WO2023022084A1 - Fluid separation membrane - Google Patents

Fluid separation membrane Download PDF

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Publication number
WO2023022084A1
WO2023022084A1 PCT/JP2022/030525 JP2022030525W WO2023022084A1 WO 2023022084 A1 WO2023022084 A1 WO 2023022084A1 JP 2022030525 W JP2022030525 W JP 2022030525W WO 2023022084 A1 WO2023022084 A1 WO 2023022084A1
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Prior art keywords
particles
layer
separation membrane
particle layer
fluid
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PCT/JP2022/030525
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French (fr)
Japanese (ja)
Inventor
矢矧奈穂子
三原崇晃
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東レ株式会社
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Publication of WO2023022084A1 publication Critical patent/WO2023022084A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material

Definitions

  • the present invention relates to fluid separation membranes.
  • Membrane separation is used as a method for selectively separating and purifying specific components from various mixed gases and mixed liquids. Membrane separation is attracting attention because it is an energy-saving method compared to other fluid separation methods such as distillation.
  • Porous materials are used in various applications, and it is known that the pore diameter of the porous material affects the separation characteristics when used for separation membranes.
  • the pore diameter of the porous material affects the separation characteristics when used for separation membranes.
  • the surface of the porous material has coarse pores, defects such as pinholes are likely to occur in the separation functional layer formed on the surface. The yield of the separation membrane deteriorates.
  • the pores of the porous material are made denser, the membrane formability is improved, but there is a problem that the permeation resistance is increased and the performance of the separation membrane is lowered.
  • Patent Document 1 a particle layer consisting of an aggregate of silica spherical particles having a uniform particle diameter is adhered to the surface of a porous support, and a smooth surface is formed while controlling the pore diameter to obtain a pin.
  • Techniques have been proposed for forming a thin separation film without defects such as holes.
  • Patent Document 2 proposes a porous carbon fiber that is flexible and has excellent heat resistance and chemical resistance. There are expectations as a possible porous support layer.
  • an object of the present invention is to provide a porous material that is flexible, has excellent productivity, and can achieve both compressive strength and fluid diffusibility, and a fluid separation membrane that has high separation performance and long-term stability.
  • the present invention for solving the above problems has the following configuration.
  • a fibrous porous support layer having a surface coated with a separation functional layer, a particle layer interposed at least partially between the porous support layer and the separation functional layer, the particle layer comprising fibers
  • a fluid separation membrane containing shaped particles and/or tabular particles.
  • the present invention it is possible to provide a porous material that is flexible, excellent in productivity, and capable of achieving both compressive strength and fluid diffusibility. Moreover, by using the porous material of the present invention as a support, a fluid separation membrane with high separation performance and long-term stability can be provided.
  • the present invention has a fibrous porous support layer whose surface is coated with a separation functional layer, a particle layer interposed at least partially between the porous support layer and the separation functional layer, and the particles
  • a layer is a fluid separation membrane containing fibrous particles and/or tabular particles.
  • the porous material of the present invention has a porous support layer and a particulate layer.
  • the porous support layer in the porous material of the present invention is not particularly limited as long as it is porous, does not hinder the permeation of fluid, and has the function of supporting the particle layer, and conventionally known materials are appropriately selected.
  • materials suitable for the porous support layer include a material having closed cells derived from a sea-island structure, a material having a structure in which a plurality of particles are connected, and a fibrous material that is folded and appropriately Examples include materials such as bonded woven fabrics and non-woven fabrics, and materials having a continuous porous structure in which the voids and the substance constituting the support are continuous with each other.
  • these materials are appropriately selected from the viewpoint of exhibiting the function of supporting the separation functional layer without impeding the permeation of the fluid.
  • the voids and substances that make up the porous support layer are continuous with each other, and the curvature of the interface is lower than that of the porous support layer in which particles are connected, so fluid permeation is not hindered.
  • the material constituting the porous support layer has a high effect of dispersing stress, and as a result, the compressive strength is increased, which is more preferable.
  • the material of the porous support layer is not particularly limited, and conventionally known materials can be appropriately selected.
  • Materials include inorganic substances such as alumina, silica, cordierite, zirconia, titania, Vycor glass, zeolite, magnesia, carbon, sintered metals, polysulfone, polyethersulfone, polyamide, polyester, and cellulose-based polymers.
  • an organic material containing at least one polymer selected from the group consisting of homopolymers and copolymers such as vinyl polymer, polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfone, and polyphenylene oxide, and an organic material composed of a carbonizable resin.
  • Carbon materials and the like can be mentioned, and porous materials made of these materials can be used.
  • Carbonizable resins include, for example, polyphenylene oxide, polyvinyl alcohol, polyacrylonitrile, phenol resin, wholly aromatic polyester, unsaturated polyester resin, alkyd resin, melamine resin, urea resin, polyimide resin, diallyl phthalate resin, lignin resin, urethane resin, Resin etc. are mentioned. You may use 2 or more types of these.
  • the material constituting the porous support layer is preferably an inorganic material from the viewpoint of heat resistance, chemical resistance and mechanical strength. Since the chemical properties of the support layer are close to each other, the interfacial adhesion is excellent.
  • element A is the element that is present in the largest number on a numerical basis.
  • Element A constituting the porous support layer is preferably the same as the element B that constitutes the fibrous grains and/or tabular grains contained in the later-described grain layer.
  • the fibrous particles and/or tabular particles at the interface are It is preferable because it has good adhesiveness to the porous support layer, does not show breakage from the peeled portion of the porous material as a whole, and tends to improve strength.
  • a fibrous material is used as the porous support layer, but it is not particularly limited as long as it is fibrous, and it can be of any shape.
  • the shape of the fiber cross section is not limited at all, and can be any shape such as a round cross section, a multilobed cross section such as a triangular cross section, a flat cross section, or a hollow cross section.
  • the cross section of the porous support layer is a hollow cross section, that is, the porous support layer has a hollow fiber shape, pressure loss is suppressed and pressure resistance is improved when a fluid flows through the porous support layer. It is preferable because it becomes possible to have it.
  • the hollowness of the hollow fibers is preferably as high as possible because the pressure loss in the direction of the fiber axis is particularly reduced and the flow of fluid is not hindered, and as low as possible, the compressive strength in the cross-sectional direction of the fiber can be increased. From these points of view, the hollowness ratio capable of balancing both is preferably in the range of 10 to 90%, more preferably in the range of 20 to 60%.
  • the hollow portion of the hollow fiber may be formed singly or plurally.
  • the outer diameter of the hollow fiber is not particularly limited, and can be arbitrarily determined in consideration of strength, flexibility, etc. according to the application. Considering handling properties such as strength, the hollow fiber porous support layer preferably has an outer diameter of 0.02 mm or more, and from the viewpoint of flexibility, the hollow fiber porous support layer has an outer diameter of 50 mm or less. is preferred.
  • the porosity of the porous support layer is preferably 10% or more, more preferably 25% or more, because the larger the porosity, the more likely it is to reduce the pressure loss of the fluid and secure a plurality of highly efficient flow paths.
  • the porosity is preferably 80% or less, more preferably 70% or less.
  • the porosity of the porous support layer is defined by setting a region of interest necessary for calculation from an image observed with a three-dimensional microscope, with A being the volume of the region of interest, and B being the volume of voids in the region of interest. , which is calculated by the following formula.
  • Porosity (%) B/A x 100
  • the three-dimensional microscopic imaging is not particularly limited as long as the solid portion and the void portion that constitute the porous support layer can be separated and observed. It is preferable to appropriately select an analysis method that can separate, observe, and analyze the solid part and the void part as electronic information, such as & view, a method of applying computed tomography using a transmission type X-ray or an electron microscope. . At this time, when the electron beam contrast between the solid portion and the void portion was weak and observation was difficult, the observation was performed after performing electron staining using an appropriate heavy metal or the like.
  • the particle layer in the porous material of the present invention has a state in which it is arranged so as to be in contact with at least a portion of the porous support layer, and is defined as an intervening state.
  • the shape of the particle layer is not particularly limited, and may be any shape such as cylindrical, linear, helical, spherical, or block-like. It is preferable because it is easy to disperse and maintain high pressure resistance.
  • the particle layer is not particularly limited as long as it is in contact with a part of the porous support layer.
  • a form in which the entire surface of one surface of the porous support layer is coated with a particle layer is also one of the preferred embodiments, since the diffusibility can be ensured.
  • the phrase “the particle layer is arranged so as to be in contact with at least a portion of the porous support layer” refers to a state in which the particle layer is in contact with at least a portion of the surface of the porous support layer.
  • the particle layer can cover the entire surface of the porous support layer, cover only one surface, or cover only a part of the surface.
  • the porous material has a separation function layer, which will be described later, it is preferable that the surface of the porous support layer on the side where the separation function layer is formed is covered with the particle layer.
  • the particle layer is a layer mainly composed of particles.
  • the layer mainly composed of particles means that the total volume of fibrous particles and tabular particles is 5% or more when the volume of the layer excluding voids is taken as 100%.
  • the portion other than the fibrous grains and/or the tabular grains in the grain layer is not particularly limited, but other grains, that is, grains other than the fibrous grains and tabular grains described later (grains having an aspect ratio of less than 10) ) or a binder resin may be contained in the particle layer.
  • the binder resin is not particularly limited as long as it has a function of bonding particles together, and conventionally known materials can be appropriately selected.
  • the particle layer may contain an inorganic material or an organic material that constitutes the separation functional layer.
  • the total volume fraction of fibrous particles and tabular particles is large, entanglement between particles easily occurs, which is preferable because it is possible to prevent peeling and destruction in the particle layer, between the particle layers, and between the particle layer and the porous support layer.
  • the total volume occupied by the fibrous particles and the tabular particles is 97% or more and 100% or less, it is particularly easy to form pores, the fluid permeation resistance can be effectively reduced, and from the viewpoint of the permeability of the fluid separation membrane. preferable.
  • the pore diameter of the particle layer surface can be easily controlled. There is an effect that the fluid separation membrane to be formed is excellent in film formability. From the above viewpoints, it is also preferable that the total volume occupied by fibrous grains and tabular grains is 20% or more and less than 97%.
  • the volume occupied by fibrous particles and tabular particles in the layer is analyzed by extracting a three-dimensional image as electronic information using a measurement method that can grasp the three-dimensional shape, such as three-dimensional microscopic photography.
  • a measurement method that can grasp the three-dimensional shape, such as three-dimensional microscopic photography.
  • an analysis method that enables separation, observation and analysis as electronic information.
  • the observation was performed after performing electron dyeing using a suitable heavy metal or the like.
  • the fibrous grains and/or tabular grains taken out were separated by an appropriate technique, and the least squares method was applied to each grain to approximate them as an ellipsoid.
  • the volume occupied by fibrous particles and tabular particles was calculated as the volume fraction of particles having an aspect ratio of 10 or more by setting a volume in which the number of particles of interest exceeds 200 as an observed three-dimensional image.
  • the particle layer of the present invention contains fibrous particles and/or tabular particles.
  • the fibrous grains and/or tabular grains of the present invention mean grains having an aspect ratio of 10 or more.
  • the fibrous particles are the three diameters of the ellipsoid obtained from the particles (three diameters perpendicular to each other through the center of the ellipsoid), where Lb is the length of the shortest diameter, and the aspect When the diameter with a ratio of 10 or more is taken as the major diameter, it refers to particles having one major diameter.
  • Tabular grains refer to grains having two major diameters, where the major diameter is defined as a diameter having an aspect ratio of 10 or more with respect to Lb.
  • the three diameters are measured from the three-dimensional data of one particle in the particle layer, taken out as digital data by a measurement method that can grasp the three-dimensional shape, such as three-dimensional microscopic photography, and the shortest diameter
  • the aspect ratio is the ratio (La/Lb) of the length Lb of the diameter to the length La of the longest diameter.
  • the aspect ratio of fibrous particles and/or tabular particles is obtained by taking 10 arbitrary particles from particles having La/Lb of 10 or more and taking the ratio of Lb and La (La/Lb) of each particle, The average value of 10 points is calculated as the aspect ratio of fibrous grains and/or tabular grains.
  • the longest length Ll of the fibrous grains and/or tabular grains is calculated as the average value of La of the 10 grains selected when the aspect ratio is calculated.
  • the shortest length Ls of fibrous grains and/or tabular grains is calculated as an average value of Lb values of 10 grains selected when calculating the aspect ratio.
  • Ll is preferably 0.05 ⁇ m or more and 1000 ⁇ m or less, more preferably 1 ⁇ m or more and 100 ⁇ m or less.
  • the interface between the support layer and the fibrous particles and/or tabular particles is formed, the adhesion between the fibrous particles and/or tabular particles and the porous support layer at the interface is good, and the porous material As a whole, no breakage from the exfoliated portion is observed, and the strength tends to be improved, which is preferable.
  • the aspect ratio of fibrous grains and/or tabular grains in the grain layer is preferably in the range of 20-10,000, more preferably in the range of 100-2000.
  • the fraction of fibrous particles and/or tabular particles is not particularly limited, but since fibrous particles easily form pores and are advantageous from the viewpoint of fluid diffusibility, A high volume fraction of fibrous particles is preferred.
  • the fibrous particles and/or tabular particles preferably contain at least one selected from the group consisting of cellulose nanofibers, carbon nanohorns, carbon nanoribbons, carbon nanotubes, graphene, and graphene oxide. This point will be explained below.
  • the fibrous particles constituting the particle layer of the present invention have a property that the fibrous particles tend to be oriented in the flow direction of the liquid when the particle layer is molded, particularly when a step of coating with a liquid is employed.
  • the orientation of the fibrous particles is preferable because it exhibits reinforcing properties in a specific direction, particularly in the direction of the fiber axis, and improves the bending rigidity in the direction orthogonal to the fiber axis.
  • Additives having fibrous shapes that are candidates for fibrous particles include, for example, whiskers, cellulose nanofibers, carbon nanohorns, carbon nanoribbons, and carbon nanotubes. Nanofibers, carbon nanohorns, carbon nanoribbons, and carbon nanotubes are preferred.
  • the tabular particles constituting the particle layer of the present invention have the property that the tabular particles tend to be plane-oriented in the flow direction of the liquid when forming the particle layer, particularly when a process of coating with a liquid is employed. , and when the orientation direction is the MD direction, it is preferable because it tends to exhibit reinforcing properties in the MD direction and the TD direction.
  • Additives having a tabular shape that are candidates for tabular particles include, for example, graphene, graphene oxide, talc, and mica. Considering the preferred range of Ls described later, graphene and graphene oxide are preferred.
  • the material of the particles is not particularly limited as long as the above effects can be exhibited, and may contain carbon, oxygen, nitrogen, boron, sulfur, silicon, etc., and may contain alkali metals, alkaline earth metals, etc. .
  • the fibrous particles and/or tabular particles of the present invention may be used singly or in combination of two or more.
  • other particles that is, particles having an aspect ratio of less than 10 may be contained within the range that does not impair the purpose of the present invention.
  • the size of the fibrous particles and/or tabular particles in the particle layer is not particularly limited, but the shortest length Ls of the fibrous particles and/or tabular particles is preferably 0.4 nm or more and 10 ⁇ m or less.
  • Ls is 0.4 nm or more
  • Ls is 10 ⁇ m or less
  • the specific surface area is large and the adhesiveness to the porous support layer is good, and the strength of the porous material is improved.
  • the surface of the particle layer formed so that the portions are in contact with each other is easily smoothed, and when used as a fluid separation membrane, the separation functional layer can be formed more easily, which is preferable. From the above viewpoint, it is more preferable that the length Ls of the shortest diameter of the particles is 1 nm or more and 100 nm or less.
  • the porosity of the particle layer is not particularly limited, it is preferably 3% or more, more preferably 5% or more, because if it is small, the adhesion between particles increases and the peeling resistance improves. Also, if the porosity is large, the pressure loss to the fluid can be reduced, so it is preferably 50% or less, more preferably 30% or less.
  • the porosity of the particle layer is defined by setting a region of interest necessary for calculation from an image observed with a three-dimensional microscope, and taking the volume of the region of interest as A and the volume of voids in the region of interest as B, as follows: It is calculated by the formula of
  • Porosity (%) B/A x 100
  • Three-dimensional microscopic imaging is not particularly limited as long as it is possible to separate and observe the solid part and the void part that make up the particle layer.
  • an analysis method capable of separating, observing, and analyzing the solid portion and the void portion as electronic information such as a method of applying computed tomography using a transmission type X-ray or an electron microscope.
  • the observation was performed after performing electron staining using an appropriate heavy metal or the like.
  • data with 10 or more particles in the data is used, and when 10 or more particles do not exist in one data, data obtained from another observation field are added and totaled A particle layer containing 10 or more particles is observed to determine the volume %.
  • the thickness of the particle layer of the present invention is not particularly limited, but the thicker the layer, the more resistant it is to damage due to external force, and the better the durability. It is preferable because From these viewpoints, the thickness of the particle layer is preferably in the range of 0.2 ⁇ m to 100 ⁇ m, more preferably in the range of 0.5 ⁇ m to 10 ⁇ m.
  • the thickness of the particle layer is defined by measuring the thickness of the thinnest portion constituting the particle layer with a microscope or the like when a cross section for observation is formed from the porous material. is calculated as the average value of the analyzed thickness.
  • the fluid separation membrane of the present invention is a fluid separation membrane comprising a separation functional layer and the porous material of the present invention, characterized in that the particle layer and the separation functional layer are arranged so as to be in contact with each other.
  • the porous material ensures fluid diffusibility and durability, prevents breakage during actual use, enables stable operation for a long period of time, and even when high pressure is applied.
  • the porous support layer and the particle layer each disperse the stress, and the porous material as a whole exerts the effect of bearing the pressure, making it possible to operate in a high-pressure environment.
  • the separation functional layer suitably combined with the porous material of the present invention is in contact with the particle layer of the porous material.
  • the separation functional layer in contact with the particle layer can efficiently disperse the internal stress in the particle layer when subjected to an external force such as pressure, so that the pressure resistance can be improved.
  • external force such as pressure
  • external force such as bending
  • an effect of suppressing separation between the particle layer and the separation functional layer can be expected.
  • the separation function layer is not particularly limited as long as it is a material having a fluid separation function, and conventionally known organic materials and inorganic materials can be appropriately selected.
  • Organic materials are not particularly limited, but examples include aromatic polyimide, cellulose acetate, polysulfone, aromatic polyamide, polyamideimide, polyetherimide, polyethersulfone, polyacrylonitrile, polyphenylene sulfide, polyphenylene oxide, polyetheretherketone, polytetra Fluoroethylene, polyvinylidene fluoride, poly(1-trimethylsilylpropyne), polydimethylsiloxane, polyvinyltrimethylsilane, poly(4-methylpentene), ethyl cellulose, natural rubber, poly(2,6-dimethylphenylene oxide), low density
  • Various polyethers such as polyethylene, high-density polyethylene, styrene, polyethyl methacrylate, polycarbonate, polyester, aliphatic polyamide
  • the separation functional layer When the separation functional layer is made of an inorganic material, it tends to have high heat resistance and chemical resistance, and the separation performance of the fluid separation membrane can be exhibited stably over a long period of time.
  • the inorganic material is not particularly limited, examples thereof include carbon materials, zeolite, silica, and metal-organic structures using the above organic materials as precursors.
  • the separation functional layer is preferably a carbide having an organic material as a precursor. Examples include those obtained by firing materials. It is particularly preferable to select phenol resin, polyacrylonitrile, polyimide, and the like.
  • the material of the separation functional layer is not particularly limited, but the carbon element ratio is preferably 70 atomic % or more and 99.5 atomic % or less.
  • the higher the carbon element ratio X in the matrix the better the film performance, chemical resistance, and heat resistance.
  • the lower the carbon content the more flexible and resistant to breakage, and the longer the durability is improved. Therefore, the carbon element ratio X of the matrix is more preferably 92 atomic % or less.
  • Constituent elements other than carbon in the separation functional layer are not particularly limited, and may contain hydrogen, oxygen, nitrogen, boron, sulfur, silicon and the like, and may also contain alkali metals, alkaline earth metals and the like. The above element ratios can be analyzed using energy dispersive X-ray spectroscopy combined with electron microscopy.
  • the elastic modulus of the separation functional layer is preferably 10 GPa or more and 300 GPa or less. Due to the high elastic modulus of the separation function layer, the effect of preventing destruction of the separation function layer is exhibited, so the effect of preventing breakage during operation as a gas separation membrane and enabling stable use for a long period of time. can get. On the other hand, the lower the modulus of elasticity, the more flexible the deformation, so that the momentary impact force can be alleviated.
  • the elastic modulus is determined by various analytical methods, and can be analyzed using a method of calculating elastic modulus using Hertz's contact theory in the nanoindentation method.
  • the separation functional layer is in a form in which a part of the inorganic material or organic material constituting the separation functional layer is combined with a particle layer of a porous material, an external force such as pressure or bending is applied as a fluid separation membrane. It is preferable because the effect of suppressing peeling at the time can be enhanced. In addition, it is preferable that the number of composites is as small as possible because the diffusion of the fluid in the particle layer can be maintained at a high level. From these points of view, the composite ratio of the separation functional layer is preferably in the range of 1% or more and 50% or less because both are excellent in balance, and more preferably 10% or more and 40% or less.
  • the composite ratio of the separation functional layer is defined by setting a region of interest necessary for calculation from an image observed with a three-dimensional microscope, and determining the volume Vm of the separation functional layer in the region of interest, the volume of the particles constituting the particle layer, and the Vp and the volume Va of the void are calculated by the following formula.
  • Composite ratio (%) of separation functional layer (Vm/(Vm+Vp+Va)) ⁇ 100
  • Three-dimensional microscopic photography is not particularly limited as long as it is possible to separate the solid part and the void part that constitute the particle layer, and further separate the solid part from the particles and the separation function layer, and observe it.
  • the separation function layer, particles, and voids are separated as electronic information, such as slice & view, which is continuously observed with a scanning electron microscope, and a method of applying computed tomography using a transmission type X-ray or electron microscope. It is preferable to appropriately select an analysis method that allows observation and analysis.
  • the pore diameter of the separation functional layer can be appropriately selected according to the object to be separated.
  • the pore diameter is preferably between 1 nm and 10 ⁇ m.
  • the pore diameter of the separation functional layer as a preferred form is preferably 0.2 nm to 2 nm.
  • the fluid separation membrane that combines the porous material and the separation functional layer of the present invention is fibrous, but has advantages such as a larger membrane area per unit volume than a film.
  • advantages such as a larger membrane area per unit volume than a film.
  • the resistance to the force applied in the cross-sectional direction is increased, it is possible to operate at high pressure, and it is possible to perform membrane separation with high efficiency, which is preferable.
  • the cross-sectional shape of the fibers of the fluid separation membrane of the present invention is not limited at all, and can be any shape such as a circular cross-section, a multi-lobed cross-section such as a triangular cross-section, a flat cross-section or a hollow cross-section.
  • the cross section of the fluid separation membrane is a hollow cross section, that is, when the fluid separation membrane has a hollow fiber shape, it is possible to provide pressure resistance while controlling the flow of the supplied fluid and the fluid after separation. preferred because it is possible.
  • the hollow area ratio is preferably in the range of 5 to 70%.
  • the cross-sectional area Y of the hollow fiber is a cross-sectional area including the cross-sectional area X of the hollow portion.
  • a plurality of hollow portions may be provided, and in that case, the total cross-sectional area of the hollow portions is defined as the cross-sectional area X of the hollow portions.
  • a porous support layer is brought into contact with a slurry solution containing fibrous particles and/or tabular particles, and the outer surface of the porous support layer is coated with fibrous particles and/or It is preferred to include the step of forming a grain layer containing tabular grains.
  • methods for bringing the slurry into contact include dip coating, spray coating, nozzle coating, liquid film transfer, and the like, and can be appropriately selected according to the type of slurry solution.
  • a suitable solvent and dispersant can be used for the slurry solution.
  • the method for producing the fluid separation membrane of the present invention preferably includes a step of coating the porous material of the present invention with a solution containing the material of the fluid separation membrane and/or the precursor of the fluid separation membrane.
  • Coating methods include, for example, dip coating, spray coating, nozzle coating, and liquid film transfer, and can be appropriately selected according to the material of the fluid separation membrane.
  • a suitable solvent and additive can be used at the time of coating.
  • the separation membrane module of the present invention is a separation membrane module having the fluid separation membrane of the present invention in a case, and more specifically, it has a form in which the fluid separation membrane of the present invention is housed in the case.
  • the separation membrane module controls the flow of fluid and has a flow path for guiding the fluid that has permeated the fluid separation membrane.
  • the material of the case is not particularly limited, but it is preferably selected appropriately according to the usage environment such as pressure resistance and heat resistance, and examples thereof include metal, resin, carbon, and composites thereof.
  • the gas separation process to which the separation membrane module of the present invention can be applied is not particularly limited, but high separation performance and long-term stability are required by placing the separation membrane module of the present invention in at least a part of the process.
  • the separation membrane module of the present invention is placed in at least part of the process.
  • Processes that require high separation performance and long-term stability include, for example, carbon dioxide separation and storage systems from the exhaust gas of power plants and blast furnaces, and removal of sulfur components from gasified fuel gas in integrated coal gasification combined cycle. , refining of biogas and natural gas, and refining of hydrogen from organic hydrides.
  • a method for producing a fluid that at least partly uses such a gas separation process may include another purification step or an additional step before or after the purification step in the separation membrane module of the present invention. may be mixed with a purified fluid to produce a fluid.
  • Alternative or different purification steps include, for example, distillation, adsorption, absorption, and the like.
  • component adjustment etc. which mix with another fluid are mentioned, for example.
  • the fluid obtained by the production method of the present invention is purified by the separation membrane module of the present invention that achieves both high separation performance and long-term stability, the energy consumption in the additional steps is suppressed, and the environmental load is low. It can be suitably used in various industrial applications as a fluid.
  • the gas permeation rate Q was calculated by the following formula. Also, the ratio of the gas permeation rates Q of the respective components was defined as the separation factor ⁇ .
  • the membrane area was calculated from the outer diameter and length of the region contributing to gas permeation.
  • Gas permeation rate Q [permeation gas amount (mol)] / [membrane area (m 2 ) x time (s) x pressure difference (Pa) “High” when the gas transmission rate Q of carbon dioxide is 30 nmol/(m 2 ⁇ Pa ⁇ s) or more, and 30 nmol/(m 2 ⁇ Pa) when the gas transmission rate Q is 20 nmol/(m 2 ⁇ Pa ⁇ s) or more ⁇ s), it was judged to be "middle”, and when the gas permeation rate Q was less than 20 nmol/(m 2 ⁇ Pa ⁇ s), it was judged to be "low”.
  • the obtained precursor of the porous carbon film was passed through an electric furnace at 250° C. and heated in an air atmosphere for 1 hour to be infusible, thereby obtaining an infusible thread.
  • the infusible yarn was carbonized at a carbonization temperature of 650° C. to obtain a porous support layer of Production Example 1 having an outer diameter of 0.3 mm, a hollow area ratio of 44%, and a porosity of 48%.
  • Example 1 After applying a slurry of carbon nanotubes (CNT) to the porous support layer of Production Example 1 by dip coating, it is dried at 50 ° C. for 12 hours using a circulation dryer, and is applied to the outer surface of the porous support layer.
  • a porous material was continuously produced with a layer of carbon nanotube (CNT) particles attached. As a result of evaluation by the method described above, no peeling was observed at the interface between the porous support layer and the particle layer.
  • An aromatic polyimide solution was applied to the obtained porous material by dip coating, the solvent was removed, and then dried at 50° C. for 12 hours in a circulating dryer to apply the aromatic polyimide to the surface of the particle layer of the porous material. A film was formed. Subsequently, the porous material coated with the aromatic polyimide was baked at 700° C. in a nitrogen atmosphere to continuously produce a fluid separation membrane.
  • the ratio of fibrous grains and/or tabular grains (percentage of grains with an aspect ratio of 10 or more in the total of grains with an aspect ratio of 10 or more and grains with an aspect ratio of less than 10) is 98% by volume
  • the fibrous particles and/or tabular particles have an aspect ratio of 1623
  • the longest length Ll is 21.9 ⁇ m
  • the shortest length Ls is 14 nm
  • the thickness of the particle layer is 1.0 ⁇ m
  • the porosity of the particle layer was 28%.
  • the carbon element ratio of the separation functional layer was 83.4 atomic %
  • the elastic modulus of the separation functional layer was 28 GPa
  • the composite ratio of the separation functional layer and the particle layer was 24 volume %.
  • Example 2 In the same manner as in Example 1, except that the slurry of carbon nanotubes (CNT) in Example 1 was replaced with a slurry in which carbon nanotubes (CNT) and carbon black (CB) were mixed at a volume ratio of 9:1. A fluid separation membrane of Example 2 was fabricated.
  • the proportion of fibrous particles and/or tabular particles was 91% by volume
  • the aspect ratio of fibrous particles and/or tabular particles was 1590
  • the longest length Ll was 11.2 ⁇ m
  • the shortest length The thickness Ls was 7 nm
  • the thickness of the particle layer was 0.8 ⁇ m
  • the porosity of the particle layer was 22%.
  • the carbon element ratio of the separation functional layer was 83.4 atomic %
  • the elastic modulus of the separation functional layer was 26 GPa
  • the composite ratio of the separation functional layer and the particle layer was 21 volume %.
  • Example 3 was prepared in the same manner as in Example 1 except that instead of the carbon nanotube (CNT) slurry in Example 1, a slurry in which carbon nanotubes (CNT) and graphene were mixed at a volume ratio of 1:1 was used. A fluid separation membrane was fabricated.
  • CNT carbon nanotube
  • the proportion of fibrous particles and/or tabular particles was 98% by volume
  • the aspect ratio of fibrous particles and/or tabular particles was 1114
  • the longest length Ll was 9.6 ⁇ m
  • the shortest length The thickness Ls was 9 nm
  • the thickness of the particle layer was 0.9 ⁇ m
  • the porosity of the particle layer was 26%.
  • the separation functional layer had a carbon element ratio of 83.6 atomic %, an elastic modulus of the separation functional layer of 27 GPa, and a composite ratio of the separation functional layer and the particle layer of 21 volume %.
  • Example 4 In the same manner as in Example 1, except that instead of the carbon nanotube (CNT) slurry in Example 1, a slurry in which carbon nanotubes (CNT) and carbon black (CB) were mixed at a volume ratio of 1:4 was used. A fluid separation membrane of Example 4 was prepared. As a result of evaluation by the above-described method, the proportion of fibrous particles and/or tabular particles was 18% by volume, the aspect ratio of fibrous particles and/or tabular particles was 1756, the longest length Ll was 13.4 ⁇ m, and the shortest length was 13.4 ⁇ m.
  • the thickness Ls was 8 nm, the thickness of the particle layer was 0.9 ⁇ m, and the porosity of the particle layer was 4%. Further, the carbon element ratio of the separation functional layer was 83.5 atomic %, the elastic modulus of the separation functional layer was 22 GPa, and the composite ratio of the separation functional layer and the particle layer was 16 volume %.
  • Example 5 A fluid separation membrane of Example 5 was produced in the same manner as in Example 1, except that carbon nanotubes (CNT) having a large aspect ratio were used in the carbon nanotube (CNT) slurry of Example 1.
  • the ratio of fibrous particles and/or tabular particles was 99% by volume
  • the aspect ratio of fibrous particles and/or tabular particles was 2592
  • the longest length Ll was 24.1 ⁇ m
  • the shortest length The thickness Ls was 9 nm
  • the thickness of the particle layer was 0.8 ⁇ m
  • the porosity of the particle layer was 35%.
  • the carbon element ratio of the separation functional layer was 83.4 atomic %
  • the elastic modulus of the separation functional layer was 28 GPa
  • the composite ratio of the separation functional layer and the particle layer was 22 volume %.
  • Example 6 A fluid separation membrane of Example 5 was produced in the same manner as in Example 1, except that carbon nanotubes (CNT) having a large aspect ratio were used in the carbon nanotube (CNT) slurry of Example 1.
  • the proportion of fibrous particles and/or tabular particles was 98% by volume
  • the aspect ratio of fibrous particles and/or tabular particles was 11040
  • the longest length Ll was 121.5 ⁇ m
  • the shortest length was 121.5 ⁇ m.
  • the thickness Ls was 11 nm
  • the thickness of the particle layer was 1.0 ⁇ m
  • the porosity of the particle layer was 54%.
  • the carbon element ratio of the separation functional layer was 83.3 atomic %
  • the elastic modulus of the separation functional layer was 25 GPa
  • the composite ratio of the separation functional layer and the particle layer was 29 volume %.
  • Example 7 was prepared in the same manner as in Example 1 except that a slurry in which graphene and carbon black (CB) were mixed at a volume ratio of 9:1 was used instead of the carbon nanotube (CNT) slurry in Example 1. A fluid separation membrane was fabricated.
  • CB graphene and carbon black
  • the proportion of fibrous particles and/or tabular particles was 92% by volume
  • the aspect ratio of fibrous particles and/or tabular particles was 718
  • the longest length Ll was 2.8 ⁇ m
  • the shortest length The thickness Ls was 4 nm
  • the thickness of the particle layer was 0.7 ⁇ m
  • the porosity of the particle layer was 18%.
  • the carbon element ratio of the separation functional layer was 83.5 atomic %
  • the elastic modulus of the separation functional layer was 24 GPa
  • the composite ratio of the separation functional layer and the particle layer was 14 volume %.
  • Example 8 was prepared in the same manner as in Example 1 except that a slurry in which graphene and carbon black (CB) were mixed at a volume ratio of 9: 1 was used instead of the carbon nanotube (CNT) slurry in Example 1. A fluid separation membrane was fabricated.
  • CB graphene and carbon black
  • the ratio of fibrous particles and/or tabular particles was 92% by volume
  • the aspect ratio of fibrous particles and/or tabular particles was 92
  • the longest length Ll was 0.8 ⁇ m
  • the shortest length The thickness Ls was 9 nm
  • the thickness of the particle layer was 0.8 ⁇ m
  • the porosity of the particle layer was 19%.
  • the carbon element ratio of the separation functional layer was 83.6 atomic %
  • the elastic modulus of the separation functional layer was 22 GPa
  • the composite ratio of the separation functional layer and the particle layer was 17 volume %.
  • Example 9 was prepared in the same manner as in Example 1 except that a slurry in which graphene and carbon black (CB) were mixed at a volume ratio of 9: 1 was used instead of the carbon nanotube (CNT) slurry in Example 1. A fluid separation membrane was fabricated.
  • CB graphene and carbon black
  • the proportion of fibrous particles and/or tabular particles was 90% by volume
  • the aspect ratio of fibrous particles and/or tabular particles was 18, the longest length Ll was 0.3 ⁇ m, and the shortest length
  • the thickness Ls was 17 nm
  • the thickness of the particle layer was 0.8 ⁇ m
  • the porosity of the particle layer was 22%.
  • the carbon element ratio of the separation functional layer was 83.5 atomic %
  • the elastic modulus of the separation functional layer was 19 GPa
  • the composite ratio of the separation functional layer and the particle layer was 20 volume %.
  • Example 10 A fluid separation membrane of Example 10 was produced in the same manner as in Example 1, except that the carbon nanotube (CNT) particle layer was applied so as to be thin.
  • CNT carbon nanotube
  • the proportion of fibrous particles and/or tabular particles was 98% by volume
  • the aspect ratio of fibrous particles and/or tabular particles was 1710
  • the longest length Ll was 26.6 ⁇ m
  • the shortest length The thickness Ls was 16 nm
  • the thickness of the particle layer was 0.4 ⁇ m
  • the porosity of the particle layer was 25%.
  • the carbon element ratio of the separation functional layer was 83.3 atomic %
  • the elastic modulus of the separation functional layer was 30 GPa
  • the composite ratio of the separation functional layer and the particle layer was 24 volume %.
  • Example 11 A fluid separation membrane of Example 11 was produced in the same manner as in Example 1, except that the carbon nanotube (CNT) particle layer was applied so as to be thin.
  • the ratio of fibrous particles and/or tabular particles was 100% by volume
  • the aspect ratio of fibrous particles and/or tabular particles was 1674
  • the longest length Ll was 24.3 ⁇ m
  • the shortest length The thickness Ls was 15 nm
  • the thickness of the particle layer was 0.1 ⁇ m
  • the porosity of the particle layer was 18%.
  • the carbon element ratio of the separation functional layer was 83.4 atomic %
  • the elastic modulus of the separation functional layer was 28 GPa
  • the composite ratio of the separation functional layer and the particle layer was 26 volume %.
  • Example 12 A fluid separation membrane of Example 12 was produced in the same manner as in Example 1, except that the carbon nanotube (CNT) particle layer was coated so as to be thick.
  • the proportion of fibrous particles and/or tabular particles was 98% by volume
  • the aspect ratio of fibrous particles and/or tabular particles was 1534
  • the longest length Ll was 19.8 ⁇ m
  • the shortest length The thickness Ls was 13 nm
  • the thickness of the particle layer was 12.4 ⁇ m
  • the porosity of the particle layer was 28%.
  • the carbon element ratio of the separation functional layer was 83.2 atomic %
  • the elastic modulus of the separation functional layer was 27 GPa
  • the composite ratio of the separation functional layer and the particle layer was 22 volume %.
  • Example 13 A fluid separation membrane of Example 13 was produced in the same manner as in Example 1, except that the carbon nanotube (CNT) particle layer was coated so as to be thick.
  • the proportion of fibrous particles and/or tabular particles was 95% by volume
  • the aspect ratio of fibrous particles and/or tabular particles was 1552
  • the longest length Ll was 20.6 ⁇ m
  • the shortest length The thickness Ls was 13 nm
  • the thickness of the particle layer was 107.3 ⁇ m
  • the porosity of the particle layer was 30%.
  • the carbon element ratio of the separation functional layer was 83.5 atomic %
  • the elastic modulus of the separation functional layer was 28 GPa
  • the composite ratio of the separation functional layer and the particle layer was 20 volume %.
  • Example 14 A fluid separation membrane of Example 14 was produced in the same manner as in Example 1, except that the porous material coated with the aromatic polyimide was used as the fluid separation membrane as it was without being baked at 700° C. in a nitrogen atmosphere.
  • the ratio of fibrous particles and/or tabular particles was 99% by volume
  • the aspect ratio of fibrous particles and/or tabular particles was 1662
  • the longest length Ll was 19.5 ⁇ m
  • the shortest length was 19.5 ⁇ m.
  • the thickness Ls was 12 nm
  • the thickness of the particle layer was 0.9 ⁇ m
  • the porosity of the particle layer was 28%.
  • the carbon element ratio of the separation functional layer was 75.6 atomic %
  • the elastic modulus of the separation functional layer was 4 GPa
  • the composite ratio of the separation functional layer and the particle layer was 20 volume %.
  • Comparative Example 1 A fluid separation membrane of Comparative Example 1 was produced in the same manner as in Example 1, except that a carbon black (CB) slurry was used instead of the carbon nanotube (CNT) slurry of Example 1.
  • CB carbon black
  • CNT carbon nanotube
  • the ratio of fibrous particles and/or tabular particles was 0% by volume
  • the thickness of the particle layer was 0.8 ⁇ m
  • the porosity of the particle layer was 6%.
  • the carbon element ratio of the separation functional layer was 83.4 atomic %
  • the elastic modulus of the separation functional layer was 20 GPa
  • the composite ratio of the separation functional layer and the particle layer was 28 volume %.
  • Comparative Example 2 A fluid separation membrane of Comparative Example 2 was produced in the same manner as in Example 1, except that the slurry of spherical silica fine particles was used in place of the slurry of carbon nanotubes (CNT) of Example 1.
  • the ratio of fibrous particles and/or tabular particles was 0% by volume, the thickness of the particle layer was 1.0 ⁇ m, and the porosity of the particle layer was 25%. Further, the carbon element ratio of the separation functional layer was 83.2 atomic %, the elastic modulus of the separation functional layer was 23 GPa, and the composite ratio of the separation functional layer and the particle layer was 16 volume %. Delamination was observed at the interface between the porous support layer and the particle layer in the porous material, and the delamination frequency was 35 locations/m. The fluid separation membrane of Comparative Example 2 did not function as a fluid separation membrane because separation between the porous material and the separation functional layer was observed. The evaluation results are also shown in Table 2.
  • the fluid separation membrane of the present invention is used for 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, purification of biogas and natural gas. , hydrogen purification from organic hydride, and the like.

Abstract

The present invention provides a fluid separation membrane which has a fibrous porous support layer coated on the surface with a separation function layer, a particle layer being at least partially interposed between the porous support layer and the separation function layer, and the particle layer containing fibrous particles and/or plate-shaped particles. The present invention can provide a fluid separation membrane having high separation performance and long-term stability.

Description

流体分離膜fluid separation membrane
　本発明は、流体分離膜に関するものである。 The present invention relates to fluid separation membranes.
　各種混合ガスや混合液体から特定の成分を選択的に分離・精製する手法として、膜分離が利用されている。膜分離法は蒸留等の他の流体分離法と比較して省エネルギーな手法であるため、注目されている。 Membrane separation is used as a method for selectively separating and purifying specific components from various mixed gases and mixed liquids. Membrane separation is attracting attention because it is an energy-saving method compared to other fluid separation methods such as distillation.
　例えば天然ガスの精製プラントでは、主成分であるメタンガスに含まれる不純物の二酸化炭素を分離し、除去する必要がある。ここに膜分離を適用する場合、数ＭＰａ以上の高いガス噴出圧に曝された環境下において、長期に渡り高い分離性能を保持することが求められている。
また、化学工業においてアルコールや酢酸中に含まれる不純物の水を分離する工程において膜分離法が使われ始めている。こうした用途においても、生産性及び品質安定性の観点から、高い分離性能及び長期安定性のある流体分離膜が求められている。
流体分離膜の支持体としては、例えば、アルミナ、シリカ、金属酸化物などの多孔質材料が知られており、用途に応じて目的とする細孔直径の制御が重要である。細孔直径が小さいと流体拡散性が低下する一方、細孔直径が大きいと圧縮強度が低下するトレードオフがある。多孔質材料はさまざまな用途に使用されるが、分離膜に用いる場合には、多孔質材料の細孔直径が分離特性を左右することが知られている。また特に、分離膜の支持体に多孔質材料を適用する場合、多孔質材料の表面に粗大な細孔があると、その表面上に形成する分離機能層にピンホールなどの欠陥ができやすく、分離膜の歩留まりが悪化する。一方、多孔質材料の細孔を緻密化すると、製膜性は向上するが透過抵抗が増大し、分離膜の性能が低下する課題があった。 For example, in a natural gas refining plant, it is necessary to separate and remove carbon dioxide as an impurity contained in methane gas, which is the main component. When membrane separation is applied here, it is required to maintain high separation performance over a long period of time in an environment exposed to a high gas ejection pressure of several MPa or more.
In the chemical industry, the membrane separation method has begun to be used in the process of separating water, which is an impurity contained in alcohol and acetic acid. Also in such applications, fluid separation membranes with high separation performance and long-term stability are required from the viewpoint of productivity and quality stability.
Porous materials such as alumina, silica, and metal oxides are known as supports for fluid separation membranes, and it is important to control the desired pore diameter depending on the application. There is a trade-off that smaller pore diameters reduce fluid diffusivity, while larger pore diameters reduce compressive strength. Porous materials are used in various applications, and it is known that the pore diameter of the porous material affects the separation characteristics when used for separation membranes. In particular, when a porous material is used as a support for a separation membrane, if the surface of the porous material has coarse pores, defects such as pinholes are likely to occur in the separation functional layer formed on the surface. The yield of the separation membrane deteriorates. On the other hand, if the pores of the porous material are made denser, the membrane formability is improved, but there is a problem that the permeation resistance is increased and the performance of the separation membrane is lowered.
　こうした背景から、細孔直径の大きな多孔質支持層に対し、その細孔直径よりも小さい細孔直径を形成する粒子層を積層することで圧縮強度と流体拡散性を両立する手法が提案されている。 Against this background, a method has been proposed that achieves both compressive strength and fluid diffusibility by laminating a particle layer that forms a pore diameter smaller than the pore diameter of a porous support layer with a large pore diameter. there is
　特許文献１には、多孔質支持体の表面に、粒子径の揃ったシリカ球状粒子の集合体からなる粒子層を被着し、細孔直径を制御しつつ平滑面を形成することで、ピンホール等の欠陥が生じることなく薄膜の分離膜を形成する手法が提案されている。一方、特許文献２には、柔軟かつ、耐熱性や耐薬品性に優れる多孔質炭素繊維が提案されていて、取り扱い時の破損を防止しつつ、高温運転や不純物環境などの過酷条件下で使用可能な多孔質支持層としての期待がある。 In Patent Document 1, a particle layer consisting of an aggregate of silica spherical particles having a uniform particle diameter is adhered to the surface of a porous support, and a smooth surface is formed while controlling the pore diameter to obtain a pin. Techniques have been proposed for forming a thin separation film without defects such as holes. On the other hand, Patent Document 2 proposes a porous carbon fiber that is flexible and has excellent heat resistance and chemical resistance. There are expectations as a possible porous support layer.
特開２００２－２９３６５６号公報JP-A-2002-293656 ＷＯ２０１９／０２１９３WO2019/02193
　前述のような柔軟性を特徴とする多孔質支持層に対し、製膜性や流体拡散性の向上を目的に、特許文献１に記載されるような球状粒子層を積層すると、球状粒子の間の接触面積が小さいことに由来する接着力の弱さのため、多孔質支持層の曲げ変形に追従できずに剥離するほか、剥離を抑制しようとした場合は粒子層の柔軟性が喪失して多孔質支持層も含めた破断が起こって連続製造不能になり生産性が低下すること、多孔質支持層と粒子層との界面での剥離も進行しやすく、剥離部分を起点とした多孔質材料全体の破壊が起こることなど、実用上の課題があり、細孔直径を任意に制御することができなかった。また、多孔質材料に製膜した流体分離膜は、運転中の経時での圧力変動により破損することがあった。 When a spherical particle layer as described in Patent Document 1 is laminated on a porous support layer characterized by flexibility as described above for the purpose of improving film-forming properties and fluid diffusibility, Due to the weak adhesive force derived from the small contact area of the porous support layer, it cannot follow the bending deformation of the porous support layer and peels off. Fracture including the porous support layer occurs, making it impossible to continuously manufacture, reducing productivity, and delamination at the interface between the porous support layer and the particle layer is likely to progress, and the porous material originates from the delamination part. There were practical problems such as the occurrence of total destruction, and it was not possible to arbitrarily control the pore diameter. In addition, fluid separation membranes formed on porous materials may be damaged due to pressure fluctuations over time during operation.
　そこで本発明は、柔軟で生産性に優れ、圧縮強度と流体拡散性を両立可能な多孔質材料と、高い分離性能及び長期安定性のある流体分離膜の提供を課題とする。 Therefore, an object of the present invention is to provide a porous material that is flexible, has excellent productivity, and can achieve both compressive strength and fluid diffusibility, and a fluid separation membrane that has high separation performance and long-term stability.
　上述の課題を解決する本発明は、以下の構成を有する。 The present invention for solving the above problems has the following configuration.
　表面が分離機能層で被覆された繊維状の多孔質支持層を有し、前記多孔質支持層と前記分離機能層との間の少なくとも一部に粒子層が介在し、前記粒子層は、繊維状粒子及び／または平板状粒子を含有する流体分離膜。 A fibrous porous support layer having a surface coated with a separation functional layer, a particle layer interposed at least partially between the porous support layer and the separation functional layer, the particle layer comprising fibers A fluid separation membrane containing shaped particles and/or tabular particles.
　本発明により、柔軟で生産性に優れ、圧縮強度と流体拡散性を両立可能な多孔質材料を提供することができる。また、本発明の多孔質材料を支持体に用いることで、高い分離性能及び長期安定性のある流体分離膜を提供できる。 According to the present invention, it is possible to provide a porous material that is flexible, excellent in productivity, and capable of achieving both compressive strength and fluid diffusibility. Moreover, by using the porous material of the present invention as a support, a fluid separation membrane with high separation performance and long-term stability can be provided.
　本発明は、表面が分離機能層で被覆された繊維状の多孔質支持層を有し、前記多孔質支持層と前記分離機能層との間の少なくとも一部に粒子層が介在し、前記粒子層は、繊維状粒子及び／または平板状粒子を含有する流体分離膜である。 The present invention has a fibrous porous support layer whose surface is coated with a separation functional layer, a particle layer interposed at least partially between the porous support layer and the separation functional layer, and the particles A layer is a fluid separation membrane containing fibrous particles and/or tabular particles.
　＜多孔質支持層＞
　本発明の多孔質材料は、多孔質支持層と粒子層を有する。 <Porous support layer>
The porous material of the present invention has a porous support layer and a particulate layer.
　本発明の多孔質材料における多孔質支持層とは、多孔質であって、流体の透過を妨げず、粒子層を支える機能を併せ持つ材料であれば特に限定されず、従来公知の材料を適宜選択できる。多孔質支持層として好適な材料の例としては、海島構造に由来する独立気泡を持つ材料、複数の粒子が連結された構造を持つ材料、繊維状の材料が折り重なり、必要に応じて適度に接着された織布、不織布などの材料、空隙と支持体を構成する物質とが互いに連続している連続多孔構造を持つ材料などが例示される。これら材料は流体の透過を妨げず、分離機能層を支える機能を発揮する観点から適宜選択されることが好ましい。中でも連続多孔構造を持つ材料は、空隙と多孔質支持層を構成する物質とが互いに連続し、界面の曲率が粒子連結した多孔質支持層と比較して低いことから、流体の透過を妨げず、かつ多孔質支持層を構成する物質が応力を分散させる効果が高く、結果として圧縮強度が高まるため、より好ましい。 The porous support layer in the porous material of the present invention is not particularly limited as long as it is porous, does not hinder the permeation of fluid, and has the function of supporting the particle layer, and conventionally known materials are appropriately selected. can. Examples of materials suitable for the porous support layer include a material having closed cells derived from a sea-island structure, a material having a structure in which a plurality of particles are connected, and a fibrous material that is folded and appropriately Examples include materials such as bonded woven fabrics and non-woven fabrics, and materials having a continuous porous structure in which the voids and the substance constituting the support are continuous with each other. It is preferable that these materials are appropriately selected from the viewpoint of exhibiting the function of supporting the separation functional layer without impeding the permeation of the fluid. In particular, in materials with a continuous porous structure, the voids and substances that make up the porous support layer are continuous with each other, and the curvature of the interface is lower than that of the porous support layer in which particles are connected, so fluid permeation is not hindered. In addition, the material constituting the porous support layer has a high effect of dispersing stress, and as a result, the compressive strength is increased, which is more preferable.
　多孔質支持層の材質は特に制限されず、従来公知の材質を適宜選択できる。材質としては、例えば、アルミナ、シリカ、コージェライト、ジルコニア、チタニア、バイコールガラス、ゼオライト、マグネシア、炭素（カーボン）、焼結金属等の無機物や、ポリスルホン、ポリエーテルスルホン、ポリアミド、ポリエステル、セルロース系ポリマー、ビニルポリマー、ポリフェニレンスルフィド、ポリフェニレンスルフィドスルホン、ポリフェニレンスルホン、及びポリフェニレンオキシドなどのホモポリマー並びにコポリマーからなる群から選択される少なくとも１種のポリマーを含有する有機物、炭化可能樹脂からなる有機材料を炭化した炭素材料等が挙げられ、これら材質を多孔質化したものを用いることができる。炭化可能樹脂としては、例えば、ポリフェニレンオキシド、ポリビニルアルコール、ポリアクリロニトリル、フェノール樹脂、全芳香族ポリエステル、不飽和ポリエステル樹脂、アルキド樹脂、メラミン樹脂、ユリア樹脂、ポリイミド樹脂、ジアリルフタレート樹脂、リグニン樹脂、ウレタン樹脂等が挙げられる。これらを２種以上用いてもよい。多孔質支持層を構成する材料は、耐熱性、耐薬品性や機械的強度の観点から、無機材料が好ましく、粒子層に含有される粒子と材料が同一の素材である場合、粒子層と多孔質支持層の化学的性質が近似しているため界面接着性に優れることから好ましい。 The material of the porous support layer is not particularly limited, and conventionally known materials can be appropriately selected. Materials include inorganic substances such as alumina, silica, cordierite, zirconia, titania, Vycor glass, zeolite, magnesia, carbon, sintered metals, polysulfone, polyethersulfone, polyamide, polyester, and cellulose-based polymers. , an organic material containing at least one polymer selected from the group consisting of homopolymers and copolymers such as vinyl polymer, polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfone, and polyphenylene oxide, and an organic material composed of a carbonizable resin. Carbon materials and the like can be mentioned, and porous materials made of these materials can be used. Carbonizable resins include, for example, polyphenylene oxide, polyvinyl alcohol, polyacrylonitrile, phenol resin, wholly aromatic polyester, unsaturated polyester resin, alkyd resin, melamine resin, urea resin, polyimide resin, diallyl phthalate resin, lignin resin, urethane resin, Resin etc. are mentioned. You may use 2 or more types of these. The material constituting the porous support layer is preferably an inorganic material from the viewpoint of heat resistance, chemical resistance and mechanical strength. Since the chemical properties of the support layer are close to each other, the interfacial adhesion is excellent.
　本発明の多孔質支持層を構成する元素のうち、ハロゲン元素及び酸素元素を除いた中で、数基準で最も多く存在する元素のことを元素Ａとすると、多孔質支持層を構成する元素Ａは、後述する粒子層中に含有される繊維状粒子及び／または平板状粒子を構成する元素Ｂと同一であることが好ましい。元素Ａと元素Ｂとが同一であると、多孔質支持層と繊維状粒子及び／または平板状粒子との界面が形成された際に、当該界面での繊維状粒子及び／または平板状粒子と多孔質支持層との接着性が良く、多孔質材料全体として剥離部分からの破壊が見られず、強度が向上する傾向が見られるため好ましい。 Among the elements constituting the porous support layer of the present invention, excluding halogen elements and oxygen elements, element A is the element that is present in the largest number on a numerical basis. Element A constituting the porous support layer is preferably the same as the element B that constitutes the fibrous grains and/or tabular grains contained in the later-described grain layer. When the element A and the element B are the same, when the interface between the porous support layer and the fibrous particles and/or tabular particles is formed, the fibrous particles and/or tabular particles at the interface are It is preferable because it has good adhesiveness to the porous support layer, does not show breakage from the peeled portion of the porous material as a whole, and tends to improve strength.
　多孔質支持層として繊維状の材料を用いるが、繊維状であれば特に制限されず、任意の形状とすることが可能である。 A fibrous material is used as the porous support layer, but it is not particularly limited as long as it is fibrous, and it can be of any shape.
　繊維断面の形状は、何ら制限されるものではなく、丸断面、三角断面等の多葉断面、扁平断面や中空断面など任意の形状とすることが可能である。特に多孔質支持層の断面が、中空断面である場合、すなわち中空糸状の形態を持つ多孔質支持層であると、多孔質支持層中を流体が流れる際の圧力損失を抑制しつつ耐圧性を持たせることが可能になるため好ましい。中空糸の中空率は、高いほど特に繊維軸方向の圧力損失が低減され流体の流れを妨げないため好ましく、また低いほど繊維断面方向の圧縮強度を大きくすることが可能である観点から好ましい。これら観点から両者をバランスさせることが可能な中空率は１０～９０％の範囲であることが好ましく、２０～６０％の範囲であるとより好ましい。中空糸の中空部は、単独でも複数形成されていても良い。 The shape of the fiber cross section is not limited at all, and can be any shape such as a round cross section, a multilobed cross section such as a triangular cross section, a flat cross section, or a hollow cross section. In particular, when the cross section of the porous support layer is a hollow cross section, that is, the porous support layer has a hollow fiber shape, pressure loss is suppressed and pressure resistance is improved when a fluid flows through the porous support layer. It is preferable because it becomes possible to have it. The hollowness of the hollow fibers is preferably as high as possible because the pressure loss in the direction of the fiber axis is particularly reduced and the flow of fluid is not hindered, and as low as possible, the compressive strength in the cross-sectional direction of the fiber can be increased. From these points of view, the hollowness ratio capable of balancing both is preferably in the range of 10 to 90%, more preferably in the range of 20 to 60%. The hollow portion of the hollow fiber may be formed singly or plurally.
　多孔質支持層が中空糸状の形態を持つ場合には、中空糸の外径は特に限定されるものではなく、用途に応じて強度や柔軟性などを考慮して任意に決定することができるが、強度などの取り扱い性を考慮した場合、中空糸状多孔質支持層の外径は０．０２ｍｍ以上であることが好ましく、柔軟性の観点から中空糸状多孔質支持層の外径は５０ｍｍ以下であることが好ましい。 When the porous support layer has a hollow fiber shape, the outer diameter of the hollow fiber is not particularly limited, and can be arbitrarily determined in consideration of strength, flexibility, etc. according to the application. Considering handling properties such as strength, the hollow fiber porous support layer preferably has an outer diameter of 0.02 mm or more, and from the viewpoint of flexibility, the hollow fiber porous support layer has an outer diameter of 50 mm or less. is preferred.
　多孔質支持層の空隙率は、大きいほど流体の圧力損失を低減して高効率な流路を複数確保しやすいため、１０％以上が好ましく、２５％以上がより好ましい。また、空隙率が小さいほど機械的強度などの取扱い性に優れるため８０％以下が好ましく、７０％以下がより好ましい。 The porosity of the porous support layer is preferably 10% or more, more preferably 25% or more, because the larger the porosity, the more likely it is to reduce the pressure loss of the fluid and secure a plurality of highly efficient flow paths. In addition, since the smaller the porosity, the better the handleability such as mechanical strength, the porosity is preferably 80% or less, more preferably 70% or less.
　ここで多孔質支持層の空隙率とは、３次元顕微鏡撮影で観察した画像から、計算に必要な着目領域を設定し、着目領域の体積をＡ、着目領域中の空隙部の体積をＢとして、以下の式で算出されたものを言う。 Here, the porosity of the porous support layer is defined by setting a region of interest necessary for calculation from an image observed with a three-dimensional microscope, with A being the volume of the region of interest, and B being the volume of voids in the region of interest. , which is calculated by the following formula.
　空隙率（％）＝Ｂ／Ａ×１００
　３次元顕微鏡撮影は、多孔質支持層を構成する固体部と空隙部とを分離、観察可能であれば特に限定されないが、イオンビームで断面を切り出しつつ連続的に走査型電子顕微鏡で観察するスライス＆ビューや、透過型のＸ線や電子顕微鏡を用いてコンピューター断層撮影を適用する方法など、固体部と空隙部とを電子情報として分離、観察および解析可能な分析手法を適宜選択することが好ましい。このとき固体部と空隙部の電子線コントラストが弱く、観察が難しい場合には、適宜重金属などを用いて電子染色を行った後に、観察を行った。 Porosity (%) = B/A x 100
The three-dimensional microscopic imaging is not particularly limited as long as the solid portion and the void portion that constitute the porous support layer can be separated and observed. It is preferable to appropriately select an analysis method that can separate, observe, and analyze the solid part and the void part as electronic information, such as & view, a method of applying computed tomography using a transmission type X-ray or an electron microscope. . At this time, when the electron beam contrast between the solid portion and the void portion was weak and observation was difficult, the observation was performed after performing electron staining using an appropriate heavy metal or the like.
　＜粒子層＞
　本発明の多孔質材料における粒子層は、多孔質支持層の少なくとも一部に接するように配置される状態を持ち、これを介在している状態と定義する。粒子層の形状は特に制限されず、円筒状、筋状、螺旋状、球状、ブロック状など任意の形状とすることが可能であるが、粒子層が円筒状であると断面方向にかかる力を分散して、耐圧性を高く保ちやすいことから好ましい。 <Particle layer>
The particle layer in the porous material of the present invention has a state in which it is arranged so as to be in contact with at least a portion of the porous support layer, and is defined as an intervening state. The shape of the particle layer is not particularly limited, and may be any shape such as cylindrical, linear, helical, spherical, or block-like. It is preferable because it is easy to disperse and maintain high pressure resistance.
　なお粒子層は、多孔質支持層の一部に接してさえいれば特に制限されないが、多孔質支持層が粒子層によって被覆される面積が大きいと、粒子層により細孔直径を制御しつつ流体拡散性を確保できることから、多孔質支持層の一方の面について全面が粒子層で被覆されている形態も好ましい態様の一つである。 The particle layer is not particularly limited as long as it is in contact with a part of the porous support layer. A form in which the entire surface of one surface of the porous support layer is coated with a particle layer is also one of the preferred embodiments, since the diffusibility can be ensured.
　ここで粒子層が多孔質支持層の少なくとも一部に接するように配置されるとは、多孔質支持層の少なくとも一部の表面に対して、粒子層が接している状態を指す。粒子層は、多孔質支持層の表面のうち、全面を覆う形態や、一方の表面のみを覆う形態、表面の一部のみを覆うように配置される形態のいずれも可能である。特に、多孔質材料が後述する分離機能層を有する態様の場合には、分離機能層が形成される側にある多孔質支持層の表面が粒子層によって覆われた形態であることが好ましい。つまり分離機能層を有する多孔質材料の場合、多孔質支持層／粒子層／分離機能層の順に積層された形態が好ましい。 Here, the phrase "the particle layer is arranged so as to be in contact with at least a portion of the porous support layer" refers to a state in which the particle layer is in contact with at least a portion of the surface of the porous support layer. The particle layer can cover the entire surface of the porous support layer, cover only one surface, or cover only a part of the surface. In particular, in the case where the porous material has a separation function layer, which will be described later, it is preferable that the surface of the porous support layer on the side where the separation function layer is formed is covered with the particle layer. In other words, in the case of a porous material having a separation functional layer, it is preferable to have a form in which porous support layer/particle layer/separation functional layer are laminated in this order.
　本発明において粒子層とは、粒子を主体とした層である。ここで粒子を主体とした層とは、その層の空隙を除く体積を１００％とした際に、繊維状粒子及び平板状粒子の合計が占める体積が５％以上であるものを指す。このとき、粒子層中の繊維状粒子及び／または平板状粒子以外の部分は特段制限されないが、他の粒子、つまり後述の繊維状粒子や平板状粒子以外の粒子（アスペクト比が１０未満の粒子）やバインダー樹脂を粒子層中に含有していてもよい。バインダー樹脂は、粒子同士を接着する機能を持つ材料であれば特に限定されず、従来公知の材料を適宜選択できる。後述する分離機能層を形成する場合には、分離機能層を構成する無機材料や有機材料を粒子層中に含有していてもよい。繊維状粒子及び平板状粒子の合計が占める体積分率が大きいと、粒子間での交絡が起こりやすく、粒子層内や粒子層間、粒子層と多孔質支持層の剥離や破壊を防止できることから好ましい。繊維状粒子及び平板状粒子の合計が占める体積は９７％以上１００％以下であると、特に細孔形成しやすく、流体の透過抵抗を効果的に低減でき、流体分離膜の透過度の観点から好ましい。一方、後述の繊維状粒子や平板状粒子以外の粒子（アスペクト比が１０未満の粒子）を粒子層中に含有していると、粒子層表面の細孔径を制御しやすくなり、粒子層表面に形成する流体分離膜の製膜性に優れる効果がある。以上の観点から、繊維状粒子及び平板状粒子の合計が占める体積は２０％以上９７％未満であることも好ましい。 In the present invention, the particle layer is a layer mainly composed of particles. Here, the layer mainly composed of particles means that the total volume of fibrous particles and tabular particles is 5% or more when the volume of the layer excluding voids is taken as 100%. At this time, the portion other than the fibrous grains and/or the tabular grains in the grain layer is not particularly limited, but other grains, that is, grains other than the fibrous grains and tabular grains described later (grains having an aspect ratio of less than 10) ) or a binder resin may be contained in the particle layer. The binder resin is not particularly limited as long as it has a function of bonding particles together, and conventionally known materials can be appropriately selected. When forming a separation functional layer, which will be described later, the particle layer may contain an inorganic material or an organic material that constitutes the separation functional layer. When the total volume fraction of fibrous particles and tabular particles is large, entanglement between particles easily occurs, which is preferable because it is possible to prevent peeling and destruction in the particle layer, between the particle layers, and between the particle layer and the porous support layer. . When the total volume occupied by the fibrous particles and the tabular particles is 97% or more and 100% or less, it is particularly easy to form pores, the fluid permeation resistance can be effectively reduced, and from the viewpoint of the permeability of the fluid separation membrane. preferable. On the other hand, when particles other than fibrous particles and tabular particles (particles having an aspect ratio of less than 10) are contained in the particle layer, the pore diameter of the particle layer surface can be easily controlled. There is an effect that the fluid separation membrane to be formed is excellent in film formability. From the above viewpoints, it is also preferable that the total volume occupied by fibrous grains and tabular grains is 20% or more and less than 97%.
　層中に繊維状粒子及び平板状粒子が占める体積は、３次元顕微鏡撮影など、３次元的に形状を把握できる測定手法によって、電子情報として３次元像を取り出して解析する。繊維状粒子及び平板状粒子とそれ以外の部分の区別の仕方としては、電子情報として分離、観察および解析可能な分析手法を適宜選択することが好ましい。このとき、繊維状粒子及び平板状粒子とそれ以外の部分の電子線コントラストが弱く、観察が難しい場合には、適宜重金属などを用いて電子染色を行った後に、観察を行った。取り出された繊維状粒子及び／または平板状粒子は、それぞれの粒子を適切な手法で分離し、個々の粒子について最小二乗法を適用し、楕円体として近似した。繊維状粒子及び平板状粒子が占める体積は、観察された３次元像として、着目粒子数が２００個を超える体積を設定し、アスペクト比１０以上となる粒子の体積分率として算出した。 The volume occupied by fibrous particles and tabular particles in the layer is analyzed by extracting a three-dimensional image as electronic information using a measurement method that can grasp the three-dimensional shape, such as three-dimensional microscopic photography. As a method of distinguishing fibrous grains and tabular grains from other portions, it is preferable to appropriately select an analysis method that enables separation, observation and analysis as electronic information. At this time, when the electron beam contrast between the fibrous particles and tabular particles and other portions was weak and observation was difficult, the observation was performed after performing electron dyeing using a suitable heavy metal or the like. The fibrous grains and/or tabular grains taken out were separated by an appropriate technique, and the least squares method was applied to each grain to approximate them as an ellipsoid. The volume occupied by fibrous particles and tabular particles was calculated as the volume fraction of particles having an aspect ratio of 10 or more by setting a volume in which the number of particles of interest exceeds 200 as an observed three-dimensional image.
　本発明の粒子層は、繊維状粒子及び／または平板状粒子を含有する。そして本発明の繊維状粒子及び／または平板状粒子とは、アスペクト比が１０以上の粒子を意味する。ここで繊維状粒子とは、粒子から得られた楕円体の３つの径（楕円体の中心を通って直交する３つの直径）のうち最も短い径の長さをＬｂとして、Ｌｂに対してアスペクト比が１０以上となる径を長径としたとき、長径が１つ存在する粒子を指す。そして平板状粒子とは、Ｌｂに対してアスペクト比が１０以上となる径を長径としたとき、長径が２つ存在する粒子を指す。 The particle layer of the present invention contains fibrous particles and/or tabular particles. The fibrous grains and/or tabular grains of the present invention mean grains having an aspect ratio of 10 or more. Here, the fibrous particles are the three diameters of the ellipsoid obtained from the particles (three diameters perpendicular to each other through the center of the ellipsoid), where Lb is the length of the shortest diameter, and the aspect When the diameter with a ratio of 10 or more is taken as the major diameter, it refers to particles having one major diameter. Tabular grains refer to grains having two major diameters, where the major diameter is defined as a diameter having an aspect ratio of 10 or more with respect to Lb.
　ここで３つの直径は、粒子層中の１粒子を３次元顕微鏡撮影など、３次元的に形状を把握できる測定手法によってデジタルデータとして取り出して、その粒子の３次元データから測定され、最も短い径の長さＬｂと、最も長い径の長さＬａとの比（Ｌａ／Ｌｂ）をアスペクト比とする。 Here, the three diameters are measured from the three-dimensional data of one particle in the particle layer, taken out as digital data by a measurement method that can grasp the three-dimensional shape, such as three-dimensional microscopic photography, and the shortest diameter The aspect ratio is the ratio (La/Lb) of the length Lb of the diameter to the length La of the longest diameter.
　繊維状粒子及び／または平板状粒子のアスペクト比は、Ｌａ／Ｌｂが１０以上の粒子から任意の粒子を１０個取り出して、それぞれの粒子のＬｂと、Ｌａの比（Ｌａ／Ｌｂ）を取り、１０点の平均値を繊維状粒子及び／または平板状粒子のアスペクト比として算出する。なお、繊維状粒子及び／または平板状粒子の最長長さＬｌは、前記アスペクト比を計算した際に選定された１０個の粒子それぞれのＬａを用い、これの平均値として算出する。繊維状粒子及び／または平板状粒子の最短長さＬｓは、前記アスペクト比を計算した際に選定された１０個の粒子それぞれのＬｂを用い、これの平均値として算出する。 The aspect ratio of fibrous particles and/or tabular particles is obtained by taking 10 arbitrary particles from particles having La/Lb of 10 or more and taking the ratio of Lb and La (La/Lb) of each particle, The average value of 10 points is calculated as the aspect ratio of fibrous grains and/or tabular grains. The longest length Ll of the fibrous grains and/or tabular grains is calculated as the average value of La of the 10 grains selected when the aspect ratio is calculated. The shortest length Ls of fibrous grains and/or tabular grains is calculated as an average value of Lb values of 10 grains selected when calculating the aspect ratio.
　最長長さＬｌは、大きいほど粒子間での交絡が起こりやすく、粒子層内や粒子層間、粒子層と多孔質支持層の剥離や破壊を防止できること、特に多孔質支持層と繊維状粒子及び／または平板状粒子との界面が形成された際に、当該界面での繊維状粒子及び／または平板状粒子と多孔質支持層との接着性が良く、多孔質材料全体として剥離部分からの破壊が見られず、強度が向上する傾向が見られることから好ましい。またＬｌが小さいほど、粒子層形成時の取り扱い性がよく、特に液体を用いて粒子層を形成する場合には液体の流動性を確保しつつ粒子層を形成できる観点から好ましい。これらの観点から、Ｌｌは０．０５μｍ以上１０００μｍ以下であることが好ましく、１μｍ以上１００μｍ以下であることがより好ましい。 The longer the maximum length Ll, the easier it is for entanglement between particles to occur, and it is possible to prevent separation and destruction in the particle layer, between the particles, and between the particle layer and the porous support layer, especially the porous support layer and the fibrous particles and/or Alternatively, when the interface with the tabular grain is formed, the adhesion between the fibrous grain and/or the tabular grain and the porous support layer at the interface is good, and the porous material as a whole is not broken from the peeled portion. It is preferable because the tendency to improve the strength is observed. In addition, the smaller Ll is, the better the handleability at the time of forming the particle layer is, particularly in the case of forming the particle layer using a liquid, it is preferable from the viewpoint that the particle layer can be formed while ensuring the fluidity of the liquid. From these points of view, Ll is preferably 0.05 μm or more and 1000 μm or less, more preferably 1 μm or more and 100 μm or less.
　繊維状粒子及び／または平板状粒子のアスペクト比は、高いほど粒子間での交絡が起こりやすく、粒子層内や粒子層間、粒子層と多孔質支持層の剥離や破壊を防止できること、特に多孔質支持層と繊維状粒子及び／または平板状粒子との界面が形成された際に、当該界面での繊維状粒子及び／または平板状粒子と多孔質支持層との接着性が良く、多孔質材料全体として剥離部分からの破壊が見られず、強度が向上する傾向が見られることから好ましい。またアスペクト比は、低いほど粒子層形成時の取り扱い性がよく、特に液体を用いて粒子層を形成する場合には液体の流動性を確保しつつ粒子層を形成できる観点から好ましい。これらの観点から、粒子層中の繊維状粒子及び／または平板状粒子のアスペクト比は、２０～１０，０００の範囲であると好ましく、１００～２０００の範囲がより好ましい。 The higher the aspect ratio of the fibrous particles and/or tabular particles, the more easily entanglement occurs between the particles, and the separation and breakage of the particle layer and the particle layer and the porous support layer can be prevented. When the interface between the support layer and the fibrous particles and/or tabular particles is formed, the adhesion between the fibrous particles and/or tabular particles and the porous support layer at the interface is good, and the porous material As a whole, no breakage from the exfoliated portion is observed, and the strength tends to be improved, which is preferable. In addition, the lower the aspect ratio, the better the handleability when forming the particle layer, and in particular, when the particle layer is formed using a liquid, it is preferable from the viewpoint that the particle layer can be formed while ensuring the fluidity of the liquid. From these points of view, the aspect ratio of fibrous grains and/or tabular grains in the grain layer is preferably in the range of 20-10,000, more preferably in the range of 100-2000.
　繊維状粒子及び／または平板状粒子の分率は特に制限されないが、繊維状粒子は細孔形成しやすく流体拡散性の観点で有利であることから、繊維状粒子及び平板状粒子の合計に占める繊維状粒子の体積分率が大きいことが好ましい。 The fraction of fibrous particles and/or tabular particles is not particularly limited, but since fibrous particles easily form pores and are advantageous from the viewpoint of fluid diffusibility, A high volume fraction of fibrous particles is preferred.
　繊維状粒子及び／又は平板状粒子は、セルロースナノファイバー、カーボンナノホーン、カーボンナノリボン、カーボンナノチューブ、グラフェン、及び酸化グラフェンからなる群より選ばれる少なくとも１種類を含有することが好ましい。この点を以下に説明する。 The fibrous particles and/or tabular particles preferably contain at least one selected from the group consisting of cellulose nanofibers, carbon nanohorns, carbon nanoribbons, carbon nanotubes, graphene, and graphene oxide. This point will be explained below.
　本発明の粒子層を構成する繊維状粒子は、粒子層の成形時において、特に液体を用いて塗布する工程を採用した場合は、液体の流動方向に繊維状粒子が配向しやすい性質があり、繊維状粒子が配向することで特定方向、特に繊維軸方向への強化性を示し、繊維軸と直交方向へは曲げ剛性が改善されることから好ましい。繊維状粒子の候補となる繊維状の形状を持つ添加物としては、例えば、ウィスカーやセルロースナノファイバー、カーボンナノホーン、カーボンナノリボン、カーボンナノチューブなどが挙げられ、後述の好ましいＬｓの範囲を考慮すると、セルロースナノファイバー、カーボンナノホーン、カーボンナノリボン、カーボンナノチューブが好ましい。 The fibrous particles constituting the particle layer of the present invention have a property that the fibrous particles tend to be oriented in the flow direction of the liquid when the particle layer is molded, particularly when a step of coating with a liquid is employed. The orientation of the fibrous particles is preferable because it exhibits reinforcing properties in a specific direction, particularly in the direction of the fiber axis, and improves the bending rigidity in the direction orthogonal to the fiber axis. Additives having fibrous shapes that are candidates for fibrous particles include, for example, whiskers, cellulose nanofibers, carbon nanohorns, carbon nanoribbons, and carbon nanotubes. Nanofibers, carbon nanohorns, carbon nanoribbons, and carbon nanotubes are preferred.
　一方、本発明の粒子層を構成する平板状粒子は、粒子層の成形時において、特に液体を用いて塗布する工程を採用した場合は、液体の流動方向に平板状粒子が面配向しやすい性質があり、配向方向がＭＤ方向であった場合は、ＭＤ方向およびＴＤ方向に対して強化性を示しやすいことから好ましい。平板状粒子の候補となる平板状の形状を持つ添加物としては、例えば、グラフェン、酸化グラフェン、タルク、マイカなどが挙げられ、後述の好ましいＬｓの範囲を考慮すると、グラフェン、酸化グラフェンが好ましい。　粒子の材質は、前記効果を発揮できれば特に限定されず、炭素、酸素、窒素、ホウ素、硫黄、珪素などを含有しても良く、またアルカリ金属、アルカリ土類金属などを含有していても良い。 On the other hand, the tabular particles constituting the particle layer of the present invention have the property that the tabular particles tend to be plane-oriented in the flow direction of the liquid when forming the particle layer, particularly when a process of coating with a liquid is employed. , and when the orientation direction is the MD direction, it is preferable because it tends to exhibit reinforcing properties in the MD direction and the TD direction. Additives having a tabular shape that are candidates for tabular particles include, for example, graphene, graphene oxide, talc, and mica. Considering the preferred range of Ls described later, graphene and graphene oxide are preferred. The material of the particles is not particularly limited as long as the above effects can be exhibited, and may contain carbon, oxygen, nitrogen, boron, sulfur, silicon, etc., and may contain alkali metals, alkaline earth metals, etc. .
　また本発明の繊維状粒子及び／または平板状粒子は、１種類でも、２種類以上を組み合わせて使用してもよい。また、用途等に応じ、本発明の目的を損なわない範囲で、他の粒子、つまりアスペクト比が１０未満の粒子を含有してもよいが、全ての粒子の合計（つまり、アスペクト比が１０以上の粒子とアスペクト比が１０未満の粒子の合計）１００体積％において、アスペクト比が１０未満の粒子の含有量は５０体積％未満の添加量にすることが好ましく、２０体積％未満であると更に好ましい。 The fibrous particles and/or tabular particles of the present invention may be used singly or in combination of two or more. In addition, depending on the application etc., other particles, that is, particles having an aspect ratio of less than 10 may be contained within the range that does not impair the purpose of the present invention. The total of particles with an aspect ratio of less than 10)) In 100% by volume, the content of particles with an aspect ratio of less than 10 is preferably less than 50% by volume, and if it is less than 20% by volume preferable.
　粒子層中の繊維状粒子及び／または平板状粒子の大きさは特に限定されないが、繊維状粒子及び／または平板状粒子の最短長さＬｓが０．４ｎｍ以上１０μｍ以下であることが好ましい。Ｌｓが０．４ｎｍ以上であると、十分な比表面積を確保しつつ取り扱いが容易になる。一方、Ｌｓが１０μｍ以下であると、比表面積が大きく多孔質支持層との接着性が良好で多孔質材料の強度が向上すること、また、粒子の柔軟性に優れるので多孔質支持層に一部が接するように形成される粒子層の表面が平滑化しやすく、流体分離膜として用いる場合には分離機能層の製膜性が向上することなどから好ましい。上記観点から、粒子の最も短い径の長さＬｓは、１ｎｍ以上１００ｎｍ以下であることがより好ましい。 The size of the fibrous particles and/or tabular particles in the particle layer is not particularly limited, but the shortest length Ls of the fibrous particles and/or tabular particles is preferably 0.4 nm or more and 10 μm or less. When Ls is 0.4 nm or more, handling becomes easy while securing a sufficient specific surface area. On the other hand, when Ls is 10 μm or less, the specific surface area is large and the adhesiveness to the porous support layer is good, and the strength of the porous material is improved. The surface of the particle layer formed so that the portions are in contact with each other is easily smoothed, and when used as a fluid separation membrane, the separation functional layer can be formed more easily, which is preferable. From the above viewpoint, it is more preferable that the length Ls of the shortest diameter of the particles is 1 nm or more and 100 nm or less.
　粒子層の空隙率は特に限定されないが、小さいと粒子間の接着力が増して剥離耐性が向上するため、３％以上が好ましく、５％以上がより好ましい。また、空隙率が大きいと流体に対する圧力損失を小さくできるため５０％以下が好ましく、３０％以下がより好ましい。ここで粒子層の空隙率とは、３次元顕微鏡撮影で観察した画像から、計算に必要な着目領域を設定し、着目領域の体積をＡ、着目領域中の空隙部の体積をＢとして、以下の式で算出されたものを言う。 Although the porosity of the particle layer is not particularly limited, it is preferably 3% or more, more preferably 5% or more, because if it is small, the adhesion between particles increases and the peeling resistance improves. Also, if the porosity is large, the pressure loss to the fluid can be reduced, so it is preferably 50% or less, more preferably 30% or less. Here, the porosity of the particle layer is defined by setting a region of interest necessary for calculation from an image observed with a three-dimensional microscope, and taking the volume of the region of interest as A and the volume of voids in the region of interest as B, as follows: It is calculated by the formula of
　空隙率（％）＝Ｂ／Ａ×１００
　３次元顕微鏡撮影は、粒子層を構成する固体部と空隙部とを分離、観察可能であれば特に限定されないが、イオンビームで断面を切り出しつつ連続的に走査型電子顕微鏡で観察するスライス＆ビューや、透過型のＸ線や電子顕微鏡を用いてコンピューター断層撮影を適用する方法など、固体部と空隙部とを電子情報として分離、観察および解析可能な分析手法を適宜選択することが好ましい。このとき固体部と空隙部の電子線コントラストが弱く、観察が難しい場合には、適宜重金属などを用いて電子染色を行った後に、観察を行った。なお、ばらつきを考慮して粒子１０以上がデータ内に存在するものを使用し、１データ内に１０以上の粒子が存在しない場合は、別の観察視野から得られたデータを加え、合計して１０以上の粒子が入った粒子層を観察して体積％を求める。 Porosity (%) = B/A x 100
Three-dimensional microscopic imaging is not particularly limited as long as it is possible to separate and observe the solid part and the void part that make up the particle layer. Alternatively, it is preferable to appropriately select an analysis method capable of separating, observing, and analyzing the solid portion and the void portion as electronic information, such as a method of applying computed tomography using a transmission type X-ray or an electron microscope. At this time, when the electron beam contrast between the solid portion and the void portion was weak and observation was difficult, the observation was performed after performing electron staining using an appropriate heavy metal or the like. In consideration of variations, data with 10 or more particles in the data is used, and when 10 or more particles do not exist in one data, data obtained from another observation field are added and totaled A particle layer containing 10 or more particles is observed to determine the volume %.
　本発明の粒子層は、その厚みは特に限定されないが、厚みが厚いほど外力による破損に強く、耐久性に優れることから好ましく、薄いほど流体の透過抵抗を低減でき、流体拡散性を向上させることができるため好ましい。これら観点から粒子層の厚みは０．２μｍ～１００μｍの範囲であることが好ましく、０．５μｍ～１０μｍの範囲であることがより好ましい。ここで粒子層の厚みは、多孔質材料から観察用の断面を形成した際に、粒子層を構成する最も薄い部分の厚みを顕微鏡などで計測することで定義され、多孔質材料の断面１０カ所を解析した厚みの平均値として算出される。 The thickness of the particle layer of the present invention is not particularly limited, but the thicker the layer, the more resistant it is to damage due to external force, and the better the durability. It is preferable because From these viewpoints, the thickness of the particle layer is preferably in the range of 0.2 μm to 100 μm, more preferably in the range of 0.5 μm to 10 μm. Here, the thickness of the particle layer is defined by measuring the thickness of the thinnest portion constituting the particle layer with a microscope or the like when a cross section for observation is formed from the porous material. is calculated as the average value of the analyzed thickness.
　＜流体分離膜＞
　本発明の多孔質材料を支持体として用い、少なくとも一部が粒子層と接するように分離機能層を層状に形成することで、流体分離膜として使用することができる。つまり本発明の流体分離膜は、分離機能層及び本発明の多孔質材料を有する流体分離膜であって、粒子層と分離機能層が、接するように配置されていることを特徴とする。本発明の流体分離膜は、多孔質材料が流体拡散性と耐久性を担保して、実使用中の破損を防止し、長期間安定した運転が可能になるほか、高圧がかかった際にも、多孔質支持層と粒子層とがそれぞれ応力を分散し、多孔質材料が全体として圧力を受け持つ効果が発揮され、高圧環境での運転が可能である。 <Fluid Separation Membrane>
By using the porous material of the present invention as a support and forming a layered separation functional layer so that at least a portion thereof is in contact with the particle layer, it can be used as a fluid separation membrane. That is, the fluid separation membrane of the present invention is a fluid separation membrane comprising a separation functional layer and the porous material of the present invention, characterized in that the particle layer and the separation functional layer are arranged so as to be in contact with each other. In the fluid separation membrane of the present invention, the porous material ensures fluid diffusibility and durability, prevents breakage during actual use, enables stable operation for a long period of time, and even when high pressure is applied. , the porous support layer and the particle layer each disperse the stress, and the porous material as a whole exerts the effect of bearing the pressure, making it possible to operate in a high-pressure environment.
　本発明の多孔質材料に好適に組み合わされる分離機能層は、多孔質材料の粒子層と接触している。粒子層と接触した分離機能層は、圧力などの外力を受けた際に、その内部応力を粒子層に高効率に分散させられるため耐圧性を高めることができる。また粒子層と分離機能層が接触していると、両者の界面での摩擦力によって曲げなどの外力を逃すことができ、粒子層と分離機能層との剥離を抑制する効果も期待できる。 The separation functional layer suitably combined with the porous material of the present invention is in contact with the particle layer of the porous material. The separation functional layer in contact with the particle layer can efficiently disperse the internal stress in the particle layer when subjected to an external force such as pressure, so that the pressure resistance can be improved. In addition, when the particle layer and the separation functional layer are in contact with each other, external force such as bending can be released due to the frictional force at the interface between the two, and an effect of suppressing separation between the particle layer and the separation functional layer can be expected.
　ここで分離機能層は、流体の分離機能を有する材料であれば特に限定されず、従来公知の有機材料や無機材料を適宜選択できる。有機材料は特に制限されないが、例えば、芳香族ポリイミド、酢酸セルロース、ポリスルホン、芳香族ポリアミド、ポリアミドイミド、ポリエーテルイミド、ポリエーテルスルホン、ポリアクリロニトリル、ポリフェニレンスルフィド、ポリフェニレンオキシド、ポリエーテルエーテルケトン、ポリテトラフルオロエチレン、ポリフッ化ビニリデン、ポリ（１－トリメチルシリルプロピン）、ポリジメチルシロキサン、ポリビニルトリメチルシラン、ポリ（４－メチルペンテン）、エチルセルロース、天然ゴム、ポリ（２，６－ジメチル酸化フェニレン）、低密度ポリエチレン、高密度ポリエチレン、スチレン、ポリエチルメタクリレート、ポリカーボネート、ポリエステル、脂肪族ポリアミド、ポリビニルアルコール、ポリエチレングリコールなどの各種ポリエーテル、ポリメタクリル酸、ポリメタクリル酸メチル、各種ミクロ多孔性高分子（ＰＩＭ）、各種熱転位高分子（ＴＲポリマー）およびそれらの共重合体、あるいは混合物が挙げられる。分離機能層は無機材料であると、耐熱性や耐薬品性が高い傾向にあり、長期的に安定して流体分離膜の分離性能を発揮できるため、無機材料であることが好ましい。無機材料は特に制限されないが、例えば、前記有機材料を前駆体とした炭素材料、ゼオライト、シリカ、金属有機構造体などが挙げられる。
後述の炭素元素比率の制御が容易である観点から、分離機能層は有機材料を前駆体とした炭化物が好ましく、例えば、前記熱可塑性樹脂、熱硬化性樹脂のうち、少なくとも１種を含む高分子材料を焼成して得られるものが挙げられる。特にフェノール樹脂、ポリアクリロニトリル、ポリイミドなどを選択することが好ましい。 Here, the separation function layer is not particularly limited as long as it is a material having a fluid separation function, and conventionally known organic materials and inorganic materials can be appropriately selected. Organic materials are not particularly limited, but examples include aromatic polyimide, cellulose acetate, polysulfone, aromatic polyamide, polyamideimide, polyetherimide, polyethersulfone, polyacrylonitrile, polyphenylene sulfide, polyphenylene oxide, polyetheretherketone, polytetra Fluoroethylene, polyvinylidene fluoride, poly(1-trimethylsilylpropyne), polydimethylsiloxane, polyvinyltrimethylsilane, poly(4-methylpentene), ethyl cellulose, natural rubber, poly(2,6-dimethylphenylene oxide), low density Various polyethers such as polyethylene, high-density polyethylene, styrene, polyethyl methacrylate, polycarbonate, polyester, aliphatic polyamide, polyvinyl alcohol, polyethylene glycol, polymethacrylic acid, polymethyl methacrylate, various microporous polymers (PIM), Various thermal transition polymers (TR polymers) and copolymers or mixtures thereof can be used. When the separation functional layer is made of an inorganic material, it tends to have high heat resistance and chemical resistance, and the separation performance of the fluid separation membrane can be exhibited stably over a long period of time. Although the inorganic material is not particularly limited, examples thereof include carbon materials, zeolite, silica, and metal-organic structures using the above organic materials as precursors.
From the viewpoint of facilitating the control of the carbon element ratio, which will be described later, the separation functional layer is preferably a carbide having an organic material as a precursor. Examples include those obtained by firing materials. It is particularly preferable to select phenol resin, polyacrylonitrile, polyimide, and the like.
　分離機能層の材質は、特に制限されないが、炭素元素比率が７０ａｔｏｍｉｃ％以上９９．５ａｔｏｍｉｃ％以下であることが好ましい。マトリックスの炭素元素比率Ｘが大きいほど膜性能や耐薬品性、耐熱性に優れることから好ましく、８０ａｔｏｍｉｃ％以上であるとより好ましい。一方、炭素量が少なくなるほど柔軟で破損に対する耐性が増すことから長期耐久性が向上するため、マトリックスの炭素元素比率Ｘは９２ａｔｏｍｉｃ％以下であるとより好ましい。分離機能層の炭素以外の構成元素は特に限定されず、水素、酸素、窒素、ホウ素、硫黄、珪素などを含有しても良く、またアルカリ金属、アルカリ土類金属などを含有しても良い。上記元素比率は、電子顕微鏡と組み合わせたエネルギー分散型Ｘ線分光分析を利用して分析することができる。 The material of the separation functional layer is not particularly limited, but the carbon element ratio is preferably 70 atomic % or more and 99.5 atomic % or less. The higher the carbon element ratio X in the matrix, the better the film performance, chemical resistance, and heat resistance. On the other hand, the lower the carbon content, the more flexible and resistant to breakage, and the longer the durability is improved. Therefore, the carbon element ratio X of the matrix is more preferably 92 atomic % or less. Constituent elements other than carbon in the separation functional layer are not particularly limited, and may contain hydrogen, oxygen, nitrogen, boron, sulfur, silicon and the like, and may also contain alkali metals, alkaline earth metals and the like. The above element ratios can be analyzed using energy dispersive X-ray spectroscopy combined with electron microscopy.
　分離機能層の弾性率は、１０ＧＰａ以上３００ＧＰａ以下であることが好ましい。分離機能層の弾性率が高いことにより、分離機能層の破壊を防止する効果が発現するため、ガス分離膜としての運転中の破損を防止して、長期間安定した使用を可能にする効果が得られる。一方で、弾性率が低いほど柔軟に変形するため瞬間的な衝撃力を緩和できることから、弾性率は１５ＧＰａ以上２００ＧＰａ以下であることがより好ましい。上記弾性率は、様々な分析手法で決定されるが、ナノインデンテーション法にてヘルツの接触理論を用いた弾性率の算出方法などを利用して分析することができる。 The elastic modulus of the separation functional layer is preferably 10 GPa or more and 300 GPa or less. Due to the high elastic modulus of the separation function layer, the effect of preventing destruction of the separation function layer is exhibited, so the effect of preventing breakage during operation as a gas separation membrane and enabling stable use for a long period of time. can get. On the other hand, the lower the modulus of elasticity, the more flexible the deformation, so that the momentary impact force can be alleviated. The elastic modulus is determined by various analytical methods, and can be analyzed using a method of calculating elastic modulus using Hertz's contact theory in the nanoindentation method.
　また分離機能層は、分離機能層を構成する無機材料や有機材料のうち、一部が多孔質材料の粒子層と複合された形態であると、流体分離膜として圧力や曲げなど外力が加わった際の剥離を抑制する効果が高く出来るため好ましい。また複合されている状態は少ないほど粒子層における流体の拡散を高く保つことができるため好ましい。これら観点から分離機能層の複合割合は、１％以上５０％以下の範囲であると両者のバランスに優れるため好ましく、１０％以上４０％以下であるとより好ましい。ここで、分離機能層の複合割合とは、３次元顕微鏡撮影で観察した画像から、計算に必要な着目領域を設定し、着目領域における分離機能層の体積Ｖｍ、粒子層を構成する粒子の体積Ｖｐ、空隙部の体積Ｖａとして、以下の式で算出されたものを言う。 In addition, if the separation functional layer is in a form in which a part of the inorganic material or organic material constituting the separation functional layer is combined with a particle layer of a porous material, an external force such as pressure or bending is applied as a fluid separation membrane. It is preferable because the effect of suppressing peeling at the time can be enhanced. In addition, it is preferable that the number of composites is as small as possible because the diffusion of the fluid in the particle layer can be maintained at a high level. From these points of view, the composite ratio of the separation functional layer is preferably in the range of 1% or more and 50% or less because both are excellent in balance, and more preferably 10% or more and 40% or less. Here, the composite ratio of the separation functional layer is defined by setting a region of interest necessary for calculation from an image observed with a three-dimensional microscope, and determining the volume Vm of the separation functional layer in the region of interest, the volume of the particles constituting the particle layer, and the Vp and the volume Va of the void are calculated by the following formula.
　分離機能層の複合割合（％）＝（Ｖｍ／（Ｖｍ＋Ｖｐ＋Ｖａ））×１００
　３次元顕微鏡撮影は、粒子層を構成する固体部と空隙部とを分離、さらに固体部は粒子と分離機能層とを分離、観察可能であれば特に限定されないが、イオンビームで断面を切り出しつつ連続的に走査型電子顕微鏡で観察するスライス＆ビューや、透過型のＸ線や電子顕微鏡を用いてコンピューター断層撮影を適用する方法など、分離機能層と粒子と空隙部とを電子情報として分離、観察および解析可能な分析手法を適宜選択することが好ましい。このとき固体部と空隙部の電子線コントラストが弱く、観察が難しい場合には、適宜重金属などを用いて電子染色を行った後に、観察を行った。なお、ばらつきを考慮して粒子１０以上がデータ内に存在するものを使用し、１データ内に１０以上の粒子が存在しない場合は、別の観察視野から得られたデータを加え、合計して１０以上の粒子が入った粒子層を観察して体積％を求める。 Composite ratio (%) of separation functional layer=(Vm/(Vm+Vp+Va))×100
Three-dimensional microscopic photography is not particularly limited as long as it is possible to separate the solid part and the void part that constitute the particle layer, and further separate the solid part from the particles and the separation function layer, and observe it. The separation function layer, particles, and voids are separated as electronic information, such as slice & view, which is continuously observed with a scanning electron microscope, and a method of applying computed tomography using a transmission type X-ray or electron microscope. It is preferable to appropriately select an analysis method that allows observation and analysis. At this time, when the electron beam contrast between the solid portion and the void portion was weak and observation was difficult, the observation was performed after performing electron staining using an appropriate heavy metal or the like. In consideration of variations, data with 10 or more particles in the data is used, and when 10 or more particles do not exist in one data, data obtained from another observation field are added and totaled A particle layer containing 10 or more particles is observed to determine the volume %.
　分離機能層の細孔直径は、分離対象物に合わせて適宜選択することができるが、分離対象が液体中に含まれる微粒子や高分子量物質である場合は、好適な形態としての分離機能層の細孔直径は、１ｎｍ～１０μｍであることが好ましい。分離対象がガスである場合は、好適な形態としての分離機能層の細孔直径は、０．２ｎｍ～２ｎｍであることが好ましい。 The pore diameter of the separation functional layer can be appropriately selected according to the object to be separated. The pore diameter is preferably between 1 nm and 10 μm. When the object to be separated is gas, the pore diameter of the separation functional layer as a preferred form is preferably 0.2 nm to 2 nm.
　本発明の多孔質材料と分離機能層とを組み合わせた流体分離膜は、繊維状であるが、フィルム状と比較して単位体積当りの膜面積を大きく取ることができるなどの利点がある。また、断面方向にかかる力に対する耐性が高くなることから、高圧での運転も可能となり、高効率での膜分離が可能となるため好ましい。 The fluid separation membrane that combines the porous material and the separation functional layer of the present invention is fibrous, but has advantages such as a larger membrane area per unit volume than a film. In addition, since the resistance to the force applied in the cross-sectional direction is increased, it is possible to operate at high pressure, and it is possible to perform membrane separation with high efficiency, which is preferable.
　本発明の流体分離膜の繊維断面の形状は、何ら制限されるものではなく、丸断面、三角断面等の多葉断面、扁平断面や中空断面など任意の形状とすることが可能である。特に流体分離膜の断面が、中空断面である場合、すなわち中空糸状の形態を持つ流体分離膜であると、供給される流体と分離後の流体の流れを制御しつつ耐圧性を持たせることが可能になるため好ましい。中空糸の断面積Ｙに対する中空部の断面積Ｘの面積比率（中空面積比率：１００×Ｘ／Ｙ）は、高いほど圧力損失が低減され流体の流れを妨げず、また低いほど耐圧性が高くなることから好ましい。これら観点から中空面積比率は５～７０％の範囲であることが好ましい。ここで中空糸の断面積Ｙは中空部の断面積Ｘを含んだ断面積である。また、中空部は複数有していてもよく、その場合は中空部の断面積の総和を中空部の断面積Ｘとする。 The cross-sectional shape of the fibers of the fluid separation membrane of the present invention is not limited at all, and can be any shape such as a circular cross-section, a multi-lobed cross-section such as a triangular cross-section, a flat cross-section or a hollow cross-section. In particular, when the cross section of the fluid separation membrane is a hollow cross section, that is, when the fluid separation membrane has a hollow fiber shape, it is possible to provide pressure resistance while controlling the flow of the supplied fluid and the fluid after separation. preferred because it is possible. The higher the area ratio of the cross-sectional area X of the hollow portion to the cross-sectional area Y of the hollow fiber (hollow area ratio: 100 x X/Y), the lower the pressure loss and the less the fluid flow is hindered, and the lower the pressure resistance is. It is preferable because From these viewpoints, the hollow area ratio is preferably in the range of 5 to 70%. Here, the cross-sectional area Y of the hollow fiber is a cross-sectional area including the cross-sectional area X of the hollow portion. In addition, a plurality of hollow portions may be provided, and in that case, the total cross-sectional area of the hollow portions is defined as the cross-sectional area X of the hollow portions.
　本発明の多孔質材料の製造方法としては、多孔質支持層に、繊維状粒子及び／又は平板状粒子を含有するスラリー溶液を接触させ、多孔質支持層の外表面に繊維状粒子及び／または平板状粒子を含有する粒子層を形成する工程を含むことが好ましい。スラリー溶液を接触させる方法としては、例えば、ディップコート法、スプレーコート法、ノズルコート法、液膜転写法などが挙げられ、スラリー溶液の種類に応じて適宜選択することができる。また、スラリー溶液には適宜溶媒、分散剤を用いることができる。 As a method for producing the porous material of the present invention, a porous support layer is brought into contact with a slurry solution containing fibrous particles and/or tabular particles, and the outer surface of the porous support layer is coated with fibrous particles and/or It is preferred to include the step of forming a grain layer containing tabular grains. Examples of methods for bringing the slurry into contact include dip coating, spray coating, nozzle coating, liquid film transfer, and the like, and can be appropriately selected according to the type of slurry solution. Moreover, a suitable solvent and dispersant can be used for the slurry solution.
　本発明の流体分離膜の製造方法としては、本発明の多孔質材料に、流体分離膜の材料及び／又は流体分離膜の前駆体を含有する溶液をコーティングする工程を含むことが好ましい。コーティングする方法としては、例えば、ディップコート法、スプレーコート法、ノズルコート法、液膜転写法などが挙げられ、流体分離膜の材料に応じて適宜選択することができる。また、コーティング時には適宜溶媒、添加剤を用いることができる。 The method for producing the fluid separation membrane of the present invention preferably includes a step of coating the porous material of the present invention with a solution containing the material of the fluid separation membrane and/or the precursor of the fluid separation membrane. Coating methods include, for example, dip coating, spray coating, nozzle coating, and liquid film transfer, and can be appropriately selected according to the material of the fluid separation membrane. Moreover, a suitable solvent and additive can be used at the time of coating.
　また本発明の分離膜モジュールは、ケース中に本発明の流体分離膜を有する分離膜モジュールであり、より具体的には本発明の流体分離膜をケースに収納した形態である。分離膜モジュールは、流体の流れを制御し、流体分離膜を透過した流体を導く流路が形成されている。またこれら流体の流れを制御する目的でケースやシール材を用いることが好ましい。ケースの材質は特に限定されないが、耐圧性や耐熱性など使用環境に合わせて適宜選択されることが好ましく、金属、樹脂、炭素やこれらの複合体が例示される。
本発明の分離膜モジュールが適用可能なガス分離プロセスは特に限定されるものではないが、本発明の分離膜モジュールをプロセスの少なくとも一部に配置することにより、高い分離性能及び長期安定性が必要なプロセスにおいて好適に用いることができ、本発明の分離膜モジュールをプロセスの少なくとも一部に配置する。高い分離性能及び長期安定性が必要なプロセスとしては、例えば、発電所や高炉等の排気ガスからの二酸化炭素分離・貯蔵システム、石炭ガス化複合発電におけるガス化した燃料ガス中からの硫黄成分除去、バイオガスや天然ガスの精製、有機ハイドライドからの水素の精製等が挙げられる。 Moreover, the separation membrane module of the present invention is a separation membrane module having the fluid separation membrane of the present invention in a case, and more specifically, it has a form in which the fluid separation membrane of the present invention is housed in the case. The separation membrane module controls the flow of fluid and has a flow path for guiding the fluid that has permeated the fluid separation membrane. Moreover, it is preferable to use a case and a sealing material for the purpose of controlling the flow of these fluids. The material of the case is not particularly limited, but it is preferably selected appropriately according to the usage environment such as pressure resistance and heat resistance, and examples thereof include metal, resin, carbon, and composites thereof.
The gas separation process to which the separation membrane module of the present invention can be applied is not particularly limited, but high separation performance and long-term stability are required by placing the separation membrane module of the present invention in at least a part of the process. The separation membrane module of the present invention is placed in at least part of the process. Processes that require high separation performance and long-term stability include, for example, carbon dioxide separation and storage systems from the exhaust gas of power plants and blast furnaces, and removal of sulfur components from gasified fuel gas in integrated coal gasification combined cycle. , refining of biogas and natural gas, and refining of hydrogen from organic hydrides.
　かかるガス分離プロセスを少なくとも一部に用いた流体の製造方法としては、本発明の分離膜モジュールにおける精製工程の前後に別の精製工程や追加工程を含んでいてもよく、異なる精製工程で精製された精製流体と混合して流体を製造してもよい。別の精製工程や異なる精製工程としては、例えば、蒸留、吸着、吸収等が挙げられる。また、追加工程としては、例えば、別の流体と混合する成分調整等が挙げられる。 A method for producing a fluid that at least partly uses such a gas separation process may include another purification step or an additional step before or after the purification step in the separation membrane module of the present invention. may be mixed with a purified fluid to produce a fluid. Alternative or different purification steps include, for example, distillation, adsorption, absorption, and the like. Moreover, as an additional process, component adjustment etc. which mix with another fluid are mentioned, for example.
　本発明の製造方法により得られた流体は、高い分離性能と長期安定性が両立された本発明の分離膜モジュールで精製されることから、上記の追加工程におけるエネルギー消費が抑制され、低環境負荷な流体として各種産業用途において好適に用いることができる。 Since the fluid obtained by the production method of the present invention is purified by the separation membrane module of the present invention that achieves both high separation performance and long-term stability, the energy consumption in the additional steps is suppressed, and the environmental load is low. It can be suitably used in various industrial applications as a fluid.
（粒子層の剥離頻度）
　多孔質支持層の外表面に粒子層を付着させて得られた多孔質材料を、繊維の長手方向に１ｍ分採取してマイクロスコープで観察することにより、粒子層の剥離箇所をカウントした。なお、多孔質支持層が外表面に露出している部分を剥離箇所と判定した。　
（ガス透過速度の測定）
　各実施例および比較例により得られた流体分離膜を用いてモジュールを作製し、ガス透過速度Ｑを測定した。測定ガスとしては二酸化炭素およびメタンを用い、ＪＩＳ　Ｋ７１２６－１（２００６）の圧力センサ法に準拠して、測定温度２５℃の条件で、外圧式により二酸化炭素およびメタンの単位時間当たりの透過側の圧力変化を測定した。ここで、供給側と透過側の圧力差を０．１１ＭＰａに設定した。 (Particle layer separation frequency)
A 1-m portion of the porous material obtained by adhering the particle layer to the outer surface of the porous support layer was sampled in the longitudinal direction of the fiber and observed with a microscope to count the peeled portions of the particle layer. In addition, the portion where the porous support layer was exposed on the outer surface was determined as the peeled portion.
(Measurement of gas permeation rate)
Modules were produced using the fluid separation membranes obtained in each example and comparative example, and the gas permeation rate Q was measured. Carbon dioxide and methane are used as measurement gases, and the permeation side of carbon dioxide and methane per unit time is measured by an external pressure method at a measurement temperature of 25 ° C. in accordance with the pressure sensor method of JIS K7126-1 (2006). Pressure changes were measured. Here, the pressure difference between the supply side and the permeate side was set to 0.11 MPa.
　続いて、ガス透過速度Ｑを下記式により算出した。また、各成分のガス透過速度Ｑの比を分離係数αとした。ここで、膜面積はガスの透過に寄与する領域における外径および長さから算出した。 Then, the gas permeation rate Q was calculated by the following formula. Also, the ratio of the gas permeation rates Q of the respective components was defined as the separation factor α. Here, the membrane area was calculated from the outer diameter and length of the region contributing to gas permeation.
　ガス透過速度Ｑ＝［透過ガス量（ｍｏｌ）］／［膜面積（ｍ２）×時間（ｓ）×圧力差（Ｐａ）
　二酸化炭素のガス透過速度Ｑが３０ｎｍｏｌ／（ｍ２・Ｐａ・ｓ）以上である場合は「大」、ガス透過速度Ｑが２０ｎｍｏｌ／（ｍ２・Ｐａ・ｓ）以上３０ｎｍｏｌ／（ｍ２・Ｐａ・ｓ）未満である場合は「中」、ガス透過速度Ｑが２０ｎｍｏｌ／（ｍ２・Ｐａ・ｓ）未満である場合は「小」と判定した。
（二酸化炭素とメタンの分離係数）
　二酸化炭素およびメタンのガス透過速度Ｑを測定し、（二酸化炭素の透過速度）／（メタンの透過速度）を二酸化炭素とメタンの分離係数として算出した。二酸化炭素とメタンの分離係数が３０以上である場合は「最優」、分離係数が２５以上３０未満である場合は「優」分離係数が２０以上２５未満である場合は「良」分離係数が１０以上２０未満である場合は「可」、分離係数が１０未満である場合は「不可」と判定した。
（製造例１）
　ポリサイエンス社製ポリアクリロニトリル（ＰＡＮ）（ＭＷ１５万）１０重量部、シグマ・アルドリッチ社製ポリビニルピロリドン（ＰＶＰ）（ＭＷ４万）１０重量部および富士フイルム和光純薬製ジメチルスルホキシド（ＤＭＳＯ）８０重量部を混合し、１００℃で撹拌して紡糸原液を調製した。 Gas permeation rate Q = [permeation gas amount (mol)] / [membrane area (m 2 ) x time (s) x pressure difference (Pa)
“High” when the gas transmission rate Q of carbon dioxide is 30 nmol/(m 2 ·Pa·s) or more, and 30 nmol/(m 2 ·Pa) when the gas transmission rate Q is 20 nmol/(m 2 ·Pa·s) or more · s), it was judged to be "middle", and when the gas permeation rate Q was less than 20 nmol/(m 2 ·Pa·s), it was judged to be "low".
(separation factor of carbon dioxide and methane)
The gas permeation rate Q of carbon dioxide and methane was measured, and (permeation rate of carbon dioxide)/(permeation rate of methane) was calculated as the separation factor of carbon dioxide and methane. "Best" if the separation factor of carbon dioxide and methane is 30 or more, "Excellent" if the separation factor is 25 or more and less than 30 "Good" if the separation factor is 20 or more and less than 25 When the separation factor was 10 or more and less than 20, it was judged as "acceptable", and when the separation factor was less than 10, it was judged as "impossible".
(Production example 1)
10 parts by weight of polyacrylonitrile (PAN) (MW 150,000) manufactured by Polyscience, 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. They were mixed and stirred at 100° C. to prepare a spinning dope.
　得られた紡糸原液を２５℃まで冷却した後、同心円状の三重口金の口金を用いて、内管からＤＭＳＯ８０重量％水溶液を、中管から前記紡糸原液を、外管からＤＭＳＯ９０重量％水溶液をそれぞれ同時に吐出した後、２５℃の純水からなる凝固浴へ導き、ローラーに巻き取ることにより原糸を得た。得られた原糸を水洗した後、循環式乾燥機を用いて２５℃で２４時間乾燥し、中空糸状の多孔質炭素膜の前駆体を作製した。 After cooling the obtained spinning stock solution to 25° C., using concentric triple nozzles, an 80% by weight DMSO aqueous solution was introduced from the inner tube, the above spinning stock solution from the middle tube, and a 90% by weight DMSO aqueous solution from the outer tube. After being discharged at the same time, the fibers were introduced into a coagulation bath of pure water at 25° C. and wound around a roller to obtain a raw yarn. After the obtained filament was washed with water, it was dried at 25° C. for 24 hours using a circulating dryer to prepare a hollow fiber-like porous carbon membrane precursor.
　得られた多孔質炭素膜の前駆体を２５０℃の電気炉中に通し、空気雰囲気下において１時間加熱して不融化処理を行い、不融化糸を得た。続いて、不融化糸を炭化温度６５０℃で炭化処理し、外径０．３ｍｍ、中空面積比率４４％、空隙率４８％である、製造例１の多孔質支持層を得た。
（実施例１）
　製造例１の多孔質支持層に、カーボンナノチューブ（ＣＮＴ）のスラリーをディップコート法で塗布した後、循環式乾燥機を用いて５０℃で１２時間乾燥して、多孔質支持層の外表面にカーボンナノチューブ（ＣＮＴ）粒子層が付着してなる、多孔質材料を連続的に作製した。前述の方法により評価した結果、多孔質支持層と粒子層との界面での剥離は認められなかった。 The obtained precursor of the porous carbon film was passed through an electric furnace at 250° C. and heated in an air atmosphere for 1 hour to be infusible, thereby obtaining an infusible thread. Subsequently, the infusible yarn was carbonized at a carbonization temperature of 650° C. to obtain a porous support layer of Production Example 1 having an outer diameter of 0.3 mm, a hollow area ratio of 44%, and a porosity of 48%.
(Example 1)
After applying a slurry of carbon nanotubes (CNT) to the porous support layer of Production Example 1 by dip coating, it is dried at 50 ° C. for 12 hours using a circulation dryer, and is applied to the outer surface of the porous support layer. A porous material was continuously produced with a layer of carbon nanotube (CNT) particles attached. As a result of evaluation by the method described above, no peeling was observed at the interface between the porous support layer and the particle layer.
　得られた多孔質材料に、芳香族ポリイミド溶液をディップコート法で塗布、脱溶媒した後、循環式乾燥機により５０℃で１２時間乾燥して、多孔質材料の粒子層表面に芳香族ポリイミドを被膜形成した。続いて、芳香族ポリイミドを被膜形成した多孔質材料を、窒素雰囲気中７００℃で焼成することで、流体分離膜を連続的に作製した。 An aromatic polyimide solution was applied to the obtained porous material by dip coating, the solvent was removed, and then dried at 50° C. for 12 hours in a circulating dryer to apply the aromatic polyimide to the surface of the particle layer of the porous material. A film was formed. Subsequently, the porous material coated with the aromatic polyimide was baked at 700° C. in a nitrogen atmosphere to continuously produce a fluid separation membrane.
　前述の方法により評価した結果、繊維状粒子及び／又は平板状粒子の割合（アスペクト比が１０以上の粒子とアスペクト比が１０未満の粒子の合計のうち、アスペクト比が１０以上の粒子の割合）は９８体積％、繊維状粒子及び／または平板状粒子のアスペクト比は１６２３、最長長さＬｌは２１．９μｍ、最短長さＬｓは１４ｎｍ、粒子層の厚みは１．０μｍ、粒子層の空隙率は２８％であった。また、分離機能層の炭素元素比率は８３．４ａｔｏｍｉｃ％、分離機能層の弾性率は２８ＧＰａ、分離機能層と粒子層の複合割合は２４体積％であった。 As a result of evaluation by the above method, the ratio of fibrous grains and/or tabular grains (percentage of grains with an aspect ratio of 10 or more in the total of grains with an aspect ratio of 10 or more and grains with an aspect ratio of less than 10) is 98% by volume, the fibrous particles and/or tabular particles have an aspect ratio of 1623, the longest length Ll is 21.9 μm, the shortest length Ls is 14 nm, the thickness of the particle layer is 1.0 μm, and the porosity of the particle layer was 28%. In addition, the carbon element ratio of the separation functional layer was 83.4 atomic %, the elastic modulus of the separation functional layer was 28 GPa, and the composite ratio of the separation functional layer and the particle layer was 24 volume %.
　得られた流体分離膜の二酸化炭素のガス透過速度は「大」、二酸化炭素とメタンの分離係数は「優」であった。評価結果を表１に示す。
（実施例２）
実施例１のカーボンナノチューブ（ＣＮＴ）のスラリーに代えて、カーボンナノチューブ（ＣＮＴ）とカーボンブラック（ＣＢ）を９：１の体積割合で混合したスラリーを用いた以外は実施例１と同様にして、実施例２の流体分離膜を作製した。
前述の方法により評価した結果、繊維状粒子及び／又は平板状粒子の割合は９１体積％、繊維状粒子及び／または平板状粒子のアスペクト比は１５９０、最長長さＬｌは１１．２μｍ、最短長さＬｓは７ｎｍ、粒子層の厚みは０．８μｍ、粒子層の空隙率は２２％であった。また、分離機能層の炭素元素比率は８３．４ａｔｏｍｉｃ％、分離機能層の弾性率は２６ＧＰａ、分離機能層と粒子層の複合割合は２１体積％であった。 The gas permeation rate of carbon dioxide of the obtained fluid separation membrane was "high", and the separation coefficient between carbon dioxide and methane was "excellent". Table 1 shows the evaluation results.
(Example 2)
In the same manner as in Example 1, except that the slurry of carbon nanotubes (CNT) in Example 1 was replaced with a slurry in which carbon nanotubes (CNT) and carbon black (CB) were mixed at a volume ratio of 9:1. A fluid separation membrane of Example 2 was fabricated.
As a result of evaluation by the above-described method, the proportion of fibrous particles and/or tabular particles was 91% by volume, the aspect ratio of fibrous particles and/or tabular particles was 1590, the longest length Ll was 11.2 μm, and the shortest length The thickness Ls was 7 nm, the thickness of the particle layer was 0.8 μm, and the porosity of the particle layer was 22%. Further, the carbon element ratio of the separation functional layer was 83.4 atomic %, the elastic modulus of the separation functional layer was 26 GPa, and the composite ratio of the separation functional layer and the particle layer was 21 volume %.
　多孔質材料には多孔質支持層と粒子層との界面での剥離は認められず、実施例２の流体分離膜の二酸化炭素のガス透過速度は「中」、二酸化炭素とメタンの分離係数は「最優」であった。評価結果を表１に併せて示す。
（実施例３）
実施例１のカーボンナノチューブ（ＣＮＴ）のスラリーに代えて、カーボンナノチューブ（ＣＮＴ）とグラフェンを１：１の体積割合で混合したスラリーを用いた以外は実施例１と同様にして、実施例３の流体分離膜を作製した。
前述の方法により評価した結果、繊維状粒子及び／又は平板状粒子の割合は９８体積％、繊維状粒子及び／または平板状粒子のアスペクト比は１１１４、最長長さＬｌは９．６μｍ、最短長さＬｓは９ｎｍ、粒子層の厚みは０．９μｍ、粒子層の空隙率は２６％であった。また、分離機能層の炭素元素比率は８３．６ａｔｏｍｉｃ％、分離機能層の弾性率は２７ＧＰａ、分離機能層と粒子層の複合割合は２１体積％であった。 No peeling was observed at the interface between the porous support layer and the particle layer in the porous material, and the gas permeation rate of carbon dioxide in the fluid separation membrane of Example 2 was "medium", and the separation factor of carbon dioxide and methane was was the "best". The evaluation results are also shown in Table 1.
(Example 3)
Example 3 was prepared in the same manner as in Example 1 except that instead of the carbon nanotube (CNT) slurry in Example 1, a slurry in which carbon nanotubes (CNT) and graphene were mixed at a volume ratio of 1:1 was used. A fluid separation membrane was fabricated.
As a result of evaluation by the above-described method, the proportion of fibrous particles and/or tabular particles was 98% by volume, the aspect ratio of fibrous particles and/or tabular particles was 1114, the longest length Ll was 9.6 μm, and the shortest length The thickness Ls was 9 nm, the thickness of the particle layer was 0.9 μm, and the porosity of the particle layer was 26%. The separation functional layer had a carbon element ratio of 83.6 atomic %, an elastic modulus of the separation functional layer of 27 GPa, and a composite ratio of the separation functional layer and the particle layer of 21 volume %.
　多孔質材料には多孔質支持層と粒子層との界面での剥離は認められず、実施例３の流体分離膜の二酸化炭素のガス透過速度は「中」、二酸化炭素とメタンの分離係数は「優」であった。評価結果を表１に併せて示す。
（実施例４）
実施例１のカーボンナノチューブ（ＣＮＴ）のスラリーに代えて、カーボンナノチューブ（ＣＮＴ）とカーボンブラック（ＣＢ）を１：４の体積割合で混合したスラリーを用いた以外は実施例１と同様にして、実施例４の流体分離膜を作製した。
前述の方法により評価した結果、繊維状粒子及び／又は平板状粒子の割合は１８体積％、繊維状粒子及び／または平板状粒子のアスペクト比は１７５６、最長長さＬｌは１３．４μｍ、最短長さＬｓは８ｎｍ、粒子層の厚みは０．９μｍ、粒子層の空隙率は４％であった。また、分離機能層の炭素元素比率は８３．５ａｔｏｍｉｃ％、分離機能層の弾性率は２２ＧＰａ、分離機能層と粒子層の複合割合は１６体積％であった。 No peeling was observed at the interface between the porous support layer and the particle layer in the porous material. It was "excellent". The evaluation results are also shown in Table 1.
(Example 4)
In the same manner as in Example 1, except that instead of the carbon nanotube (CNT) slurry in Example 1, a slurry in which carbon nanotubes (CNT) and carbon black (CB) were mixed at a volume ratio of 1:4 was used. A fluid separation membrane of Example 4 was prepared.
As a result of evaluation by the above-described method, the proportion of fibrous particles and/or tabular particles was 18% by volume, the aspect ratio of fibrous particles and/or tabular particles was 1756, the longest length Ll was 13.4 μm, and the shortest length was 13.4 μm. The thickness Ls was 8 nm, the thickness of the particle layer was 0.9 μm, and the porosity of the particle layer was 4%. Further, the carbon element ratio of the separation functional layer was 83.5 atomic %, the elastic modulus of the separation functional layer was 22 GPa, and the composite ratio of the separation functional layer and the particle layer was 16 volume %.
　多孔質材料には多孔質支持層と粒子層との界面での剥離が認められ、剥離頻度は７箇所/ｍであった。実施例４の流体分離膜の二酸化炭素のガス透過速度は「小」、二酸化炭素とメタンの分離係数は「優」であった。評価結果を表１に併せて示す。
（実施例５）
実施例１のカーボンナノチューブ（ＣＮＴ）のスラリーにおいて、アスペクト比の大きいカーボンナノチューブ（ＣＮＴ）を用いた以外は実施例１と同様にして、実施例５の流体分離膜を作製した。
前述の方法により評価した結果、繊維状粒子及び／又は平板状粒子の割合は９９体積％、繊維状粒子及び／または平板状粒子のアスペクト比は２５９２、最長長さＬｌは２４．１μｍ、最短長さＬｓは９ｎｍ、粒子層の厚みは０．８μｍ、粒子層の空隙率は３５％であった。また、分離機能層の炭素元素比率は８３．４ａｔｏｍｉｃ％、分離機能層の弾性率は２８ＧＰａ、分離機能層と粒子層の複合割合は２２体積％であった。 Delamination was observed at the interface between the porous support layer and the particle layer in the porous material, and the delamination frequency was 7 locations/m. The gas permeation rate of carbon dioxide of the fluid separation membrane of Example 4 was "low", and the separation factor between carbon dioxide and methane was "excellent". The evaluation results are also shown in Table 1.
(Example 5)
A fluid separation membrane of Example 5 was produced in the same manner as in Example 1, except that carbon nanotubes (CNT) having a large aspect ratio were used in the carbon nanotube (CNT) slurry of Example 1.
As a result of evaluation by the above-described method, the ratio of fibrous particles and/or tabular particles was 99% by volume, the aspect ratio of fibrous particles and/or tabular particles was 2592, the longest length Ll was 24.1 μm, and the shortest length The thickness Ls was 9 nm, the thickness of the particle layer was 0.8 μm, and the porosity of the particle layer was 35%. In addition, the carbon element ratio of the separation functional layer was 83.4 atomic %, the elastic modulus of the separation functional layer was 28 GPa, and the composite ratio of the separation functional layer and the particle layer was 22 volume %.
　多孔質材料には多孔質支持層と粒子層との界面での剥離は認められず、実施例５の流体分離膜の二酸化炭素のガス透過速度は「大」、二酸化炭素とメタンの分離係数は「良」であった。評価結果を表１に併せて示す。
（実施例６）
実施例１のカーボンナノチューブ（ＣＮＴ）のスラリーにおいて、アスペクト比の大きいカーボンナノチューブ（ＣＮＴ）を用いた以外は実施例１と同様にして、実施例５の流体分離膜を作製した。
前述の方法により評価した結果、繊維状粒子及び／又は平板状粒子の割合は９８体積％、繊維状粒子及び／または平板状粒子のアスペクト比は１１０４０、最長長さＬｌは１２１．５μｍ、最短長さＬｓは１１ｎｍ、粒子層の厚みは１．０μｍ、粒子層の空隙率は５４％であった。また、分離機能層の炭素元素比率は８３．３ａｔｏｍｉｃ％、分離機能層の弾性率は２５ＧＰａ、分離機能層と粒子層の複合割合は２９体積％であった。 No peeling was observed at the interface between the porous support layer and the particle layer in the porous material, and the gas permeation rate of carbon dioxide in the fluid separation membrane of Example 5 was "high", and the separation factor of carbon dioxide and methane was It was "good". The evaluation results are also shown in Table 1.
(Example 6)
A fluid separation membrane of Example 5 was produced in the same manner as in Example 1, except that carbon nanotubes (CNT) having a large aspect ratio were used in the carbon nanotube (CNT) slurry of Example 1.
As a result of evaluation by the above-described method, the proportion of fibrous particles and/or tabular particles was 98% by volume, the aspect ratio of fibrous particles and/or tabular particles was 11040, the longest length Ll was 121.5 μm, and the shortest length was 121.5 μm. The thickness Ls was 11 nm, the thickness of the particle layer was 1.0 μm, and the porosity of the particle layer was 54%. In addition, the carbon element ratio of the separation functional layer was 83.3 atomic %, the elastic modulus of the separation functional layer was 25 GPa, and the composite ratio of the separation functional layer and the particle layer was 29 volume %.
　多孔質材料には多孔質支持層と粒子層との界面での剥離は認められず、実施例６の流体分離膜の二酸化炭素のガス透過速度は「大」、二酸化炭素とメタンの分離係数は「可」であった。評価結果を表１に併せて示す。
（実施例７）
実施例１のカーボンナノチューブ（ＣＮＴ）のスラリーに代えて、グラフェンとカーボンブラック（ＣＢ）を９：１の体積割合で混合したスラリーを用いた以外は実施例１と同様にして、実施例７の流体分離膜を作製した。
前述の方法により評価した結果、繊維状粒子及び／又は平板状粒子の割合は９２体積％、繊維状粒子及び／または平板状粒子のアスペクト比は７１８、最長長さＬｌは２．８μｍ、最短長さＬｓは４ｎｍ、粒子層の厚みは０．７μｍ、粒子層の空隙率は１８％であった。また、分離機能層の炭素元素比率は８３．５ａｔｏｍｉｃ％、分離機能層の弾性率は２４ＧＰａ、分離機能層と粒子層の複合割合は１４体積％であった。 No peeling was observed at the interface between the porous support layer and the particle layer in the porous material, the gas permeation rate of carbon dioxide in the fluid separation membrane of Example 6 was "high", and the separation factor of carbon dioxide and methane was It was "possible". The evaluation results are also shown in Table 1.
(Example 7)
Example 7 was prepared in the same manner as in Example 1 except that a slurry in which graphene and carbon black (CB) were mixed at a volume ratio of 9:1 was used instead of the carbon nanotube (CNT) slurry in Example 1. A fluid separation membrane was fabricated.
As a result of evaluation by the above-described method, the proportion of fibrous particles and/or tabular particles was 92% by volume, the aspect ratio of fibrous particles and/or tabular particles was 718, the longest length Ll was 2.8 µm, and the shortest length The thickness Ls was 4 nm, the thickness of the particle layer was 0.7 μm, and the porosity of the particle layer was 18%. Further, the carbon element ratio of the separation functional layer was 83.5 atomic %, the elastic modulus of the separation functional layer was 24 GPa, and the composite ratio of the separation functional layer and the particle layer was 14 volume %.
　多孔質材料には多孔質支持層と粒子層との界面での剥離は認められず、実施例７の流体分離膜の二酸化炭素のガス透過速度は「中」、二酸化炭素とメタンの分離係数は「優」であった。評価結果を表１に併せて示す。
（実施例８）
実施例１のカーボンナノチューブ（ＣＮＴ）のスラリーに代えて、グラフェンとカーボンブラック（ＣＢ）を９：１の体積割合で混合したスラリーを用いた以外は実施例１と同様にして、実施例８の流体分離膜を作製した。
前述の方法により評価した結果、繊維状粒子及び／又は平板状粒子の割合は９２体積％、繊維状粒子及び／または平板状粒子のアスペクト比は９２、最長長さＬｌは０．８μｍ、最短長さＬｓは９ｎｍ、粒子層の厚みは０．８μｍ、粒子層の空隙率は１９％であった。また、分離機能層の炭素元素比率は８３．６ａｔｏｍｉｃ％、分離機能層の弾性率は２２ＧＰａ、分離機能層と粒子層の複合割合は１７体積％であった。 No peeling was observed at the interface between the porous support layer and the particle layer in the porous material. It was "excellent". The evaluation results are also shown in Table 1.
(Example 8)
Example 8 was prepared in the same manner as in Example 1 except that a slurry in which graphene and carbon black (CB) were mixed at a volume ratio of 9: 1 was used instead of the carbon nanotube (CNT) slurry in Example 1. A fluid separation membrane was fabricated.
As a result of evaluation by the above-described method, the ratio of fibrous particles and/or tabular particles was 92% by volume, the aspect ratio of fibrous particles and/or tabular particles was 92, the longest length Ll was 0.8 µm, and the shortest length The thickness Ls was 9 nm, the thickness of the particle layer was 0.8 μm, and the porosity of the particle layer was 19%. In addition, the carbon element ratio of the separation functional layer was 83.6 atomic %, the elastic modulus of the separation functional layer was 22 GPa, and the composite ratio of the separation functional layer and the particle layer was 17 volume %.
　多孔質材料には多孔質支持層と粒子層との界面での剥離が認められ、剥離頻度は５箇所/ｍであった。実施例８の流体分離膜の二酸化炭素のガス透過速度は「中」、二酸化炭素とメタンの分離係数は「優」であった。評価結果を表１に併せて示す。
（実施例９）
実施例１のカーボンナノチューブ（ＣＮＴ）のスラリーに代えて、グラフェンとカーボンブラック（ＣＢ）を９：１の体積割合で混合したスラリーを用いた以外は実施例１と同様にして、実施例９の流体分離膜を作製した。
前述の方法により評価した結果、繊維状粒子及び／又は平板状粒子の割合は９０体積％、繊維状粒子及び／または平板状粒子のアスペクト比は１８、最長長さＬｌは０．３μｍ、最短長さＬｓは１７ｎｍ、粒子層の厚みは０．８μｍ、粒子層の空隙率は２２％であった。また、分離機能層の炭素元素比率は８３．５ａｔｏｍｉｃ％、分離機能層の弾性率は１９ＧＰａ、分離機能層と粒子層の複合割合は２０体積％であった。 Peeling was observed at the interface between the porous support layer and the particle layer in the porous material, and the peeling frequency was 5 locations/m. The gas permeation rate of carbon dioxide of the fluid separation membrane of Example 8 was "medium", and the separation factor between carbon dioxide and methane was "excellent". The evaluation results are also shown in Table 1.
(Example 9)
Example 9 was prepared in the same manner as in Example 1 except that a slurry in which graphene and carbon black (CB) were mixed at a volume ratio of 9: 1 was used instead of the carbon nanotube (CNT) slurry in Example 1. A fluid separation membrane was fabricated.
As a result of evaluation by the above-described method, the proportion of fibrous particles and/or tabular particles was 90% by volume, the aspect ratio of fibrous particles and/or tabular particles was 18, the longest length Ll was 0.3 μm, and the shortest length The thickness Ls was 17 nm, the thickness of the particle layer was 0.8 μm, and the porosity of the particle layer was 22%. Further, the carbon element ratio of the separation functional layer was 83.5 atomic %, the elastic modulus of the separation functional layer was 19 GPa, and the composite ratio of the separation functional layer and the particle layer was 20 volume %.
　多孔質材料には多孔質支持層と粒子層との界面での剥離が認められ、剥離頻度は１４箇所/ｍであった。実施例９の流体分離膜の二酸化炭素のガス透過速度は「中」、二酸化炭素とメタンの分離係数は「良」であった。評価結果を表２に併せて示す。
（実施例１０）
カーボンナノチューブ（ＣＮＴ）粒子層が薄くなるよう塗布した以外は実施例１と同様にして、実施例１０の流体分離膜を作製した。
前述の方法により評価した結果、繊維状粒子及び／又は平板状粒子の割合は９８体積％、繊維状粒子及び／または平板状粒子のアスペクト比は１７１０、最長長さＬｌは２６．６μｍ、最短長さＬｓは１６ｎｍ、粒子層の厚みは０．４μｍ、粒子層の空隙率は２５％であった。また、分離機能層の炭素元素比率は８３．３ａｔｏｍｉｃ％、分離機能層の弾性率は３０ＧＰａ、分離機能層と粒子層の複合割合は２４体積％であった。 Delamination was observed at the interface between the porous support layer and the particle layer in the porous material, and the delamination frequency was 14 locations/m. The gas permeation rate of carbon dioxide of the fluid separation membrane of Example 9 was "medium", and the separation factor between carbon dioxide and methane was "good". The evaluation results are also shown in Table 2.
(Example 10)
A fluid separation membrane of Example 10 was produced in the same manner as in Example 1, except that the carbon nanotube (CNT) particle layer was applied so as to be thin.
As a result of evaluation by the above-described method, the proportion of fibrous particles and/or tabular particles was 98% by volume, the aspect ratio of fibrous particles and/or tabular particles was 1710, the longest length Ll was 26.6 μm, and the shortest length The thickness Ls was 16 nm, the thickness of the particle layer was 0.4 μm, and the porosity of the particle layer was 25%. Further, the carbon element ratio of the separation functional layer was 83.3 atomic %, the elastic modulus of the separation functional layer was 30 GPa, and the composite ratio of the separation functional layer and the particle layer was 24 volume %.
　多孔質材料には多孔質支持層と粒子層との界面での剥離は認められず、実施例１０の流体分離膜の二酸化炭素のガス透過速度は「大」、二酸化炭素とメタンの分離係数は「良」であった。評価結果を表２に併せて示す。
（実施例１１）
カーボンナノチューブ（ＣＮＴ）粒子層が薄くなるよう塗布した以外は実施例１と同様にして、実施例１１の流体分離膜を作製した。
前述の方法により評価した結果、繊維状粒子及び／又は平板状粒子の割合は１００体積％、繊維状粒子及び／または平板状粒子のアスペクト比は１６７４、最長長さＬｌは２４．３μｍ、最短長さＬｓは１５ｎｍ、粒子層の厚みは０．１μｍ、粒子層の空隙率は１８％であった。また、分離機能層の炭素元素比率は８３．４ａｔｏｍｉｃ％、分離機能層の弾性率は２８ＧＰａ、分離機能層と粒子層の複合割合は２６体積％であった。 No peeling was observed at the interface between the porous support layer and the particle layer in the porous material, and the gas permeation rate of carbon dioxide in the fluid separation membrane of Example 10 was "high", and the separation factor of carbon dioxide and methane was It was "good". The evaluation results are also shown in Table 2.
(Example 11)
A fluid separation membrane of Example 11 was produced in the same manner as in Example 1, except that the carbon nanotube (CNT) particle layer was applied so as to be thin.
As a result of evaluation by the above-described method, the ratio of fibrous particles and/or tabular particles was 100% by volume, the aspect ratio of fibrous particles and/or tabular particles was 1674, the longest length Ll was 24.3 μm, and the shortest length The thickness Ls was 15 nm, the thickness of the particle layer was 0.1 μm, and the porosity of the particle layer was 18%. Further, the carbon element ratio of the separation functional layer was 83.4 atomic %, the elastic modulus of the separation functional layer was 28 GPa, and the composite ratio of the separation functional layer and the particle layer was 26 volume %.
　多孔質材料には多孔質支持層と粒子層との界面での剥離が認められ、剥離頻度は５箇所/ｍであった。実施例１１の流体分離膜の二酸化炭素のガス透過速度は「大」、二酸化炭素とメタンの分離係数は「良」であった。評価結果を表２に併せて示す。
（実施例１２）
カーボンナノチューブ（ＣＮＴ）粒子層が厚くなるよう塗布した以外は実施例１と同様にして、実施例１２の流体分離膜を作製した。
前述の方法により評価した結果、繊維状粒子及び／又は平板状粒子の割合は９８体積％、繊維状粒子及び／または平板状粒子のアスペクト比は１５３４、最長長さＬｌは１９．８μｍ、最短長さＬｓは１３ｎｍ、粒子層の厚みは１２．４μｍ、粒子層の空隙率は２８％であった。また、分離機能層の炭素元素比率は８３．２ａｔｏｍｉｃ％、分離機能層の弾性率は２７ＧＰａ、分離機能層と粒子層の複合割合は２２体積％であった。 Peeling was observed at the interface between the porous support layer and the particle layer in the porous material, and the peeling frequency was 5 locations/m. The gas permeation rate of carbon dioxide of the fluid separation membrane of Example 11 was "high", and the separation factor between carbon dioxide and methane was "good". The evaluation results are also shown in Table 2.
(Example 12)
A fluid separation membrane of Example 12 was produced in the same manner as in Example 1, except that the carbon nanotube (CNT) particle layer was coated so as to be thick.
As a result of evaluation by the above-described method, the proportion of fibrous particles and/or tabular particles was 98% by volume, the aspect ratio of fibrous particles and/or tabular particles was 1534, the longest length Ll was 19.8 µm, and the shortest length The thickness Ls was 13 nm, the thickness of the particle layer was 12.4 μm, and the porosity of the particle layer was 28%. Further, the carbon element ratio of the separation functional layer was 83.2 atomic %, the elastic modulus of the separation functional layer was 27 GPa, and the composite ratio of the separation functional layer and the particle layer was 22 volume %.
　多孔質材料には多孔質支持層と粒子層との界面での剥離は認められず、実施例１２の流体分離膜の二酸化炭素のガス透過速度は「中」、二酸化炭素とメタンの分離係数は「優」であった。評価結果を表２に併せて示す。
（実施例１３）
カーボンナノチューブ（ＣＮＴ）粒子層が厚くなるよう塗布した以外は実施例１と同様にして、実施例１３の流体分離膜を作製した。
前述の方法により評価した結果、繊維状粒子及び／又は平板状粒子の割合は９５体積％、繊維状粒子及び／または平板状粒子のアスペクト比は１５５２、最長長さＬｌは２０．６μｍ、最短長さＬｓは１３ｎｍ、粒子層の厚みは１０７．３μｍ、粒子層の空隙率は３０％であった。また、分離機能層の炭素元素比率は８３．５ａｔｏｍｉｃ％、分離機能層の弾性率は２８ＧＰａ、分離機能層と粒子層の複合割合は２０体積％であった。 No peeling was observed at the interface between the porous support layer and the particle layer in the porous material. It was "excellent". The evaluation results are also shown in Table 2.
(Example 13)
A fluid separation membrane of Example 13 was produced in the same manner as in Example 1, except that the carbon nanotube (CNT) particle layer was coated so as to be thick.
As a result of evaluation by the above-described method, the proportion of fibrous particles and/or tabular particles was 95% by volume, the aspect ratio of fibrous particles and/or tabular particles was 1552, the longest length Ll was 20.6 μm, and the shortest length The thickness Ls was 13 nm, the thickness of the particle layer was 107.3 μm, and the porosity of the particle layer was 30%. Further, the carbon element ratio of the separation functional layer was 83.5 atomic %, the elastic modulus of the separation functional layer was 28 GPa, and the composite ratio of the separation functional layer and the particle layer was 20 volume %.
　多孔質材料には多孔質支持層と粒子層との界面での剥離は認められず、実施例１３の流体分離膜の二酸化炭素のガス透過速度は「小」、二酸化炭素とメタンの分離係数は「優」であった。評価結果を表２に併せて示す。
（実施例１４）
芳香族ポリイミドを被膜形成した多孔質材料を、窒素雰囲気中７００℃で焼成せずにそのまま流体分離膜とした以外は実施例１と同様にして、実施例１４の流体分離膜を作製した。
前述の方法により評価した結果、繊維状粒子及び／又は平板状粒子の割合は９９体積％、繊維状粒子及び／または平板状粒子のアスペクト比は１６６２、最長長さＬｌは１９．５μｍ、最短長さＬｓは１２ｎｍ、粒子層の厚みは０．９μｍ、粒子層の空隙率は２８％であった。また、分離機能層の炭素元素比率は７５．６ａｔｏｍｉｃ％、分離機能層の弾性率は４ＧＰａ、分離機能層と粒子層の複合割合は２０体積％であった。 No peeling was observed at the interface between the porous support layer and the particle layer in the porous material, the gas permeation rate of carbon dioxide in the fluid separation membrane of Example 13 was "low", and the separation factor of carbon dioxide and methane was It was "excellent". The evaluation results are also shown in Table 2.
(Example 14)
A fluid separation membrane of Example 14 was produced in the same manner as in Example 1, except that the porous material coated with the aromatic polyimide was used as the fluid separation membrane as it was without being baked at 700° C. in a nitrogen atmosphere.
As a result of evaluation by the above-described method, the ratio of fibrous particles and/or tabular particles was 99% by volume, the aspect ratio of fibrous particles and/or tabular particles was 1662, the longest length Ll was 19.5 μm, and the shortest length was 19.5 μm. The thickness Ls was 12 nm, the thickness of the particle layer was 0.9 μm, and the porosity of the particle layer was 28%. Further, the carbon element ratio of the separation functional layer was 75.6 atomic %, the elastic modulus of the separation functional layer was 4 GPa, and the composite ratio of the separation functional layer and the particle layer was 20 volume %.
　多孔質材料には多孔質支持層と粒子層との界面での剥離は認められず、実施例１４の流体分離膜の二酸化炭素のガス透過速度は「中」、二酸化炭素とメタンの分離係数は「良」であった。評価結果を表２に併せて示す。
（比較例１）
実施例１のカーボンナノチューブ（ＣＮＴ）のスラリーに代えて、カーボンブラック（ＣＢ）のスラリーを用いた以外は実施例１と同様にして、比較例１の流体分離膜を作製した。
前述の方法により評価した結果、繊維状粒子及び／又は平板状粒子の割合は０体積％、粒子層の厚みは０．８μｍ、粒子層の空隙率は６％であった。また、分離機能層の炭素元素比率は８３．４ａｔｏｍｉｃ％、分離機能層の弾性率は２０ＧＰａ、分離機能層と粒子層の複合割合は２８体積％であった。 No peeling was observed at the interface between the porous support layer and the particle layer in the porous material. It was "good". The evaluation results are also shown in Table 2.
(Comparative example 1)
A fluid separation membrane of Comparative Example 1 was produced in the same manner as in Example 1, except that a carbon black (CB) slurry was used instead of the carbon nanotube (CNT) slurry of Example 1.
As a result of evaluation by the above method, the ratio of fibrous particles and/or tabular particles was 0% by volume, the thickness of the particle layer was 0.8 μm, and the porosity of the particle layer was 6%. Further, the carbon element ratio of the separation functional layer was 83.4 atomic %, the elastic modulus of the separation functional layer was 20 GPa, and the composite ratio of the separation functional layer and the particle layer was 28 volume %.
　多孔質材料には多孔質支持層と粒子層との界面での剥離が認められ、剥離頻度は２３箇所/ｍであった。比較例１の流体分離膜は、多孔質材料と分離機能層との剥離が認められ、流体分離膜として機能しなかった。評価結果を表２に併せて示す。
（比較例２）
実施例１のカーボンナノチューブ（ＣＮＴ）のスラリーに代えて、球状シリカ微粒子のスラリーを用いた以外は実施例１と同様にして、比較例２の流体分離膜を作製した。
前述の方法により評価した結果、繊維状粒子及び／又は平板状粒子の割合は０体積％、粒子層の厚みは１．０μｍ、粒子層の空隙率は２５％であった。また、分離機能層の炭素元素比率は８３．２ａｔｏｍｉｃ％、分離機能層の弾性率は２３ＧＰａ、分離機能層と粒子層の複合割合は１６体積％であった。
多孔質材料には多孔質支持層と粒子層との界面での剥離が認められ、剥離頻度は３５箇所/ｍであった。比較例２の流体分離膜は、多孔質材料と分離機能層との剥離が認められ、流体分離膜として機能しなかった。評価結果を表２に併せて示す。 Delamination was observed at the interface between the porous support layer and the particle layer in the porous material, and the delamination frequency was 23 locations/m. The fluid separation membrane of Comparative Example 1 did not function as a fluid separation membrane because separation between the porous material and the separation functional layer was observed. The evaluation results are also shown in Table 2.
(Comparative example 2)
A fluid separation membrane of Comparative Example 2 was produced in the same manner as in Example 1, except that the slurry of spherical silica fine particles was used in place of the slurry of carbon nanotubes (CNT) of Example 1.
As a result of evaluation by the above method, the ratio of fibrous particles and/or tabular particles was 0% by volume, the thickness of the particle layer was 1.0 μm, and the porosity of the particle layer was 25%. Further, the carbon element ratio of the separation functional layer was 83.2 atomic %, the elastic modulus of the separation functional layer was 23 GPa, and the composite ratio of the separation functional layer and the particle layer was 16 volume %.
Delamination was observed at the interface between the porous support layer and the particle layer in the porous material, and the delamination frequency was 35 locations/m. The fluid separation membrane of Comparative Example 2 did not function as a fluid separation membrane because separation between the porous material and the separation functional layer was observed. The evaluation results are also shown in Table 2.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　本発明の流体分離膜は、発電所や高炉等の排気ガスからの二酸化炭素分離・貯蔵システム、石炭ガス化複合発電におけるガス化した燃料ガス中からの硫黄成分除去、バイオガスや天然ガスの精製、有機ハイドライドからの水素精製等に好適に用いることができる。 The fluid separation membrane of the present invention is used for 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, purification of biogas and natural gas. , hydrogen purification from organic hydride, and the like.

Claims (23)

  1. 　表面が分離機能層で被覆された繊維状の多孔質支持層を有し、前記多孔質支持層と前記分離機能層との間の少なくとも一部に粒子層が介在し、前記粒子層は、繊維状粒子及び／または平板状粒子を含有する流体分離膜。 A fibrous porous support layer having a surface coated with a separation functional layer, a particle layer interposed at least partially between the porous support layer and the separation functional layer, the particle layer comprising fibers A fluid separation membrane containing shaped particles and/or tabular particles.
  2. 　前記分離機能層を構成する元素のうち、炭素が占める割合が７０ａｔｏｍｉｃ％以上９９．５ａｔｏｍｉｃ％以下である請求項１に記載の流体分離膜。 The fluid separation membrane according to claim 1, wherein carbon accounts for 70 atomic % or more and 99.5 atomic % or less of the elements constituting the separation functional layer.
  3. 前記分離機能層の弾性率が１０ＧＰａ以上３００ＧＰａ以下である請求項１に記載の流体分離膜。 2. The fluid separation membrane according to claim 1, wherein the separation functional layer has an elastic modulus of 10 GPa or more and 300 GPa or less.
  4. 前記流体がガスである請求項1に記載の流体分離膜。 2. The fluid separation membrane according to claim 1, wherein said fluid is gas.
  5. 　前記多孔質支持層が中空糸状である請求項１に記載の流体分離膜。 The fluid separation membrane according to claim 1, wherein the porous support layer is hollow fiber.
  6. 前記繊維状粒子及び／または前記平板状粒子の最長長さＬｌが、０．０５μｍ以上１０００μｍ以下である請求項１に記載の流体分離膜。 2. The fluid separation membrane according to claim 1, wherein the fibrous particles and/or the tabular particles have a maximum length Ll of 0.05 μm or more and 1000 μm or less.
  7. 　前記繊維状粒子及び／又は前記平板状粒子のアスペクト比が、２０以上１００００以下である請求項１に記載の流体分離膜。 The fluid separation membrane according to claim 1, wherein the fibrous particles and/or the tabular particles have an aspect ratio of 20 or more and 10,000 or less.
  8. 　前記繊維状粒子及び／又は前記平板状粒子が、セルロースナノファイバー、カーボンナノホーン、カーボンナノリボン、カーボンナノチューブ、グラフェン、及び酸化グラフェンからなる群より選ばれる少なくとも１種類を含有する請求項１に記載の流体分離膜。 2. The fluid according to claim 1, wherein the fibrous particles and/or the tabular particles contain at least one selected from the group consisting of cellulose nanofibers, carbon nanohorns, carbon nanoribbons, carbon nanotubes, graphene, and graphene oxide. Separation membrane.
  9. 　繊維状の多孔質支持層及び粒子層を有する多孔質材料であって、
    　前記粒子層は、前記多孔質支持層の少なくとも一部の表面に接するように配置されており、前記粒子層は、繊維状粒子及び／または平板状粒子を含有する多孔質材料。     A porous material having a fibrous porous support layer and a particle layer,
    The particle layer is arranged so as to be in contact with at least a part of the surface of the porous support layer, and the particle layer is a porous material containing fibrous particles and/or tabular particles.
  10. 　前記多孔質支持層が中空糸状である請求項９に記載の多孔質材料。 The porous material according to claim 9, wherein the porous support layer is hollow fiber.
  11. 　前記中空糸状の多孔質支持層の外径が０．０２ｍｍ以上５０ｍｍ以下である請求項１０に記載の多孔質材料。 The porous material according to claim 10, wherein the hollow fiber porous support layer has an outer diameter of 0.02 mm or more and 50 mm or less.
  12. 　前記多孔質支持層の空隙率が１０％以上８０％以下である請求項９に記載の多孔質材料。 The porous material according to claim 9, wherein the porous support layer has a porosity of 10% or more and 80% or less.
  13. 　前記繊維状粒子及び／又は前記平板状粒子のアスペクト比が２０以上１００００以下である、請求項９に記載の多孔質材料。 The porous material according to claim 9, wherein the fibrous particles and/or the tabular particles have an aspect ratio of 20 or more and 10,000 or less.
  14. 　前記多孔質支持層が無機材料からなる請求項９に記載の多孔質材料。 The porous material according to claim 9, wherein the porous support layer is made of an inorganic material.
  15. 　前記粒子層の空隙率が３％以上５０％以下である請求項９に記載の多孔質材料。 The porous material according to claim 9, wherein the particle layer has a porosity of 3% or more and 50% or less.
  16. 　前記粒子層の平均厚みが０．１μｍ以上１００μｍ以下である請求項９に記載の多孔質材料。 The porous material according to claim 9, wherein the particle layer has an average thickness of 0.1 µm or more and 100 µm or less.
  17. 　前記繊維状粒子及び／又は前記平板状粒子における最短長さＬｓが０．４ｎｍ以上１０μｍ以下である請求項９に記載の多孔質材料。 The porous material according to claim 9, wherein the fibrous particles and/or the tabular particles have a shortest length Ls of 0.4 nm or more and 10 µm or less.
  18. 　前記繊維状粒子及び／又は前記平板状粒子が、セルロースナノファイバー、カーボンナノホーン、カーボンナノリボン、カーボンナノチューブ、グラフェン、及び酸化グラフェンからなる群より選ばれる少なくとも１種類を含有する、請求項９に記載の多孔質材料。 10. The fibrous particles and/or tabular particles according to claim 9, containing at least one selected from the group consisting of cellulose nanofibers, carbon nanohorns, carbon nanoribbons, carbon nanotubes, graphene, and graphene oxide. porous material.
  19. 　多孔質支持層に、繊維状粒子及び／又は平板状粒子を含有するスラリー溶液を接触させ、前記多孔質支持層の外表面に繊維状粒子及び／または平板状粒子を含有する粒子層を形成する工程を含む多孔質材料の製造方法。 A slurry solution containing fibrous particles and/or tabular particles is brought into contact with the porous support layer to form a particle layer containing fibrous particles and/or tabular particles on the outer surface of the porous support layer. A method for producing a porous material comprising steps.
  20. 　請求項１９に記載の多孔質材料に、流体分離膜の材料及び／又は流体分離膜の前駆体を含有する溶液をコーティングする工程を含む流体分離膜の製造方法。 A method for producing a fluid separation membrane, comprising the step of coating the porous material according to claim 19 with a solution containing a fluid separation membrane material and/or a fluid separation membrane precursor.
  21. ケース中に請求項１に記載の流体分離膜を有する、分離膜モジュール。 A separation membrane module comprising the fluid separation membrane according to claim 1 in a case.
  22. 請求項２１に記載の分離膜モジュールをプロセスの少なくとも一部に配置したことを特徴とするガス分離プロセス。 22. A gas separation process characterized by disposing the separation membrane module according to claim 21 in at least part of the process.
  23. 請求項２２に記載のガス分離プロセスを少なくとも一部に用いた流体の製造方法。 23. A method of producing a fluid using, at least in part, the gas separation process of claim 22.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011526834A (en) * 2008-06-30 2011-10-20 ナノエイシス テクノロジーズ，インコーポレイティド Nanotube embedded membrane for selective permeability
CN103881124A (en) * 2014-03-06 2014-06-25 河海大学 Polyamide film loading graphene oxide nanometer sheet and preparation method and application thereof
WO2016013676A1 (en) * 2014-07-24 2016-01-28 東レ株式会社 Carbon film for fluid separation, fluid separation film module, and method for producing carbon film for fluid separation
WO2018079612A1 (en) * 2016-10-26 2018-05-03 昭和電工株式会社 Nanocarbon separation membrane, composite nanocarbon separation membrane, and production method for nanocarbon separation membrane
WO2018079604A1 (en) * 2016-10-26 2018-05-03 昭和電工株式会社 Nanocarbon separation membrane, composite nanocarbon separation membrane, and production method for nanocarbon separation membrane
WO2019021963A1 (en) * 2017-07-25 2019-01-31 東レ株式会社 Fluid separation membrane
JP2019516549A (en) * 2016-05-20 2019-06-20 日東電工株式会社 Selective Permeable Graphene Oxide Membrane
JP2021087907A (en) * 2019-12-03 2021-06-10 国立大学法人信州大学 Method for producing semipermeable composite membrane and semipermeable composite membrane

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011526834A (en) * 2008-06-30 2011-10-20 ナノエイシス テクノロジーズ，インコーポレイティド Nanotube embedded membrane for selective permeability
CN103881124A (en) * 2014-03-06 2014-06-25 河海大学 Polyamide film loading graphene oxide nanometer sheet and preparation method and application thereof
WO2016013676A1 (en) * 2014-07-24 2016-01-28 東レ株式会社 Carbon film for fluid separation, fluid separation film module, and method for producing carbon film for fluid separation
JP2019516549A (en) * 2016-05-20 2019-06-20 日東電工株式会社 Selective Permeable Graphene Oxide Membrane
WO2018079612A1 (en) * 2016-10-26 2018-05-03 昭和電工株式会社 Nanocarbon separation membrane, composite nanocarbon separation membrane, and production method for nanocarbon separation membrane
WO2018079604A1 (en) * 2016-10-26 2018-05-03 昭和電工株式会社 Nanocarbon separation membrane, composite nanocarbon separation membrane, and production method for nanocarbon separation membrane
WO2019021963A1 (en) * 2017-07-25 2019-01-31 東レ株式会社 Fluid separation membrane
JP2021087907A (en) * 2019-12-03 2021-06-10 国立大学法人信州大学 Method for producing semipermeable composite membrane and semipermeable composite membrane

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