Fluid separation membrane module and fluid separation membrane plant

Abstract

To provide a fluid separation membrane module storing separation membranes each having a coated surface, while securing intermembrane distance.SOLUTION: There is provided a fluid separation membrane module including fluid separation membranes and spacers. In the fluid separation membrane module, at least a part of the spacers is arranged between the fluid separation membranes, and at least a part of the surface of the fluid separation membrane has a coating layer 1.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a fluid separation membrane module, a fluid separation membrane plant, and a purified fluid. [Background technology]

[0002] Membrane separation is a method for selectively separating and purifying specific gas components from a mixture containing multiple gas components. Because membrane separation utilizes pressure differences, it has the advantage of consuming less energy than other separation and purification methods.

[0003] The gas separation membrane used in membrane separation methods consists of a gas separation functional layer that has higher gas permeability for specific gas components (permeable gases) than for other gas components (non-permeable gases), and a permeable layer (including a flow path and a support) that does not substantially contribute to gas separation.

[0004] The performance of a gas separation membrane is expressed by the permeability of the permeable gas and the gas permeation selectivity, which is the ratio of the permeability of the permeable gas to the permeable gas. The higher the permeability of the permeable gas and the gas permeation selectivity, the higher the membrane separation efficiency.

[0005] Generally, the thinner the separation functional layer, the higher the permeability of the permeating gas. On the other hand, as the separation functional layer becomes thinner, the risk of defects such as pinholes and cracks occurring in the separation functional layer increases. Since such defects significantly impair the gas permeation selectivity of the separation functional layer, a defect repair method is known in which the surface of the gas separation membrane is coated with silicone or the like (see, for example, Non-Patent Document 1).

[0006] Furthermore, in order to increase the membrane area per unit volume, gas separation membranes are used as gas separation membrane modules packed into a partitioned space. When the gas separation membrane is a hollow fiber membrane, it is used as a hollow fiber membrane module containing multiple hollow fiber membranes, and when the gas separation membrane is a flat membrane, it is used as a spiral module in which a flat gas separation membrane is wound around a central pipe. A known method for repairing defects in a gas separation membrane module is to coat the surface of the gas separation membrane with silicone or the like by passing a silicone solution or the like through the space in the gas separation membrane module through which the gas to be separated passes (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2018-167150 [Non-patent literature]

[0008] [Non-Patent Document 1] Journal of Membrane Science 1997,131,85-94. Summary of the Invention [Problem to be solved by the invention]

[0009] Non-Patent Document 1 discloses a method for improving gas permeation selectivity by immersing a hollow fiber carbon membrane in a polydimethylsiloxane solution, removing the polydimethylsiloxane solution, and then drying and heating the membrane to cover defects in the carbon membrane with a polydimethylsiloxane layer. However, in the method of Non-Patent Document 1, the entire surface of the carbon membrane is coated with a polydimethylsiloxane layer. Therefore, when a module containing multiple carbon membranes is fabricated, friction and adhesion may occur between the polydimethylsiloxane layers on the surface of adjacent carbon membranes, which may cause the carbon membrane to break or hinder the passage of the target gas to be separated. In addition, the method of Non-Patent Document 1 does not allow for repair of defects that occur during module fabrication, so if defects occur during module fabrication, gas permeation selectivity will be significantly reduced.

[0010] Patent Document 1 discloses a method for manufacturing a module in which a gas separation membrane is disposed within an exterior housing, the method comprising: a porous support having a hollow tubular structure; and a gas separation layer disposed on the outside or inside of the porous support, the gas separation layer having an inorganic membrane and a grain boundary membrane disposed at the grain boundaries of the inorganic membrane. The method includes the following steps: disposing the gas separation layer within the exterior housing; adding a solution containing an organic material to a first space between the gas separation layer and the exterior housing; and reducing the pressure in a second space inside the gas separation layer to fill the grain boundaries of the gas separation layer with the organic material. However, with the method of Patent Document 1, when removing the solution containing the organic material and drying the membrane, the organic material may adhere the gas separation membranes to each other, or the gas separation membrane may bend and break due to drying shrinkage of the organic material solution. Adhesion of the gas separation membranes to each other reduces the surface area of ​​the gas separation membrane capable of separating gases, thereby reducing membrane utilization efficiency. Furthermore, breakage of the gas separation membrane significantly reduces gas separation efficiency.

[0011] Therefore, an object of the present invention is to provide a fluid separation membrane module that houses separation membranes with coated surfaces while ensuring an inter-membrane distance. [Means for solving the problem]

[0012] To solve the above problems, the present invention has the following configuration: A fluid separation membrane module including a fluid separation membrane and a spacer, wherein at least a portion of the spacer is disposed between the fluid separation membranes, and a coating layer 1 is formed on at least a portion of the surface of the fluid separation membrane. [Effects of the Invention]

[0013] In the fluid separation membrane module of the present invention, the spacers ensure the distance between the fluid separation membranes, thereby reducing friction between the coating layers 1 on the surfaces of adjacent fluid separation membranes and adhesion between the coating layers 1 on the surfaces of adjacent fluid separation membranes. In addition, the presence of the coating layers 1 limits the movement of the spacers, thereby reducing damage to the surfaces of the fluid separation membranes that would otherwise occur due to spacer movement during module fabrication or operation. [Brief explanation of the drawings]

[0014] [Figure 1] 1 is a schematic diagram showing a cross section including an inlet / outlet for fluids to be separated of one embodiment of a fluid separation membrane module of the present invention. [Figure 2] FIG. 1 is a schematic diagram showing one embodiment of the arrangement of a fluid separation membrane and spacers of the present invention. [Figure 3] FIG. 2 is a schematic diagram showing another embodiment of the arrangement of a fluid separation membrane and spacers of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0015] The fluid separation membrane module of the present invention (hereinafter sometimes simply referred to as "module") is a fluid separation membrane module including a fluid separation membrane and a spacer, characterized in that at least a portion of the spacer is disposed between the membranes of the fluid separation membrane, and that at least a portion of the surface of the fluid separation membrane has a coating layer 1.

[0016] The present invention will now be described by way of example with reference to the drawings, but the present invention should not be construed as being limited to the examples.

[0017] A cross-sectional view of one embodiment of a fluid separation membrane module of the present invention is shown in Figure 1. Figure 1 is a cross-sectional view of a module containing hollow fiber fluid separation membranes, including an inlet and outlet for fluids to be separated.

[0018] The module of the present invention includes a fluid separation membrane and a spacer, that is, a fluid separation membrane 1 and a spacer 3 housed in a vessel 10 having an inlet / outlet 8 for the fluid to be separated.

[0019] The module of the present invention also has a coating layer 1 on at least a portion of the surface of the fluid separation membrane. That is, the fluid separation membrane 1 in Fig. 1 has a hollow portion 2 and coating layers 1; 4 on the surface.

[0020] A preferred embodiment of the module of the present invention is one in which the surface of the spacer has a coating layer 2. That is, the spacer 3 in Fig. 1 has a coating layer 2;5 on its surface.

[0021] Furthermore, in the module of the present invention, the fluid separation membranes are preferably fixed in a potting region, and the surface of the potting region on the inner side of the fluid separation membrane module has a coating layer 3. In this regard, the fluid separation membranes 1 bundled in parallel in Figure 1 have both ends fixed (potted) to each other in a potting region 7 and are also fixed to a vessel 10. The potting region 7 has coating layers 3; 6 on the surface on the inner side of the fluid separation membrane module.

[0022] The fluid separation membrane 1 penetrates the potting portion 7 and is connected from the outlet 9 for the permeated fluid of the vessel 10 to an external flow path (such as a flow path for recovering the fluid that has permeated the fluid separation membrane) not shown.

[0023] The mixed gases and mixed liquids to be separated by the module of the present invention are not particularly limited, but examples include carbon dioxide separation and storage systems from exhaust gases of power plants, blast furnaces, etc., removal of sulfur components from gasified fuel gas in integrated coal gasification combined cycle power generation, purification of biogas and natural gas, purification of hydrogen from organic hydrides, etc. In other words, in the module of the present invention, the fluid separation membrane is preferably a gas separation membrane.

[0024] In the module of the present invention, the cross-sectional shape of the vessel is preferably elliptical or circular, more preferably circular, from the viewpoint of improving the pressure resistance of the vessel. Here, the cross section of the vessel refers to a cross section of the vessel perpendicular to the longitudinal direction of the fluid separation membrane. Examples of materials for the vessel include metal, resin, fiber-reinforced plastic (FRP), etc., and can be selected appropriately depending on the environment of the installation location and the conditions of use. For applications requiring pressure resistance and heat resistance, metals that combine strength and moldability are preferred, and stainless steel is more preferred.

[0025] The inlet and outlet ports for the fluid to be separated, which are arranged in the vessel, have the function of directing the fluid to be separated to the fluid separation membrane. When the fluid separation membrane is used in a dead-end filtration system, it is sufficient that it has one inlet and outlet port for the fluid to be separated. When it is used in a cross-flow filtration system, it is preferable that it has two or more inlet and outlet ports for the fluid to be separated. The vessel may have multiple inlet and outlet ports for the fluid to be separated as long as the mechanical strength of the vessel is maintained. In this case, it is preferable to place a fabric such as mesh or felt between the inlet and outlet port and the fluid separation membrane to the extent that it does not hinder the passage of the fluid, which has the effect of diffusing the fluid and protecting the fluid separation membrane.

[0026] In the module of the present invention, methods for fixing the fluid separation membrane to the vessel include fixing the fluid separation membrane directly to the inner surface of the vessel with a potting material, and fixing a separation membrane element, in which multiple fluid separation membranes are fixed with a potting material, to the vessel via an adapter or the like (an O-ring is one example) that can ensure liquid-tightness or airtightness. Fixing the membrane to the vessel via an adapter or the like is preferred because it allows the separation membrane element alone to be replaced when the performance of the separation membrane element deteriorates over time.

[0027] The potting portion of a module or separation membrane element may be in one location or in multiple locations, but from the viewpoint of sufficiently fixing the position of the fluid separation membrane and maintaining the effective surface area of ​​the fluid separation membrane, it is preferable to fix multiple fluid separation membranes bundled in a substantially linear shape at two locations on both ends with potting material. Also, multiple bundled fluid separation membranes may be folded into a U-shape and fixed at both ends with potting material at one location, or only one end of the fluid separation membrane may be fixed with potting material and the other end may be sealed with a means other than potting material.

[0028] In one embodiment of the present invention, the separation membrane element may have a casing (hereinafter referred to as "element casing") separate from the vessel. The element casing preferably has an inlet and outlet for the fluid to be separated. The shape of the element casing is not particularly limited as long as it does not prevent it from being housed in the vessel. Examples of materials for the element casing include metal, resin, and fiber-reinforced plastic (FRP), and can be selected appropriately depending on the conditions of use. Resin is preferred because it has a high ability to follow the cure shrinkage of the potting material, and polyphenylene sulfide, polytetrafluoroethylene, polyethylene, polypropylene, polyether ether ketone, polyphenylene ether, polyetherimide, polyamideimide, and polysulfone are more preferred because they combine moldability and chemical resistance.

[0029] Examples of the potting material include thermoplastic resins and thermosetting resins, and may further contain other additives.

[0030] Examples of thermoplastic resins used as potting materials include polyethylene, polyethersulfone, polystyrene, polyphenylene sulfide, polyarylate, polyester, liquid crystal polyester, polyamide, and polymethyl methacrylate. Examples of thermosetting resins include epoxy resin, unsaturated polyester resin, urethane resin, urea resin, phenolic resin, melamine resin, and silicone resin. Two or more of these may be used. Among these, epoxy resin and urethane resin are preferred from the viewpoint of a balance between moldability, curing time, adhesiveness, hardness, and the like.

[0031] Additives suitable for use in the potting material include, for example, fillers, surfactants, silane coupling agents, and rubber components. Examples of fillers include silica, talc, zeolite, calcium hydroxide, and calcium carbonate, which have the effects of suppressing heat generation during curing, improving strength, and thickening the material. Surfactants and silane coupling agents also have the effects of improving the handleability of the potting material when mixed and improving the infiltration of the potting material between carbon membranes for fluid separation when injected. Rubber components also have the effect of improving the toughness of the cured and molded potting material. The rubber component may be contained in the form of rubber particles.

[0032] The module of the present invention is a fluid separation membrane module including a fluid separation membrane and a spacer, characterized in that at least a portion of the surface of the fluid separation membrane has a coating layer 1. As described above, in conventional technologies, modules consisting of fluid separation membranes with coated surfaces have problems such as rupture of the fluid separation membrane or obstruction of the passage of the fluid to be separated due to friction between the coating layers 1 on the surfaces of adjacent fluid separation membranes or adhesion between the coating layers 1 on the surfaces of adjacent fluid separation membranes. The module of the present invention houses spacers along with the fluid separation membranes, ensuring distance between the fluid separation membranes within the module and suppressing friction between the coating layers 1 on the surfaces of adjacent fluid separation membranes and adhesion between the coating layers 1, thereby preventing rupture of the fluid separation membrane and obstruction of the permeation of the fluid to be separated. In addition, friction between the spacers and the coating layer 1 makes them less likely to move, thereby suppressing displacement of the spacers during fabrication and operation of the separation membrane module and enabling uniform passage of the fluid to be separated.

[0033] When the coating layer 1 non-selectively coats the surface of the fluid separation membrane, it is more preferable that the entire surface of the fluid separation membrane has the coating layer 1. This ensures that the surface of the fluid separation membrane is coated reliably.

[0034] On the other hand, for example, when defects in a fluid separation membrane are selectively repaired by counter diffusion or the like, it is more preferable to have the coating layer 1 on at least a portion of the surface of the fluid separation membrane. This makes it possible to maintain the packing rate of the fluid separation membrane within the fluid separation membrane module and the permeability of the fluid to be separated.

[0035] A fluid separation membrane is a membrane that exhibits higher permeability to specific components (permeating components) contained in a fluid to be separated relative to other components (non-permeating components). The shape of the fluid separation membrane is not particularly limited, and it may be a flat membrane or a hollow fiber membrane. However, hollow fiber membranes are preferred because they facilitate increasing the membrane area per unit volume of a module when used in a separation membrane module. When the fluid separation membrane is a hollow fiber membrane, the inner diameter of the hollow fiber membrane is preferably 10 μm or more and 2,000 μm or less. By making the inner diameter of the hollow fiber membrane 10 μm or more, fluid permeability can be improved. The inner diameter of the hollow fiber membrane is more preferably 20 μm or more, and even more preferably 50 μm or more. On the other hand, by making the inner diameter of the hollow fiber membrane 2,000 μm or less, the outer diameter of the hollow fiber membrane can be reduced, thereby increasing the membrane area of ​​the fluid separation membrane per unit volume when used in a fluid separation membrane module. The inner diameter of the fluid separation membrane is more preferably 1,000 μm or less, and even more preferably 500 μm or less.

[0036] Examples of fluid separation membranes include inorganic membranes such as zeolite membranes, metal-organic framework (MOF) membranes, and carbon membranes, as well as polymer membranes. When the fluid separation membrane module is used in harsh environments such as high temperatures or acidic or alkaline environments, the fluid separation membrane is preferably an inorganic membrane with excellent heat resistance and chemical resistance, and is more preferably a zeolite membrane or a carbon membrane. In the fluid separation membrane module of the present invention, the spacers prevent the fluid separation membranes from contacting each other, so that even inorganic membranes that are hard and brittle and therefore prone to surface defects or breakage upon contact can be suitably used.

[0037] Zeolite membranes suitable for use as fluid separation membranes include membranes made of aluminosilicates, such as NaX type (FAU), ZSM-5, MOR, silicalite, and A type. Two or more of these may be used. Zeolite species preferably have a Si / Al ratio similar to that of the zeolite grown secondary by hydrothermal synthesis.

[0038] Examples of MOF membranes suitable as fluid separation membranes include membranes made of Cu-BTC, MOF-5, IRMOF-3, MIL-47, MIL-53, MIL-96, MMOF, SIM-1, ZIF-7, ZIF-8, ZIF-22, ZIF-69, and ZIF-90. Two or more of these may be used.

[0039] Examples of carbon membranes suitable as fluid separation membranes include membranes obtained by carbonizing polyphenylene oxide, polyvinyl alcohol, polyacrylonitrile, phenolic resin, wholly aromatic polyester, unsaturated polyester resin, alkyd resin, melamine resin, urea resin, polyimide resin, diallyl phthalate resin, lignin resin, urethane resin, etc. Two or more of these may be used.

[0040] Examples of polymer membranes suitable as fluid separation membranes include membranes made of aromatic polyimide, cellulose acetate, polysulfone, aromatic polyamide, polyetherimide, polyethersulfone, polyacrylonitrile, polyphenylene sulfide, polyetheretherketone, polytetrafluoroethylene, polyvinylidene fluoride, poly(1-trimethylsilylpropyne), polydimethylsiloxane, polyvinyltrimethylsilane, poly(4-methylpentene), ethyl cellulose, natural rubber, poly(2,6-dimethylphenylene oxide), low-density polyethylene, high-density polyethylene, styrene, polyethyl methacrylate, polycarbonate, polyester, aliphatic polyamide, polymethyl methacrylate, polyvinyl alcohol, silicone, etc. Two or more of these may be used.

[0041] Nanoparticles can be added to fluid separation membranes to improve the permeability of permeating components. Examples of nanoparticles include silica, titania, zeolite, metal oxides, MOFs, and carbon nanotubes (CNTs).

[0042] In one embodiment of the present invention, the fluid separation membrane may include a support. When the fluid separation membrane of the present invention includes a support, it is more preferable that the support is disposed on only one surface of the fluid separation membrane.

[0043] Examples of the support include porous inorganic materials such as alumina, silica, cordierite, zirconia, titania, Vycor glass, zeolite, magnesia, and sintered metal; porous organic materials containing at least one polymer selected from the group consisting of homopolymers and copolymers of polysulfone, polyethersulfone, polyamide, polyester, cellulose-based polymer, vinyl polymer, polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfone, and polyphenylene oxide; and porous carbon materials obtained by carbonizing porous organic materials made of carbonizable resins. Examples of carbonizable resins include polyphenylene oxide, polyvinyl alcohol, polyacrylonitrile, phenolic resin, wholly aromatic polyester, unsaturated polyester resin, alkyd resin, melamine resin, urea resin, polyimide resin, diallyl phthalate resin, lignin resin, and urethane resin. Two or more of these may be used.

[0044] The coating layer 1 is a layer that covers at least a portion of the surface of the fluid separation membrane, and can improve separation selectivity by covering, for example, defective sites on the surface of the fluid separation membrane.

[0045] Examples of the coating layer 1 include a layer containing at least one compound selected from the group consisting of polyolefin, fluororesin, polystyrene, silicone, microporous polymer (PIM), phenolic resin, and urethane resin. It is more preferable to contain at least one compound selected from the group consisting of silicone and PIM, as this allows for easier coating onto the surface of the fluid separation membrane.

[0046] The abundance ratio of the above compound contained in the coating layer 1 is preferably 20 wt% or more and 100 wt% or less, relative to 100 wt% of the total weight of the coating layer 1. When the abundance ratio of the above compound contained in the coating layer 1 is 20 wt% or more, the physical properties of the above compound are more likely to be reflected in the physical properties of the coating layer 1. The abundance ratio of the above compound contained in the coating layer 1 is more preferably 50 wt% or more, and even more preferably 80 wt% or more.

[0047] Suitable polyolefins for use as the compound in the coating layer 1 include, for example, polyethylene, polypropylene, polymethylpentene, and the like.

[0048] An example of a fluororesin suitable as a compound in the coating layer 1 is tetrafluoroethylene.

[0049] Examples of silicones suitable as compounds in the coating layer 1 include polydimethylsiloxane.

[0050] A phenolic resin suitable as a compound in the coating layer 1 is a resin obtained by the reaction of a phenol with an aldehyde, for example, a phenolic resin formed by a counter-diffusion reaction between a water-soluble phenolic resin solution obtained by polycondensation of a phenol with an aldehyde and a curing gas of the water-soluble phenolic resin solution.

[0051] The water-soluble phenolic resin solution includes, for example, phenolic resins obtained by reacting phenols, including phenol, cresol, resorcinol, bisphenol A, and other substituted phenols, as raw materials with aldehyde compounds or the like in the presence of an alkaline catalyst.

[0052] Examples of the curing gas for the water-soluble phenolic resin solution include acidic gases such as carbon dioxide, hydrogen sulfide, sulfur oxides, nitrogen oxides, inorganic acids (hydrogen chloride, etc.), and organic acids (carboxylic acids, etc.), as well as gases that generate acids upon reaction with the water-soluble phenolic resin solution, such as esters (organic esters, inorganic esters, etc.). A mixture of multiple curing gases may be used, or a mixed gas with an inert gas may be used.

[0053] Because of their high safety, carbon dioxide or methyl formate is preferably used as the hardening gas for the water-soluble phenolic resin solution, and carbon dioxide is more preferably used.

[0054] A urethane resin suitable as a compound in the coating layer 1 is a resin obtained by a polyaddition reaction between a polyol compound and a polyisocyanate compound, such as a urethane resin formed by a counter-diffusion reaction between a mixed solution of a phenolic resin (a polyol compound) and a polyisocyanate compound and an amine gas that acts as a catalyst for the polyaddition reaction.

[0055] Examples of the phenolic resin include phenolic resins obtained by reacting phenols, including phenol, cresol, resorcinol, bisphenol A, and other substituted phenols, as raw materials with an aldehyde compound or the like in the presence of an alkaline catalyst.

[0056] Polyisocyanate compounds are organic compounds having two or more isocyanate groups in one molecule, and include aliphatic and aromatic polyisocyanate compounds, as well as modified products thereof. Examples of aliphatic polyisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and methylcyclohexane diisocyanate. Examples of aromatic polyisocyanates include toluene diisocyanate, diphenylmethane diisocyanate, and polymeric diphenylmethane diisocyanate. Examples of modified products thereof include carbodiimide modified products and prepolymer modified products.

[0057] Examples of the amine gas used to form the urethane resin include triethylamine, dimethylethylamine, and dimethylisopropylamine.

[0058] The thickness of the coating layer 1 is not particularly limited, but is preferably 0.1 μm or more and 100 μm or less. When the thickness of the coating layer 1 is 0.1 μm or more, the surface of the fluid separation membrane can be reliably coated. The thickness of the coating layer 1 is more preferably 1 μm or more, and even more preferably 2 μm or more. On the other hand, when the thickness of the coating layer 1 is 100 μm or less, the filling rate of the fluid separation membrane in the fluid separation membrane module and the permeability of the fluid to be separated can be maintained. The thickness of the coating layer 1 is more preferably 50 μm or less, and even more preferably 20 μm or less.

[0059] The thickness of coating layer 1 can be measured, for example, by observing the cross section of the fluid separation membrane having coating layer 1 with a transmission electron microscope (SEM) or the like. The cross section of the fluid separation membrane having coating layer 1 can be obtained by embedding the fluid separation membrane having coating layer 1 in a resin or the like that can be distinguished from coating layer 1 during observation, and cutting the membrane in a direction perpendicular to the depth direction of coating layer 1.

[0060] In the module of the present invention, the fluid separation membrane having coating layer 1 on at least a portion of its surface preferably has a bending radius of 100 cm or less. Having a bending radius of 100 cm or less for the fluid separation membrane having coating layer 1 can prevent breakage of the fluid separation membrane during module fabrication and operation. The bending radius is more preferably 10 cm or less, and even more preferably 5 cm or less. Fluid separation membranes having coating layer 1 with a small bending radius are highly flexible and therefore prone to localized close proximity within the module, which can easily cause friction between the coating layers 1 on the surfaces of adjacent fluid separation membranes and adhesion between the coating layers 1. However, since the fluid separation membrane module of the present invention uses spacers to ensure distance between the fluid separation membranes, even fluid separation membranes having coating layer 1 with a small bending radius can be suitably used. Meanwhile, while there is no particular lower limit for the bending radius of the fluid separation membrane having coating layer 1, a bending radius of 0.1 cm or more is preferred. Having a bending radius of 0.1 cm or more improves dimensional stability when handling fluid separation membranes having coating layer 1 as a bundle, improving module fabrication efficiency. The bending radius is more preferably 0.2 cm or more, and even more preferably 0.5 cm or more.

[0061] The bending radius of a fluid separation membrane having coating layer 1 can be determined by sampling a fluid separation membrane having coating layer 1 from a module to a length of 10 cm or more, and determining the radius of a cylinder at which the fluid separation membrane does not break when the sampled fluid separation membrane having coating layer 1 is wrapped around a cylinder by 360° or more along the normal direction of the cylinder. If the bending radius of the fluid separation membrane having coating layer 1 is 1.5 cm or more, evaluation is performed by appropriately reducing the angle at which the sampled fluid separation membrane having coating layer 1 is wrapped around the cylinder along the normal direction of the cylinder, and the radius of the cylinder at which the fluid separation membrane does not break can be considered to be the bending radius of the fluid separation membrane having coating layer 1.

[0062] In one embodiment of the present invention, the fluid separation membrane having the coating layer 1 has a water permeability of 100 μL / hr / m 2 / Pa or less. The water permeability of the fluid separation membrane having the coating layer 1 is preferably 100 μL / hr / m 2 A fluid separation membrane having a water permeability of 10 μL / hr / m or less can be suitably used as a gas separation membrane because the pore size of the separation functional layer is small. 2 / Pa or less is more preferable, and 1 μL / hr / m 2 / Pa or less is more preferable.

[0063] The water permeability of a fluid separation membrane having coating layer 1 can be calculated using the following formula 1 from the amount of permeated water recovered from the permeated fluid outlet of the module when pure water is supplied from the inlet / outlet of the fluid to be separated of the module.

[0064] Water permeability (μL / hr / m 2 / Pa)=Q w / (P×T×A)...Equation 1 [In Equation 1, Qw represents the amount of permeated water (μL), P represents the pressure of the feed water (Pa), T represents the permeation time (hr), and A represents the membrane area (m 2 ) represents. The spacers are placed between the fluid separation membranes to ensure a distance between the fluid separation membranes, thereby suppressing friction between the coating layers 1 on the surfaces of the fluid separation membranes and adhesion between the coating layers 1 on the surfaces of adjacent fluid separation membranes.

[0065] The spacer is not particularly limited, but is preferably selected from the group consisting of a film, a nonwoven fabric, a woven fabric, a knitted fabric, a fiber, a rod, and a particle. Two or more of these may be combined. When the fluid separation membrane is a flat membrane, the spacer is preferably a film, a nonwoven fabric, a woven fabric, or a knitted fabric, because they are easily arranged between the fluid separation membranes. When the fluid separation membrane is a hollow fiber membrane, the spacer is preferably a fiber or a rod.

[0066] Furthermore, when the fluid separation membrane is a hollow fiber, spacers can be uniformly arranged around the fluid separation membrane, and therefore, one preferred embodiment of the present invention is one in which spacers spirally wrap around one or more fluid separation membranes.

[0067] Figures 2 and 3 show schematic diagrams of an embodiment in which spacers are spirally coated around one or more fluid separation membranes. Figure 2 is a schematic diagram of an embodiment in which one fluid separation membrane 1 is spirally coated with one spacer 3 at a pitch of 12, and Figure 3 is a schematic diagram of an embodiment in which two fluid separation membranes 1 are spirally coated with two spacers 3, each at a pitch of 12. In Figures 2 and 3, at least a portion of the surface of the fluid separation membrane 1 has coating layers 1; 4, not shown.

[0068] The covering of the periphery of the fluid separation membrane with the spacer may be a single covering in which the spacer is wrapped once around the fluid separation membrane, a double covering in which the spacer is wrapped twice around the fluid separation membrane, or a multi-stage covering in which the spacer is further spirally wrapped around multiple fluid separation membranes wrapped around the spacer.

[0069] In the fluid separation membrane module of the present invention, the presence of coating layer 1 between the fluid separation membrane and the spacer makes the spacer less likely to move, thereby preventing the spacer from shifting during fabrication and operation of the separation membrane module and allowing the fluid to be separated to pass through uniformly. In addition, damage to the surface of the fluid separation membrane caused by friction between the fluid separation membrane and the spacer can be prevented.

[0070] Examples of the spacer include polyester, nylon, polyolefin, fluororesin, polyacetal, thermoplastic elastomer, metal oxide, etc. Two or more of these may be used.

[0071] Furthermore, when the spacer is a fiber, the spacer may be either a monofilament or a multifilament, but a multifilament is preferred because it is flexible and easy to handle. Furthermore, the spacer is more preferably a false-twisted yarn because it is highly bulky and makes it easy to ensure the distance between the fluid separation membranes. As false-twisted yarn suitable for the spacer, polyester yarn and nylon yarn are preferred because they are easy to false-twist.

[0072] In one embodiment of the present invention, the spacer may have a coating layer 2 on its surface. The presence of coating layer 2 on at least a portion of the spacer surface makes the spacer less likely to move due to friction or adhesion between coating layer 1 and coating layer 2, further suppressing displacement of the spacer during fabrication and operation of the separation membrane module and allowing the fluid to be separated to pass through uniformly. In addition, damage to the surface of the fluid separation membrane resulting from friction between the fluid separation membrane and the spacer can be further suppressed.

[0073] In one embodiment of the present invention in which spacers are spirally wrapped around one or more of the fluid separation membranes, the total fineness and pitch of the spacers preferably satisfy the following formula 1.

[0074] 1 < F0 / L < 100...Equation 1 [In the formula, F0 represents the total fineness of the spacers (unit: dtex), and L represents the spacer pitch (unit: mm)] In formula 1, when F0 / L is 1 or more, the total fineness of the spacers is sufficiently large relative to the spacer pitch, and the distance between the fluid separation membranes can be more effectively secured. F0 / L is more preferably 2 or more, and even more preferably 5 or more. On the other hand, although there is no particular upper limit for F0 / L, when it is 100 or less, the fluid separation membranes can be highly packed in the module. F0 / L is more preferably 50 or less, and even more preferably 10 or less.

[0075] The total fineness of the spacer can be measured by JIS L 1013 (2010) Method B. When the spacer has a coating layer 2, the total fineness measured including the coating layer 2 is considered to be the total fineness of the spacer.

[0076] The spacer pitch can be measured from the length in the fiber axis direction when the spacer is wrapped around one or more fluid separation membranes one turn. When the spacer pitch is small relative to the longitudinal length of the module, it is preferable to calculate the spacer pitch by measuring the length in the fiber axis direction of one or more fluid separation membranes around which the spacer is wrapped five or more times, and dividing the length by the number of times the spacer is wrapped.

[0077] Coating layer 2 may have the same composition as or a different composition from coating layer 1. Furthermore, coating layer 1 and coating layer 2 may have a clear boundary therebetween or may be integrated.

[0078] In one embodiment of the present invention, the fluid separation membrane may be fixed at a potting site, and a coating layer 3 may be provided on the surface of the potting site on the inner side of the fluid separation membrane module.

[0079] In one embodiment of the present invention, coating layer 3 is preferably made of an elastomer. By using coating layer 3 as an elastomer, vibration of the fluid separation membrane near the potting site during module fabrication and operation can be reduced, thereby preventing damage to the fluid separation membrane.

[0080] Suitable elastomers for the coating layer 3 include thermosetting elastomers and thermoplastic elastomers, and are selected appropriately depending on the operating conditions of the module. Examples of thermosetting elastomers include vulcanized rubber, urethane rubber, silicone rubber, and fluororubber. Examples of thermoplastic elastomers include polystyrene elastomers, olefin elastomers, polyvinyl chloride elastomers, polyurethane elastomers, polyester elastomers, polyamide elastomers, and acrylic elastomers.

[0081] Coating layer 3 may have the same composition as or a different composition from coating layer 1 and coating layer 2. Furthermore, coating layer 3 may have a clear boundary with coating layer 1 and coating layer 2, or may be integrated. From the viewpoint of workability during production of a fluid separation membrane module, coating layer 1, coating layer 2, and coating layer 3 preferably have the same composition.

[0082] The thickness of the coating layer 3 is preferably 10 μm or more and 50,000 μm or less. When the thickness of the coating layer 3 is 10 μm or more, it is possible to reduce vibration of the fluid separation membrane near the potting site during operation of the fluid separation membrane module. The thickness of the coating layer 3 is more preferably 100 μm or more, and even more preferably 1,000 μm or more. On the other hand, when the thickness of the coating layer 3 is 50,000 μm or less, it is possible to ensure a sufficient surface area of ​​the fluid separation membrane. The thickness of the coating layer 3 is more preferably 20,000 μm or less, and even more preferably 10,000 μm or less.

[0083] The thickness of the coating layer 3 can be measured, for example, by observing the cross section of the potting portion having the coating layer 3 with a transmission electron microscope (SEM) or the like. The cross section of the potting portion having the coating layer 3 can be obtained by embedding the potting portion having the coating layer 3 in a resin or the like that can be distinguished from the coating layer 3 upon observation, and cutting the potting portion in a direction perpendicular to the depth direction of the coating layer 3.

[0084] In the fluid separation membrane module of the present invention, the composition of the coating layer can be analyzed by elemental analysis of the coating layer, for example.

[0085] The method for producing the fluid separation membrane module of the present invention is not particularly limited, and may be a method (hereinafter referred to as production method 1) in which a fluid separation membrane module containing a fluid separation membrane without coating layer 1 and a spacer is produced, and then a liquid containing a raw material compound for coating layer 1 (hereinafter referred to as coating 1 liquid) is circulated inside the gas separation membrane module to form coating layer 1, or a method (hereinafter referred to as production method 2) in which a fluid separation membrane with coating layer 1 and a spacer are housed. Production method 1 is more preferred because it allows for repair of defects on the fluid separation membrane surface that occur during module production.

[0086] The method for manufacturing a fluid separation membrane module of the present invention is not particularly limited, but is preferably a method for manufacturing a fluid separation membrane module having a coating layer 1 on at least a portion of the surface of the fluid separation membrane, and includes the following steps:

[0087] Production method 1 includes the following steps.

[0088] Step 1: A step of preparing a module containing a fluid separation membrane without a coating layer 1 and a spacer.

[0089] Step 2: A step of passing the first coating solution through one of the spaces partitioned by the fluid separation membrane inside the fluid separation membrane module.

[0090] Step 3: Removing the first coating solution.

[0091] Step 4: A step of forming the coating layer 1.

[0092] In the above step 1, the spacer may have a coating layer 2 before being housed in the module, or a coating layer 2 having the same composition as the coating layer 1 may be formed when the coating layer 1 is formed. Alternatively, both may be formed.

[0093] In the above step 2, it is more preferable to reduce the pressure in the other space partitioned by the fluid separation membrane, which ensures that the Coating 1 solution reaches the defective areas of the fluid separation membrane.

[0094] The first coating liquid can be a melt or solution of the raw material compounds of the coating layer 1. From the viewpoint of ease of handling, it is preferable to use a solution. The raw material compounds of the coating layer 1 can be, for example, a compound selected from the group consisting of polyolefins such as polyethylene, polypropylene, and polymethylpentene, fluororesins such as tetrafluoroethylene, silicones such as polystyrene and polydimethylsiloxane, and microporous polymers (PIM). Furthermore, when the first coating liquid is a solution, a good solvent or dispersion medium for the raw material compounds of the coating layer 1 can be used as the solvent.

[0095] In the above step 3, the coating 1 liquid can be removed by, for example, discharging it from the inlet / outlet of the module for the fluid to be separated. The coating 1 liquid can be discharged from the inlet / outlet of the module for the fluid to be separated by tilting the module and discharging it under its own weight, by suctioning it with a syringe or the like, or by applying centrifugal force. However, applying centrifugal force when removing the coating 1 liquid is more preferable. Applying centrifugal force makes it easier to remove excess coating 1 liquid remaining between the fluid separation membranes, thereby reducing the thickness of the coating layer 1, and thus enabling coating without impairing the permeability of the fluid to be separated or the permeability of the permeating components.

[0096] In step 4, the coating layer 1 can be formed by, for example, cooling, drying, heating, etc. These methods may also be combined.

[0097] In the module of the present invention, the distance between the fluid separation membranes is ensured by the spacers, Even when flexible fluid separation membranes with a small bending radius are stored, adhesion and breakage of the fluid separation membranes due to the flow and volume changes of the coating liquid in steps 3 and 4 can be suppressed.

[0098] Furthermore, in an embodiment in which the fluid separation membrane module of the present invention has a coating layer 3, the method for forming the coating layer 3 is not particularly limited, and may be a manufacturing method in which the coating layer 3 is formed one location at a time while the module is left to stand, or a manufacturing method in which the coating layers 3 are formed simultaneously by applying centrifugal force. When the compositions of coating layer 1 and coating layer 3 are different and it is preferable that coating layer 3 not be coated on the fluid separation membrane, a manufacturing method in which the coating layer 3 is formed one location at a time while the module is left to stand is preferred. On the other hand, when it is acceptable for coating layer 3 to adhere to the fluid separation membrane, a method in which the coating layer 3 is formed simultaneously at multiple locations by applying centrifugal force is preferred. This shortens the production time, and particularly when coating layer 1 and coating layer 3 have the same composition, coating layer 1 and coating layer 3 can be formed simultaneously.

[0099] The mixed fluids to be separated by the module of the present invention are not particularly limited, but examples include carbon dioxide separation and storage systems from exhaust gases of power plants and blast furnaces, removal of sulfur components from gasified fuel gas in integrated coal gasification combined cycle power generation, purification of biogas and natural gas, and hydrogen purification from organic hydrides.

[0100] The fluid separation membrane plant of the present invention (hereinafter, sometimes simply referred to as "plant") is a plant including the module of the present invention. In addition to the module, the plant preferably includes pretreatment equipment, purified fluid recovery equipment, by-product fluid recovery equipment, etc. The pretreatment equipment is equipment for removing impurities from the fluid to be separated before separation and adjusting the composition of the fluid to be separated before separation. The purified fluid recovery equipment is equipment for recovering a purified fluid obtained by removing unnecessary components from the fluid to be separated before separation, and for further purifying it as necessary or supplying it to a pipeline, etc. The by-product fluid recovery equipment is equipment for recovering a by-product fluid removed from the fluid to be separated before separation, and, as an example, discharging it after detoxifying it. In the plant of the present invention, the module, pretreatment equipment, purified fluid recovery equipment, and by-product fluid recovery equipment are preferably connected by piping, etc., and the fluid to be separated before separation is preferably continuously separated into a purified fluid and a by-product fluid.

[0101] The plant preferably includes a plurality of modules depending on the processing amount of the fluid to be separated. The plurality of modules may be connected in series or in parallel with respect to the fluid to be separated. From the viewpoint of module production efficiency, it is preferable that the modules are connected in series, and from the viewpoint of partial module replacement, it is preferable that the modules are connected in parallel. One preferred embodiment of the plant of the present invention is an embodiment in which modules are connected in series, and the modules connected in series are further connected in parallel. In this way, it is possible to achieve both the advantages of connecting modules in series and the advantages of connecting modules in parallel.

[0102] The mixed gases and mixed liquids to be separated by the plant of the present invention are not particularly limited, but examples include carbon dioxide separation and storage systems from exhaust gases of power plants, blast furnaces, etc., removal of sulfur components from gasified fuel gas in integrated coal gasification combined cycle power generation, purification of biogas and natural gas, purification of hydrogen from organic hydrides, etc. In other words, in the plant of the present invention, the fluid separation membrane is preferably a gas separation membrane.

[0103] The purified fluid of the present invention is a fluid purified by the module of the present invention. The purified fluid may be purified by including a separate or additional purification step before or after the purification step in the module of the present invention, or may be mixed with a purified fluid purified by a different purification step. Examples of separate or different purification steps include distillation, adsorption, and absorption. Examples of additional steps include component adjustment by mixing with another fluid.

[0104] The purified fluid of the present invention requires only a small amount of energy for purification in the module, and therefore can be suitably used in various industrial applications as a purified fluid with a low environmental impact. [Example]

[0105] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these. Example 8 should be read as Comparative Example 4. Moreover, Example 3 should be read as Reference Example 1. The evaluations in each of the examples and comparative examples were carried out by the following methods.

[0106] (Fluid separation membrane breakage during module fabrication) The fabricated module was visually observed, and if rupture in the fluid separation membrane was observed through the acrylic pipe vessel, it was judged as "yes" to the rupture. If no rupture was observed visually, all but one of the inlet and outlet ports for the fluids to be separated were sealed, and the entire module was immersed in water with 0.2 MPaG of compressed air supplied from the remaining inlet and outlet port for the fluid to be separated. If bubbles were generated from the opening of the fluid separation membrane, it was judged as "yes" to the rupture, and if no bubbles were observed, it was judged as "no."

[0107] (Bending radius of fluid separation membrane with coating layer 1) A fluid separation membrane having coating layer 1 of 10 cm or more was cut out from the produced fluid separation membrane module, and the radius of a cylinder at which the fluid separation membrane having coating layer 1 was not broken when the cut-out fluid separation membrane having coating layer 1 was wrapped around the cylinder by 360° or more along the normal direction of the cylinder was determined. Five or more fluid separation membranes having coating layer 1 were cut out, and the average radius of the obtained cylinders, expressed to one significant digit, was used as the bending radius of the fluid separation membrane having coating layer 1.

[0108] In Comparative Example 3, the bending radius of the fluid separation membrane not having coating layer 1 was obtained by similar measurement. Furthermore, for modules in which the fluid separation membrane had "yes" fracture during module fabrication, the bending radius of the fluid separation membrane having coating layer 1 was not evaluated.

[0109] (Water permeability of fluid separation membrane having coating layer 1) Pure water at 0.1 MPaG was supplied to the inlet / outlet for the fluid to be separated of the fabricated fluid separation membrane module, and the pure water that permeated the fluid separation membrane was collected from the outlet for the permeated fluid for 10 minutes. The water permeability of the fluid separation membrane having coating layer 1 was calculated from the amount of collected pure water using the following formula 1.

[0110] Water permeability (μL / hr / m 2 / Pa)=Q w / (P×T×A)...Equation 1 [In Equation 1, Q w represents the amount of permeated water (μL), P represents the pressure of the feed water (Pa), T represents the permeation time (hr), and A represents the membrane area (m 2 ) represents. In Comparative Example 3, the water permeability of the fluid separation membrane not having coating layer 1 was obtained by similar measurements. Furthermore, for modules in which the fluid separation membrane was found to have ruptured during module fabrication, the water permeability of the fluid separation membrane having coating layer 1 was not evaluated.

[0111] (Thickness of coating layer 3) Epoxy resin was injected into the inlet and outlet of the fluid to be separated of the fabricated fluid separation membrane module and allowed to harden. The fluid separation membrane module was then cut perpendicular to the depth direction of the coating layer 3, and the area near the potting site was observed with a microscope SEM (Keyence VHX-7000) (magnification: 1000x). The thickness of the coating layer 3 was measured at five or more locations, and the average value, expressed to one significant digit, was used as the thickness of the coating layer 3 of the fluid separation membrane module.

[0112] (Module membrane utilization efficiency) The permeable gas of the fluid separation membrane was supplied at 0.2 MPaG from the inlet / outlet of the fluid to be separated in the module, and the permeable gas was collected from the outlet of the permeable fluid. The permeation rate of the permeable gas in the module (nmol / Pa m 2 On the other hand, the permeation rate (nmol / Pa m) of the permeable gas in one fluid separation membrane with coating layer 1, which was fabricated using the same fluid separation membrane and coating layer 1 as the evaluation module, was calculated in the same manner. 2 ·s) was calculated. When the ratio of the two (permeation rate of permeable gas in the module / permeation rate of permeable gas in one module) was 0.8 or higher, the module membrane utilization efficiency was rated as "excellent," when it was 0.6 or higher but less than 0.8, the module membrane utilization efficiency was rated as "good," when it was 0.4 or higher but less than 0.6, the module membrane utilization efficiency was rated as "fair," and when it was less than 0.4, the module membrane utilization efficiency was rated as "poor." Note that modules in which the fluid separation membrane was "broken" during module fabrication were not evaluated for membrane utilization efficiency.

[0113] (Module impact resistance) The fabricated fluid separation membrane module was fixed to a micromixer (Taitec, E-36) and shaken at 2500 rpm for 30 minutes. A non-permeable gas was supplied to the fluid separation membrane from the inlet and outlet of the module for the fluid to be separated at 0.2 MPaG. The permeation rate of the non-permeable gas (nmol / Pa m) before and after shaking was measured. 2·s) was measured, and if the ratio of the two (permeation amount of non-permeable gas after shaking / permeation amount of non-permeable gas before shaking) was less than 2, the module impact resistance was rated as "excellent," if it was 2 or more but less than 5, the module impact resistance was rated as "good," if it was 5 or more but less than 10, the module impact resistance was rated as "fair," and if it was 10 or more, the module impact resistance was rated as "poor." Modules in which the fluid separation membrane was "broken" during module production were not evaluated for impact resistance.

[0114] (Production Example 1) A spinning dope was prepared by mixing 10 parts by weight of polyacrylonitrile (PAN) (MW 150,000) manufactured by Polysciences, 10 parts by weight of polyvinylpyrrolidone (PVP) (MW 40,000) manufactured by Sigma-Aldrich, and 80 parts by weight of dimethyl sulfoxide (DMSO) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., and stirring at 100°C.

[0115] The obtained spinning dope was cooled to 25°C, and then a concentric triple spinneret was used to simultaneously discharge an 80 wt% aqueous DMSO solution from the inner tube, the spinning dope from the middle tube, and a 90 wt% aqueous DMSO solution from the outer tube, and then the spinning dope was introduced into a coagulation bath of pure water at 25°C and wound up on a roller to obtain a raw fiber. The obtained raw fiber was washed with water and then dried at 25°C for 24 hours using a circulating dryer to produce a precursor of a hollow fiber porous carbon membrane.

[0116] The obtained porous carbon membrane precursor was passed through an electric furnace at 250°C and heated in an air atmosphere for 1 hour to perform infusibilization treatment, thereby obtaining an infusibilized yarn. Subsequently, the infusibilized yarn was carbonized at a carbonization temperature of 650°C to obtain a fluid separation carbon membrane of Production Example 1, which is a carbon membrane for fluid separation having an outer diameter of 300 µm and an inner diameter of 100 µm.

[0117] Example 1 One fluid separation membrane of Production Example 1 was used as a core yarn, and a spacer polyester false twisted yarn of 170 dtex was spirally wound around it at a pitch of 1 cm.

[0118] One hundred fluid separation membranes of Production Example 1 wound with polyester false twist textured yarn were bundled and housed in an acrylic pipe (inner diameter 5 mm) with an inlet and outlet for the fluid to be separated, and one end of the acrylic pipe was statically potted with epoxy resin. After the epoxy resin hardened, the potted portion at one end was cut with a rotary saw to open the fluid separation membrane.

[0119] Next, a 10 wt % hexane solution (hereinafter referred to as PDMS solution) of polydimethylsiloxane (Silgard, manufactured by Toray DuPont Co., Ltd.) was injected through the inlet and outlet for the fluid to be separated. After the surface of the fluid separation membrane was thoroughly immersed in the PDMS solution, the Silgard solution was discharged through the inlet and outlet for the fluid to be separated, and after drying, the membrane was heated in an oven at 70°C for 30 minutes to form coating layers 1 to 3, thereby obtaining the fluid separation membrane module of Example 1.

[0120] The fluid separation membrane module of Example 1 has an F0 / L of 16.7, and has coating layers 1, 2, and 3 made of PDMS, which is silicone.

[0121] As a result of evaluation using the above-mentioned method, there was no breakage of the fluid separation membrane during module fabrication, the bending radius of the fluid separation membrane having coating layer 1 was 10 cm or less, and the water permeability of the fluid separation membrane having coating layer 1 was 1 μL / hr / m 2 / Pa or less, the thickness of the coating layer 3 was 100 μm, the membrane utilization efficiency of the module was "good", and the impact resistance of the module was "good".

[0122] Example 2 A fluid separation membrane module was produced in the same manner as in Example 1.

[0123] Next, an acrylic elastomer (Yutaka Make, BE-2) was injected into the inlet and outlet of the module for the fluid to be separated so as not to come into contact with the fluid separation membrane, and the acrylic elastomer was hardened on the surface of the potting area on the inside of the module, thereby forming a coating layer 3 made of acrylic elastomer on the surface of the potting area on the inside of the module, thereby obtaining the fluid separation membrane module of Example 2.

[0124] The fluid separation membrane module of Example 2 has an F0 / L of 16.7, and has coating layer 1 and coating layer 2 made of PDMS, which is silicone, and coating layer 3 made of PDMS, which is silicone, and an acrylic elastomer.

[0125] As a result of evaluation using the above-mentioned method, there was no breakage of the fluid separation membrane during module fabrication, the bending radius of the fluid separation membrane having coating layer 1 was 10 cm or less, and the water permeability of the fluid separation membrane having coating layer 1 was 1 μL / hr / m 2 / Pa or less, the thickness of the coating layer 3 was 50,000 μm, the membrane utilization efficiency of the module was "good", and the impact resistance of the module was "excellent".

[0126] Example 3 The outer surface of the fluid separation membrane of Preparation Example 1 was thoroughly immersed in a PDMS solution, then dried and heated in an oven at 70°C for 30 minutes to obtain a fluid separation membrane having a coating layer 1 made of PDMS, a silicone.

[0127] A bundle of 100 membranes was prepared, each consisting of a core thread of a fluid separation membrane with a PDMS layer on its surface and a spacer of 170 dtex polyester false-twisted yarn wound spirally at a pitch of 1 cm. The bundle was then housed in an acrylic pipe (inner diameter 5 mm) with an inlet and outlet for the fluids to be separated, and each end of the acrylic pipe was statically potted with epoxy resin. After the epoxy resin hardened, the potted area at one end was cut with a rotary saw to open the fluid separation membrane, yielding a fluid separation membrane module of Example 3.

[0128] The fluid separation membrane module of Example 3 has an F0 / L of 16.7 and has coating layer 1 made of PDMS, which is silicone, but does not have coating layer 2 or 3.

[0129] As a result of evaluation using the above-mentioned method, there was no breakage of the fluid separation membrane during module fabrication, the bending radius of the fluid separation membrane having coating layer 1 was 10 cm or less, and the water permeability of the fluid separation membrane having coating layer 1 was 1 μL / hr / m 2 / Pa or less, the membrane utilization efficiency of the module was "excellent," and the impact resistance of the module was "fair."

[0130] Example 4 A 170 dtex polyester false twist textured yarn was spirally wound around one core yarn of the fluid separation membrane of Production Example 1 at a pitch of 1 cm. The outer surface of the fluid separation membrane of Production Example 1 wrapped with the polyester false twist textured yarn was thoroughly immersed in a PDMS solution, dried, and heated in an oven at 70°C for 30 minutes to form coating layers 1 and 2 made of PDMS, a silicone.

[0131] One hundred of the resulting membranes were bundled together with the polyester false twisted yarn and housed in an acrylic pipe (inner diameter 5 mm) with an inlet and outlet for the fluid to be separated, and one end of the acrylic pipe was statically potted with epoxy resin. After the epoxy resin hardened, the potted portion at one end was cut with a rotary saw to open the fluid separation membrane, thereby obtaining the fluid separation membrane module of Example 4.

[0132] The fluid separation membrane module of Example 4 has an F0 / L of 16.7, and has coating layer 1 and coating layer 2 made of PDMS, which is silicone, but does not have coating layer 3.

[0133] As a result of evaluation using the above-mentioned method, there was no breakage of the fluid separation membrane during module fabrication, the bending radius of the fluid separation membrane having coating layer 1 was 10 cm or less, and the water permeability of the fluid separation membrane having coating layer 1 was 1 μL / hr / m 2 / Pa or less, the membrane utilization efficiency of the module was "good" and the impact resistance of the module was "fair".

[0134] Example 5 A fluid separation membrane module was produced in the same manner as in Example 4.

[0135] Next, an acrylic elastomer (Yutaka Make, BE-2) was injected into the inlet and outlet of the module for the fluid to be separated so as not to come into contact with the fluid separation membrane, and the acrylic elastomer was hardened on the surface of the potting area on the inside of the module, thereby forming a coating layer 3 made of acrylic elastomer on the surface of the potting area on the inside of the module, thereby obtaining the fluid separation membrane module of Example 5.

[0136] The fluid separation membrane module of Example 5 has an F0 / L of 16.7, and has coating layer 1 and coating layer 2 made of PDMS, which is silicone, and coating layer 3 made of an acrylic elastomer.

[0137] As a result of evaluation using the above-mentioned method, there was no breakage of the fluid separation membrane during module fabrication, the bending radius of the fluid separation membrane having coating layer 1 was 10 cm or less, and the water permeability of the fluid separation membrane having coating layer 1 was 1 μL / hr / m 2 / Pa or less, the thickness of the coating layer 3 was 100 μm, the membrane utilization efficiency of the module was "excellent", and the impact resistance of the module was "good".

[0138] (Production Example 2) Alumina with an average pore size of 100 nm to 250 nm, an outer diameter of 2 mm, and a length of 10 cm was used as a porous support, and the MOF ZIF-8 was synthesized on the surface as a gas separation functional layer. To synthesize ZIF-8, a methanol solution (0.4 mol / L) of zinc nitrate hexahydrate was prepared and applied to the outer surface of the porous support.

[0139] Next, a DMF solution (0.5 mol / L) of 2-methylimidazole was prepared and supplied to the inner cavity of the porous support and allowed to stand for 72 hours. After draining, the support was washed with methanol and dried to obtain a fluid separation membrane of Production Example 2.

[0140] Example 6 A fluid separation membrane module of Example 6 was obtained in the same manner as in Example 1, except that the fluid separation membrane of Production Example 2 was used instead of the fluid separation membrane of Production Example 1.

[0141] The fluid separation membrane module of Example 6 has an F0 / L of 16.7 and has coating layers 1, 2, and 3 made of PDMS, which is silicone.

[0142] As a result of evaluation using the above-mentioned method, there was no breakage of the fluid separation membrane during module fabrication, the bending radius of the fluid separation membrane with coating layer 1 was 100 cm or more, and the water permeability of the fluid separation membrane with coating layer 1 was 1 μL / hr / m 2 / Pa or less, the thickness of the coating layer 3 was 100 μm, the membrane utilization efficiency of the module was "good", and the impact resistance of the module was "good".

[0143] Example 7 A fluid separation membrane module of Example 7 was obtained in the same manner as in Example 1, except that a 7 dtex polyester textured yarn was used instead of the 170 dtex polyester false twist textured yarn used as the spacer.

[0144] The fluid separation membrane module of Example 7 has an F0 / L of 0.7 and has coating layers 1, 2, and 3 made of PDMS, which is silicone.

[0145] As a result of evaluation using the above-mentioned method, there was no breakage of the fluid separation membrane during module fabrication, the bending radius of the fluid separation membrane having coating layer 1 was 10 cm or less, and the water permeability of the fluid separation membrane having coating layer 1 was 1 μL / hr / m 2 / Pa or less, the thickness of the coating layer 3 was 100 μm, the membrane utilization efficiency of the module was "fair", and the impact resistance of the module was "fair".

[0146] Example 8 The fluid separation membrane module of Example 8 was obtained in the same manner as Example 1, except that one fluid separation membrane of Manufacturing Example 1 was used as the core yarn and a spacer 170 dtex polyester false twist textured yarn was wound spirally at a pitch of 1 cm, and the fluid separation membrane of Manufacturing Example 1 was aligned with the spacer 170 dtex polyester false twist textured yarn.

[0147] The fluid separation membrane module of Example 8 has F0 / L of 0 since L can be considered to be infinite, and has coating layer 1, coating layer 2 and coating layer 3 made of PDMS, which is silicone.

[0148] As a result of evaluation using the above-mentioned method, there was no breakage of the fluid separation membrane during module fabrication, the bending radius of the fluid separation membrane having coating layer 1 was 10 cm or less, and the water permeability of the fluid separation membrane having coating layer 1 was 1 μL / hr / m 2 / Pa or less, the thickness of the coating layer 3 was 100 μm, the membrane utilization efficiency of the module was "fair", and the impact resistance of the module was "fair".

[0149] (Comparative Example 1) One hundred fluid separation membranes of Production Example 1 were bundled and housed in an acrylic pipe (inner diameter 5 mm) with an inlet and outlet for the fluid to be separated, and one end of the acrylic pipe was statically potted with epoxy resin. After the epoxy resin hardened, the potted portion at one end was cut with a rotary saw to open the fluid separation membrane.

[0150] Next, a 10 wt% hexane solution (hereinafter referred to as PDMS solution) of polydimethylsiloxane (Silgard, manufactured by Toray DuPont Co., Ltd.) was injected through the inlet and outlet for the fluid to be separated. After the surface of the fluid separation membrane was thoroughly immersed in the PDMS solution, the Silgard solution was discharged through the inlet and outlet for the fluid to be separated, and after drying, the membrane was heated in an oven at 70°C for 30 minutes to form coating layer 1 and coating layer 3, thereby obtaining the fluid separation membrane module of Example 1.

[0151] The fluid separation membrane module of Comparative Example 1 has F0 / L of 0 because F0 can be considered to be 0, and has coating layer 1 and coating layer 3 made of PDMS, which is silicone, but does not have coating layer 2. Also, it has no spacers.

[0152] As a result of evaluation using the above-mentioned method, it was found that the fluid separation membrane was broken during module fabrication.

[0153] (Comparative Example 2) The outer surface of the fluid separation membrane of Preparation Example 1 was thoroughly immersed in a PDMS solution, dried, and heated in an oven at 70°C for 30 minutes to obtain a fluid separation membrane having a PDMS layer, which is coating layer 1, on its surface.

[0154] One hundred of the resulting fluid separation membranes having a PDMS layer on their surface were bundled and housed in an acrylic pipe (inner diameter 5 mm) with an inlet and outlet for the fluid to be separated, and one end of the acrylic pipe was statically potted with epoxy resin. After the epoxy resin hardened, the potted portion at one end was cut with a rotary saw to open the fluid separation membrane, yielding a fluid separation membrane module of Comparative Example 2.

[0155] The fluid separation membrane module of Comparative Example 2 has F0 / L of 0 because F0 can be considered to be 0, and has coating layer 1 made of PDMS, which is silicone, but does not have coating layer 2 or 3. Also, it has no spacers.

[0156] As a result of evaluation by the above-mentioned method, it was found that the fluid separation membrane was "broken" during module fabrication.

[0157] (Comparative Example 3) A fluid separation membrane module of Comparative Example 3 was obtained in the same manner as Comparative Example 1, except that the fluid separation membrane of Production Example 2 was used instead of the fluid separation membrane of Production Example 1.

[0158] The fluid separation membrane module of Comparative Example 3 has F0 / L of 0 because F0 can be considered to be 0, and has coating layer 1 and coating layer 3 made of PDMS, which is silicone, but does not have coating layer 2. Also, it has no spacers.

[0159] As a result of evaluation using the above-mentioned method, there was no breakage of the fluid separation membrane during module fabrication, the bending radius of the fluid separation membrane without coating layer 1 was 100 cm or more, and the water permeability of the fluid separation membrane without coating layer 1 was 1 μL / hr / m 2 / Pa or less, the thickness of the coating layer 3 was 100 μm, the membrane utilization efficiency of the module was "poor", and the impact resistance of the module was "good". [Explanation of symbols]

[0160] 1:Fluid separation membrane 2: Hollow part 3: Spacer 4: Coating layer 1 5: Coating layer 2 6: Coating layer 3 7: Potting area 8: Inlet / outlet for fluid to be separated 9: Inlet / outlet for permeating fluid 10: Vessel 11: Thickness of coating layer 3 12: Pitch

Claims

1. A fluid separation membrane module including a fluid separation membrane and a spacer, the spacer is a fiber, A coating layer 2 is provided on the surface of the spacer, At least a portion of the spacer is disposed between the membranes of the fluid separation membrane; The spacer is spirally wrapped around one of the fluid separation membranes. The fluid separation membrane has a coating layer 1 on at least a part of its surface, the coating layer 1 contains at least one compound selected from the group consisting of a fluororesin, a polystyrene, a silicone, a microporous polymer (PIM), a phenolic resin, and a urethane resin; A fluid separation membrane module, wherein the second coating layer has the same composition as the first coating layer.

2. 2. The fluid separation membrane module according to claim 1, wherein the fluid separation membrane is a gas separation membrane.

3. 3. The fluid separation membrane module according to claim 1, wherein the fluid separation membrane is an inorganic membrane.

4. 4. The fluid separation membrane module according to claim 1, wherein the fluid separation membrane having said coating layer 1 has a bending radius of 100 cm or less.

5. 5. The fluid separation membrane module according to claim 1, wherein the spacer is a false twist textured yarn.

6. The fluid separation membrane module according to claim 5 , wherein the total fineness and pitch of the spacers satisfy the following formula 1: 1 < F ０ / L < 100 ・・・Form 1 [In the formula, F ０ represents the total fineness of the spacer (unit: dtex), and L represents the spacer pitch (unit: mm).

7. the fluid separation membrane is fixed at a potting site; 7. The fluid separation membrane module according to claim 1, wherein a coating layer 3 is provided on the surface of the potting portion on the inner side of the fluid separation membrane module.

8. 8. The fluid separation membrane module according to claim 7, wherein the coating layer has a thickness of 10 μm or more and 50,000 μm or less.

9. The fluid separation membrane having the coating layer 1 has a water permeability of 100 μL / hr / m ２ The fluid separation membrane module according to any one of claims 1 to 8, wherein the viscosity is 1 / Pa or less.

10. A fluid separation membrane plant comprising the fluid separation membrane module according to any one of claims 1 to 9.

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