive to obtain a membrane with the structure shown in FIG. 1 and an effective inner membrane surface area of ​​0.02 m. 2 A supported membrane module was fabricated.

[0142] (Formation of separation functional layer) An aqueous solution (first solution) containing 2.1% by mass of m-phenylenediamine (MPD) and 0.15% by mass of sodium lauryl sulfate (SDS) was passed through the inside of the hollow fiber support membrane in the support membrane module for 20 minutes. After the first solution was removed by gravity from the piping at the bottom of the module, the outer part of the support membrane module was depressurized to 10 kPaA while the inside of the hollow fiber was wet with the first solution, and this depressurized state was maintained for 1 minute. Then, air was passed through the inside of the hollow fiber at a linear speed of 210 cm / sec for 1 minute to remove excess first solution. Next, an n-hexane solution (second solution) containing 0.18% by mass of trimesoyl chloride (TMC) was passed through the inside of the hollow fiber for 2 minutes to perform interfacial polymerization, and a polymer was formed on the inner surface of the hollow fiber to obtain a composite membrane. Thereafter, excess second solution was removed by flowing nitrogen gas at a linear speed of 210 cm / sec for 1 minute, and then 25°C water was flowed inside the hollow fiber at a linear speed of 5 cm / sec for 5 minutes to wash the surface. The module was then placed in an autoclave (AC; Tommy Seiko Co., Ltd., SX-500) with both ends of the hollow fiber membrane open, and curing was performed by flowing high-temperature steam at 121°C inside the autoclave for 20 minutes (moist heat treatment), to obtain a moist heat treated membrane. Furthermore, the inner surface of the hollow fiber support membrane of the moist heat treated membrane was washed with water at 20°C for 30 minutes. By the above procedure, a forward osmosis membrane module was obtained. In addition, in the forward osmosis membrane obtained in Example 1, the arithmetic mean height (Sa) of the separation functional layer was 121 nm, and the IR 1720 / IR 1650 The value was 0.11.

[0143] [Examples 2 to 8, 10 to 12] After the wet heat treatment and before washing with water, the wet heat treated membrane was immersed in an aqueous solution of a hydrophilic organic compound of the type and concentration shown in Table 1 to perform hydrophilization treatment, and then washed with water for 1 hour or more. Except for this, a forward osmosis membrane module was obtained in the same manner as in Example 1. The hydrophilization treatment time is as shown in Table 1.

[0144] [Example 9] A forward osmosis membrane module was obtained in the same manner as in Example 8, except that polyethersulfone (manufactured by BASF, Ultrason E2020P) was used instead of polysulfone.

[0145] [Examples 13 and 14] A forward osmosis membrane module was obtained in the same manner as in Example 1 (for Example 13) or Example 5 (for Example 14), except that as the wet heat treatment, hot water at 85°C was passed through the inside of the hollow fibers for 20 minutes instead of the autoclave treatment.

[0146] [Example 15] The conditions for producing the hollow fiber support membrane were as shown in Tables 1 and 2. A forward osmosis membrane module was obtained in the same manner as in Example 5, except that the membrane area was the same.

[0147] [Example 16] The conditions for forming the hollow fiber support membrane and the conditions for forming the separation functional layer were as shown in Tables 1 to 3, and a forward osmosis membrane module was obtained in the same manner as in Example 8, except that the membrane area was the same.

[0148] [Comparative Examples 1 and 2] A forward osmosis membrane module was obtained in the same manner as in Example 1 (Comparative Example 1) or Example 8 (Comparative Example 2), except that instead of the wet heat treatment, the module was placed in a dryer and dried at 50°C as a dry heat treatment.

[0149] [Comparative Example 3] A forward osmosis membrane module was obtained in the same manner as in Example 8, except that in forming the separation functional layer, sodium lauryl sulfate, which is an additive for polymerization, was not used, and further, the monomer concentration was set as shown in Table 3, so that no uneven structure was provided in the separation functional layer. In the forward osmosis membrane obtained in Comparative Example 3, the arithmetic mean height (Sa) of the separation functional layer was 24 nm.

[0150] [Comparative Example 4] (Preparation of flat porous support membrane) Polyester non-woven fabric (air permeability: 2cc / (cm 2 A 20% by weight dimethylformamide (DMF) solution of polysulfone was cast on the substrate at 25°C to a thickness of 190 μm, and the substrate was immersed in a coagulation liquid at 25°C and left for 20 minutes to produce a flat support membrane having a thickness of 200 μm, which is made of a laminate of a polyester nonwoven fabric substrate and a polysulfone porous support. The surface of the support membrane on the polysulfone porous support side was contacted with an aqueous solution (first solution) containing 2.1% by mass of m-phenylenediamine and 0.15% by mass of sodium lauryl sulfate for 20 minutes. Thereafter, air was passed over the surface of the first solution application surface to remove excess solution. Subsequently, an n-hexane solution (second solution) containing 0.18% by mass of trimesic acid chloride was contacted with the first solution application surface for 2 minutes to perform interfacial polymerization, thereby forming a separation functional layer on the porous support. After that, nitrogen gas was passed over the surface on which the separation functional layer was formed to remove excess second solution, and then water at 25°C was passed over the surface of the support membrane on which the separation functional layer was formed for 5 minutes. Next, the support membrane on which the separation functional layer was formed was placed in an autoclave, and high-temperature steam at 121°C was passed over it for 20 minutes, after which the moist heat-treated membrane was immersed in an aqueous solution of hydrophilic organic compounds of the types and concentrations shown in Table 1 to perform hydrophilization treatment, and then washed with water at 20°C for 60 minutes to obtain a flat forward osmosis membrane.

[0151] The obtained forward osmosis membrane was cut to a predetermined size and placed in a housing so that the membrane area was 0.02 m 2 A flat membrane cell was prepared. Unlike hollow fibers, the position of the separation functional layer in flat membranes is indicated by the front and back. The back here refers to the side that was in contact with the nonwoven fabric when the support membrane was produced, and the front refers to the side that was in more contact with the coagulation liquid.

[0152] [Example 17] The conditions for producing the hollow fiber support membrane were as shown in Tables 1 and 2. A forward osmosis membrane module was obtained in the same manner as in Example 8, except that the membrane area was the same.

[0153] [Comparative Examples 5 and 6] A forward osmosis membrane module was obtained in the same manner as in Example 1 (Comparative Example 6) or Example 8 (Comparative Example 7), except that a mixture of polyethersulfone (manufactured by BASF, Ultrason E2020P):hydroxyl-modified polyethersulfone (manufactured by BASF, trade name Ultrason E2020PSR) = 50:50 (molar ratio) was used instead of polysulfone, and the membrane production conditions for the hollow fiber support membrane were as shown in Tables 1 and 2.

[0154] [Example 18] The conditions for producing the hollow fiber support membrane were as shown in Tables 1 and 2. A forward osmosis membrane module was obtained in the same manner as in Example 16, except that the membrane area was the same.

[0155] [Comparative Examples 7 and 8] A forward osmosis membrane module was obtained in the same manner as in Example 1 (Comparative Example 7) or Example 8 (Comparative Example 8), except that the conditions for forming the hollow fiber support membrane were as shown in Tables 1 and 2.

[0156] [Comparative Example 9] A forward osmosis membrane module was obtained in the same manner as in Example 1, except that the conditions for forming the hollow fiber support membrane were as shown in Tables 1 and 2. In Comparative Example 9, prior to use, trimesoyl chloride (TMC) was heated to 35°C to become liquid, and 50 mL of purified water was added to TMC, which was then stirred for 2 hours to partially deactivate the functional groups, and then the TMC was dissolved in n-hexane to prepare a second solution for use.

[0157] The results are shown in Tables 1 to 3.

[0158] [Table 1]

[0159] [Table 2]

[0160] [Table 3] The abbreviations in the table stand for the following: PSf: Polysulfone PES: Polyethersulfone PES-OH: Hydroxy-terminated polyethersulfone EtOH: Ethanol MeOH: Methanol IPA: Isopropanol (2-propanol) tBuOH: tert-butyl alcohol AC: Autoclave NMP: N-methyl-2-pyrrolidone DMF: N,N-dimethylformamide TEG: Tetraethylene glycol MPD: m-phenylenediamine SDS: Sodium lauryl sulfate TMC: 1,3,5-trimesic acid chloride [Explanation of symbols]

[0161] 1. Hollow fiber membrane module 2, 3 Outer conduit 4. Hollow fiber membrane 5, 6 Adhesive fixing part 7, 8 Header 9, 10 Inner duct

Claims

1. A hollow fiber forward osmosis membrane having a porous support membrane, which is a hollow fiber support membrane, and a separation functional layer disposed on the porous support membrane, The porous support membrane is in contact with only the separation functional layer, The separation functional layer is a polyamide layer, The ratio of the relative element concentration obtained by curve fitting centered at 533 eV in the O1s spectrum to the relative element concentration obtained from the N1s spectrum when the surface of the separation functional layer is measured by X-ray photoelectron spectroscopy (O 533eV / N ratio) is 0.35 to 0.53, In IR measurement of the surface of the separation functional layer, -1 The intensity of the peak top at 1720 cm -1 Peak top intensity ratio (IR 1720 / IR 1650 ) is 0.20 or less.

2. The ratio (O 533eV 2. The forward osmosis membrane according to claim 1, wherein the A / N ratio is 0.35 to 0.

51.

3. 2. The forward osmosis membrane according to claim 1, wherein the ratio of the number of oxygen atoms to the number of nitrogen atoms (O / N ratio) when the surface of the separation functional layer is measured by X-ray photoelectron spectroscopy is 1.30 to 1.

70.

4. 2. The forward osmosis membrane according to claim 1, wherein the ratio of the number of oxygen atoms to the number of nitrogen atoms (O / N ratio) when the surface of the separation functional layer is measured by X-ray photoelectron spectroscopy is 1.40 to 1.

65.

5. The forward osmosis membrane according to claim 1 , wherein the separation functional layer is disposed on an inner surface of the hollow fiber membrane.

6. 2. The forward osmosis membrane of claim 1, wherein the porous support membrane comprises polysulfone or polyethersulfone as a main component.

7. The forward osmosis membrane according to claim 1, wherein the ethanol swelling rate of the porous support membrane is 1% to 5%.

8. 2. The forward osmosis membrane according to claim 1, wherein the surface pore size of the surface of the porous support membrane in contact with the separation functional layer is 1 nm to 15 nm.

9. 2. The forward osmosis membrane according to claim 1, wherein the surface pore size of the surface of the porous support membrane that is in contact with the separation functional layer is 2.5 nm or more.

10. The forward osmosis membrane according to claim 1 , wherein the surface pore size of the surface of the porous support membrane that is in contact with the separation functional layer is 11 nm or less.

11. 2. The forward osmosis membrane according to claim 1, wherein the porous support membrane has a thickness of 50 μm to 400 μm.

12. The forward osmosis membrane according to claim 1 , wherein the separation functional layer has an uneven structure.

13. The forward osmosis membrane according to claim 1 , wherein the separation functional layer has an arithmetic mean height of 60 nm or more.

14. A method for producing a forward osmosis membrane having a porous support membrane and a separation functional layer disposed on the porous support membrane, comprising: A step of forming a polymer constituting a separation functional layer on a porous support membrane to obtain a composite membrane; a step of subjecting the composite membrane to a moist heat treatment in a heated and pressurized moist gas atmosphere to obtain a moist heat treated membrane; contacting the heat-and-moisture treatment film with a hydrophilic organic compound; Including, The porous support membrane is a hollow fiber support membrane, and the surface pore size of the porous support membrane is 15 nm or less; The forward osmosis membrane is a hollow fiber forward osmosis membrane, Purified water was placed as a raw material liquid on the separation functional layer side through the forward osmosis membrane, and a 3.5 mass% sodium chloride aqueous solution was placed as a draw solution on the porous support membrane side. When forward osmosis evaluation was performed while pressurizing the draw solution side to 40 kPa, The amount of water permeating into the draw solution F is 5.0 kg / (m 2 × hr) or more, and The water permeability F (kg / (m 2 × hr)) and the amount of salt back-diffusion R (g / (m 2 × hr)) is expressed by the following formula: R≦0.05×e 0.225×F A method for satisfying the relationship expressed by

15. The method according to claim 14 , wherein the porous support membrane is in contact with only the separation functional layer.

16. The method according to claim 14, wherein the separation functional layer is disposed on an inner surface of the hollow fiber membrane.

17. The method of claim 14, wherein the porous support membrane comprises polysulfone or polyethersulfone as a major component.

18. The method according to claim 14, wherein the separation functional layer is a layer of crosslinked polyamide obtained by reacting a polyfunctional amine with a polyfunctional acid halide.

19. The method according to claim 14, wherein the moist heat treatment is carried out by contacting the composite membrane with water vapor at 100°C or higher.

20. The method according to claim 14, wherein the hydrophilic organic compound is an alcohol having 1 to 4 carbon atoms.

21. The method according to claim 14 , wherein the contacting is carried out by contacting the heat-moisture treatment film with an aqueous solution containing the hydrophilic organic compound at a concentration of 40% by mass or more.

22. The method of claim 14, wherein the contacting is for 5 minutes or more.

23. 15. The method of claim 14, wherein said contacting is performed by one or more selected from the group consisting of immersion, flow-through, and filtration.

24. The method according to claim 14, wherein the ethanol swelling ratio of the porous support membrane is 1% to 5%.

25. The method according to claim 14, wherein the surface pore size of the porous support membrane is from 3 nm to 10 nm.

26. The method according to claim 14, wherein the porous support membrane has a membrane thickness of 50 μm to 400 μm.

27. 15. The method of claim 14, wherein the salt permeation selectivity R / F, which is the ratio of the salt back-diffusion amount R to the water permeation amount F, is 0.10 g / kg or less.

28. 15. The method of claim 14, wherein the salt permeation selectivity R / F, which is the ratio of the salt back-diffusion amount R to the water permeation amount F, is 0.07 g / kg or less.

29. 15. The method of claim 14, wherein the salt permeation selectivity R / F, which is the ratio of the salt back-diffusion amount R to the water permeation amount F, is 0.035 g / kg or less.

30. The water permeability F is 8.0 kg / (m 2 15. The method according to claim 14, wherein the heating time is equal to or greater than 1 s.

31. The water permeability F is 10.0 kg / (m 2 15. The method according to claim 14, wherein the heating time is equal to or greater than 1 s.

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