WO2023022084A1 - Membrane de séparation de fluide - Google Patents

Membrane de séparation de fluide 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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English (en)
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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Priority to JP2022580788A priority Critical patent/JPWO2023022084A1/ja
Publication of WO2023022084A1 publication Critical patent/WO2023022084A1/fr

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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

La présente invention concerne une membrane de séparation de fluide qui a une couche de support poreuse fibreuse revêtue sur la surface avec une couche à fonction de séparation, une couche de particules étant au moins partiellement interposée entre la couche de support poreuse et la couche de fonction de séparation, et la couche de particules contenant des particules fibreuses et/ou des particules en forme de plaque. La présente invention peut fournir une membrane de séparation de fluide ayant une performance de séparation élevée et une stabilité à long terme.
PCT/JP2022/030525 2021-08-19 2022-08-10 Membrane de séparation de fluide WO2023022084A1 (fr)

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WO2018079612A1 (fr) * 2016-10-26 2018-05-03 昭和電工株式会社 Membrane de séparation à nanocarbone, membrane de séparation à nanocarbone composite, et procédé de production de membrane de séparation à nanocarbone
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JP2011526834A (ja) * 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 選択透過性のためのナノチューブが埋め込まれた膜
CN103881124A (zh) * 2014-03-06 2014-06-25 河海大学 一种负载氧化石墨烯纳米薄片的聚酰胺薄膜及其制备方法和应用
WO2016013676A1 (fr) * 2014-07-24 2016-01-28 東レ株式会社 Film de carbone servant à la séparation de fluides, module de film de séparation de fluides, et procédé de production d'un film de carbone servant à la séparation de fluides
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