WO2016121436A1 - Module de séparation de gaz acide - Google Patents

Module de séparation de gaz acide Download PDF

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Publication number
WO2016121436A1
WO2016121436A1 PCT/JP2016/050329 JP2016050329W WO2016121436A1 WO 2016121436 A1 WO2016121436 A1 WO 2016121436A1 JP 2016050329 W JP2016050329 W JP 2016050329W WO 2016121436 A1 WO2016121436 A1 WO 2016121436A1
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WO
WIPO (PCT)
Prior art keywords
support
gas separation
facilitated transport
membrane
acidic gas
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PCT/JP2016/050329
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English (en)
Japanese (ja)
Inventor
澤田　真
大介 平木
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富士フイルム株式会社
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Priority to JP2016571890A priority Critical patent/JP6419850B2/ja
Publication of WO2016121436A1 publication Critical patent/WO2016121436A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/08—Flat membrane modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/10—Spiral-wound membrane modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/10—Spiral-wound membrane modules
    • B01D63/101—Spiral winding
    • 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
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B01D69/1071—Woven, non-woven or net mesh
    • 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
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1213—Laminated layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1216—Three or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
    • B01D71/701—Polydimethylsiloxane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment

Definitions

  • the present invention relates to an acid gas separation module that separates an acid gas from a raw material gas using a facilitated transport membrane. Specifically, the present invention relates to an acidic gas separation module having good durability.
  • an acidic gas separation module that separates an acidic gas from a raw material gas using an acidic gas separation membrane that selectively permeates the acidic gas has been developed.
  • Patent Document 1 includes a carbon dioxide carrier on a carbon dioxide permeable support as an acidic gas separation membrane (carbon dioxide separation gel membrane) for separating carbon dioxide (carbon dioxide) from a raw material gas.
  • An acidic gas separation membrane having a hydrogel membrane formed by absorbing an aqueous solution into a vinyl alcohol-acrylate copolymer having a crosslinked structure is disclosed.
  • Patent Document 1 as a method for producing this acidic gas separation membrane, an uncrosslinked vinyl alcohol-acrylate copolymer aqueous solution is coated on a carbon dioxide permeable support in the form of a membrane, A method for producing an acidic gas separation membrane is also disclosed in which an aqueous solution is heated and cross-linked to insolubilize water, and the water-insolubilized material absorbs a carbon dioxide carrier aqueous solution and gels.
  • the acid gas separation membrane shown in Patent Document 1 is an acid gas separation membrane using a so-called facilitated transport membrane.
  • the facilitated transport membrane has a carrier that reacts with an acidic gas such as the above-mentioned carbon dioxide carrier in the membrane, and the acidic gas is separated from the source gas by transporting the acidic gas to the opposite side of the membrane by this carrier. .
  • Such an acid gas separation membrane usually has a configuration in which a facilitated transport membrane is formed on a porous support such as a nonwoven fabric or a porous membrane.
  • the facilitated transport film needs to retain a large amount of moisture in the film in order to sufficiently function the carrier. Therefore, a polymer having extremely high water absorption and water retention is used for the facilitated transport film.
  • a polymer having extremely high water absorption and water retention is used for the facilitated transport film.
  • the facilitated transport membrane As the content of a carrier such as a metal carbonate increases, the water absorption increases and the separation performance of the acid gas improves. That is, the facilitated transport film is often a very soft (low viscosity), gel film.
  • a raw material gas having a temperature of 100 to 130 ° C. and a humidity of about 90% is supplied at a pressure of about 1.5 MPa when the acidic gas is separated.
  • the carrier gradually reaches the support from the facilitated transport membrane and permeates the support. If the carrier flows out from the facilitated transport film, the acid gas separation performance is lowered accordingly. Therefore, the acid gas module using the facilitated transport membrane cannot be said to have sufficient durability.
  • Patent Document 2 discloses that a facilitated transport film (polymer compound layer) is formed on a hydrophobic support (porous film) having a heat resistance of 100 ° C. or higher.
  • a carrier diffusion suppression layer is provided between the support and the facilitated transport membrane.
  • siloxane, silicone rubber, polybutadiene, ethylcellulose, polyvinylidene fluoride, polypropylene, polysulfone, polyetherimide, polyethersulfite, polyacrylic acid, polyvinyl alcohol, etc. are exemplified as the material for forming the carrier diffusion suppressing layer.
  • the thickness of the carrier diffusion suppressing layer is exemplified as 0.01 to 100 ⁇ m.
  • Patent Document 2 by providing a carrier diffusion suppression layer on the surface of the support, it is possible to suppress carriers that have escaped from the facilitated transport film from reaching the support and permeating the support.
  • the source gas having a temperature of 100 to 130 ° C. and a humidity of about 90% is supplied at a pressure of about 1.5 MPa.
  • the facilitated transport film has insufficient adhesion, and the facilitated transport film may drop off during the acid gas separation operation. Some are not good enough.
  • durability required for the acid gas separation module has become stricter, and it is desired to more suitably reduce the carriers that pass through the support through the facilitated transport membrane.
  • An object of the present invention is to solve such problems of the prior art, and is an acidic gas separation module using an acidic gas separation membrane having a facilitated transport membrane, which is an enhanced transport membrane at the time of acid gas separation operation. It is an object of the present invention to provide an acidic gas separation module with excellent durability, which can suppress the falling off of the carrier and also prevent the carrier from passing through the facilitated transport membrane and the support.
  • the acidic gas separation module of the present invention comprises a porous support, a carrier diffusion suppression layer formed at least partially in the porous support, and the porous support and carrier diffusion.
  • An acidic gas separation membrane having a facilitated transport membrane containing a carrier reacting with an acidic gas and a hydrophilic compound for supporting the carrier, formed on the suppression layer, and a supply gas flow channel serving as a raw material gas flow channel A member for
  • the projected area ratio (Ps) of the porous support on the surface of the porous support is 50% or more
  • the carrier in the cross section in the thickness direction of the porous support Provided is an acidic gas separation module characterized in that the projected area ratio (Pc) of the diffusion suppression layer is 30% or more.
  • the thickness of the porous support is preferably 200 ⁇ m or less.
  • the product of the projected area ratio (Ps) of the porous support and the projected area ratio (Pc) of the carrier diffusion suppression layer is preferably 2000 or more.
  • a carrier diffusion suppression layer has as a main component the compound which has at least 1 of an epoxy group, an amino group, a methoxy group, an ethoxy group, a hydroxyl group, and a carboxyl group.
  • the carrier diffusion suppressing layer is preferably a polydimethylsiloxane derivative.
  • the facilitated transport membrane is prevented from falling off, and carriers are prevented from exiting the facilitated transport membrane and further from the porous support, thereby being durable. It is possible to obtain an acidic gas separation module excellent in the above.
  • FIG. 3A is a schematic cross-sectional view of a part of the acidic gas separation membrane of the acidic gas separation module shown in FIG. 1
  • FIG. 3B is the surface of the facilitated transport membrane forming surface of the acidic gas separation module shown in FIG.
  • 4 (A) and 4 (B) are conceptual diagrams for explaining a method for producing the acidic gas separation module shown in FIG. It is a conceptual diagram for demonstrating the production method of the acidic gas separation module shown in FIG.
  • 6 (A) and 6 (B) are conceptual diagrams for explaining a method for producing the acidic gas separation module shown in FIG. It is a conceptual diagram for demonstrating the production method of the acidic gas separation module shown in FIG. It is a conceptual diagram for demonstrating the production method of the acidic gas separation module shown in FIG.
  • FIG. 1 is a partially cutaway schematic perspective view of an example of the acid gas separation module of the present invention.
  • the acid gas separation module is also simply referred to as a separation module.
  • the separation module 10 basically includes a central cylinder 12, a laminate wound product 14 obtained by winding a laminate 14 a having an acidic gas separation membrane 20, a telescope prevention plate 16, and the like. It is comprised.
  • the laminated body 14 a is a laminated body including the acidic gas separation membrane 20, the supply gas flow path member 24, and the permeate gas flow path member 26.
  • the acidic gas separation membrane 20 is composed of a facilitated transport membrane 20a, a porous support 20b, and a carrier diffusion suppression layer 20c.
  • the separation module 10 separates carbon dioxide as an acidic gas Gc from a raw material gas G containing carbon monoxide, carbon dioxide (CO 2 ), water (water vapor), and hydrogen.
  • the separation module 10 in the illustrated example is a so-called spiral type separation module. Therefore, the separation module 10 stacks a plurality of sheet-like laminates 14a to be described later, and winds the laminate around the central cylinder 12 to form the laminate wound product 14.
  • the telescoping prevention plate 16 is provided through the central tube 12 on both end surfaces of the lens. That is, the laminate wound product 14 is a substantially cylindrical product formed by the laminate 14a that is laminated and wound. The outermost peripheral surface of the wound laminate 14 a is covered with a gas impermeable coating layer 18.
  • the separation module of the present invention is not limited to the spiral type as shown in the drawings, and may be a so-called flat plate type in which the sheet-like laminate 14a is maintained in a flat plate shape.
  • the raw material gas G from which the acidic gas is separated passes through the opening 16 d of the telescope prevention plate 16 on the back side in FIG. It is supplied inside the body 14a.
  • the source gas G supplied to the stacked body 14a is separated from the acidic gas Gc while flowing in the stacked body 14a.
  • the acidic gas Gc separated from the raw material gas G by the laminated body 14a is discharged from the central cylinder 12, and the raw material gas G from which the acidic gas has been separated (hereinafter referred to as residual gas Gr for convenience) It is discharged from the end surface opposite to the supply side of the roll 14, and is discharged to the outside of the separation module 10 through the opening 16 d of the telescope prevention plate 16.
  • the central tube (permeate gas collecting tube) 12 is a cylindrical tube whose end surface on the source gas G supply side is closed, and a plurality of through holes 12a are formed on the peripheral surface (tube wall).
  • the acidic gas Gc separated from the raw material gas G passes through a permeating gas passage member 26 described later, reaches the inside of the central cylinder 12 from the through hole 12a, and is discharged from the open end 12b of the central cylinder 12.
  • the aperture ratio is preferably 1 to 80%, more preferably 1 to 75%, and further preferably 1.5 to 70%.
  • the opening ratio of the center tube 12 is particularly preferably 1.5 to 25%.
  • the opening ratio of the central cylinder 12 is an area ratio of the through-holes 12 a occupying the outer peripheral surface of the central cylinder 12 in the formation region of the through-holes 12 a in the length direction of the central cylinder 12.
  • the through hole 12a is preferably a circular hole having a diameter of 0.5 to 20 mm. Furthermore, it is preferable that the through holes 12 a are formed uniformly on the peripheral surface of the central cylinder 12.
  • the center tube 12 may be provided with a supply port (supply unit) for supplying a gas (sweep gas) for flowing the separated acidic gas Gc to the open end 12b side as necessary. Furthermore, it is preferable that a slit (not shown) is provided in the tube wall of the central cylinder 12 along the axial direction. This slit will be described in detail later.
  • the laminate 14a is formed by laminating the acidic gas separation membrane 20, the supply gas flow path member 24, and the permeate gas flow path member 26.
  • Reference numeral 30 in FIG. 1 denotes an adhesive layer 30 that bonds the acidic gas separation membrane 20 and the permeate gas flow path member 26 and bonds the stacked bodies 14a together.
  • This adhesive layer 30 also acts as a wall portion constituting the flow path, in which the flow path of the acidic gas Gc in the permeating gas flow path member 26 is formed in an envelope shape opened on the central tube 12 side.
  • the separation module 10 in the illustrated example is formed by stacking a plurality of the laminates 14 a and winding the laminate of the laminates 14 a around the central cylinder 12.
  • a direction corresponding to the winding of the laminated body 14a indicated by an arrow y in the drawing is a winding direction
  • a direction orthogonal to the winding direction indicated by an arrow x in the drawing is a width direction.
  • the laminate 14a constituting the laminate wound product 14 may be one. However, by laminating and winding a plurality of laminated bodies 14a, the membrane area of the acidic gas separation membrane 20 can be increased, and the amount of acidic gas Gc separated by one separation module can be improved.
  • the number of stacked layers 14a may be appropriately set according to the processing speed and processing amount required for the separation module 10, the size of the separation module 10, and the like.
  • the number of laminated bodies 14a to be laminated is preferably 50 or less, more preferably 45 or less, and particularly preferably 40 or less. By setting the number of laminated bodies 14a to be this number, winding of the laminated body 14a around the central cylinder 12 becomes easy, and the workability can be improved.
  • the laminated body 14a includes a supply gas flow path member 24 sandwiched between two folded acid gas separation membranes 20 to form a sandwiching body 36.
  • the permeate gas flow path member 26 is laminated. This configuration will be described in detail later.
  • the raw material gas G is supplied from one end face of the stacked body roll 14 through the opening 16 d of the telescope prevention plate 16. That is, the source gas G is supplied to the end portion (end surface) in the width direction (arrow x direction) of each stacked body 14a.
  • the source gas G supplied to the end face in the width direction of the stacked body 14 a flows in the width direction through the supply gas flow path member 24.
  • the acidic gas Gc in contact with the acidic gas separation membrane 20 (facilitated transport membrane 20a) is separated from the source gas G by the carrier of the facilitated transport membrane 20a and transported in the stacking direction, and the acidic gas separation membrane.
  • the acidic gas Gc that has flowed into the permeate gas flow path member 26 flows in the permeate gas flow path member 26 in the winding direction (the direction of the arrow y), reaches the central cylinder 12, and is centered from the through hole 12 a of the central cylinder 12. It flows into the cylinder 12.
  • the acidic gas Gc that has flowed into the center tube 12 flows through the center tube 12 in the width direction and is discharged from the open end 12b.
  • the residual gas Gr from which the acidic gas Gc has been removed flows in the width direction of the supply gas flow path member 24 and is discharged from the opposite end face of the laminate wound body 14. It is discharged to the outside of the separation module 10 through the part 16d.
  • the supply gas flow path member 24 is supplied with the source gas G from the end in the width direction, and brings the source gas G flowing in the member into contact with the acidic gas separation membrane 20.
  • a supply gas flow path member 24 functions as a spacer of the acid gas separation membrane 20 folded in half as described above, and constitutes a flow path for the source gas G.
  • the supply gas flow path member 24 preferably makes the source gas G turbulent.
  • the supply gas flow path member 24 is preferably a member having a net shape (mesh shape / mesh structure), a woven fabric shape, a nonwoven fabric shape, a porous shape, or the like.
  • Various materials can be used as the material for forming the supply gas flow path member 24 as long as it has sufficient heat resistance and moisture resistance.
  • Examples include paper materials such as paper, fine paper, coated paper, cast coated paper, and synthetic paper, resin materials such as cellulose, polyester, polyolefin, polyamide, polyimide, polysulfone, aramid, and polycarbonate, and inorganic materials such as metal, glass, and ceramics. A material etc. are illustrated suitably.
  • the resin material examples include polyethylene, polystyrene (PS), polyethylene terephthalate, polytetrafluoroethylene (PTFE), polyethersulfone (PES), polyphenylene sulfide (PPS), polysulfone (PSF), and polypropylene (PP).
  • PS polystyrene
  • PTFE polytetrafluoroethylene
  • PES polyethersulfone
  • PPS polyphenylene sulfide
  • PSF polysulfone
  • PP polypropylene
  • Polyimide, polyetherimide, polyetheretherketone, polyvinylidene fluoride and the like are preferably exemplified.
  • a plurality of materials may be used in combination as the material for forming such a supply gas flow path member 24.
  • the thickness of the supply gas flow path member 24 may be appropriately determined according to the supply amount of the source gas G, the required processing capacity, and the like. Specifically, 100 to 1000 ⁇ m is preferable, 150 to 950 ⁇ m is more preferable, and 200 to 900 ⁇ m is particularly preferable.
  • the acidic gas separation membrane 20 has a facilitated transport membrane 20a and a porous support 20b that supports the facilitated transport membrane 20a. Moreover, in the separation module 10 of the present invention, the acidic gas separation membrane 20 has a carrier diffusion suppression layer 20c at least partially located in the porous support 20b. In other words, at least a part of the carrier diffusion suppressing layer 20c is infiltrated into the porous support 20b.
  • the facilitated transport film 20a contains at least a carrier that reacts with the acidic gas Gc contained in the source gas G flowing through the supply gas flow path member 24, and a hydrophilic compound that supports the carrier. Such a facilitated transport film 20a has a function of selectively allowing the acidic gas Gc to permeate from the source gas G.
  • the porous support 20b substantially supports the facilitated transport film 20a.
  • the carrier diffusion suppression layer 20c is a layer for preventing the carriers of the facilitated transport film 20a from being removed from the facilitated transport film 20a and further from the porous support 20b.
  • the acidic gas separation membrane 20 including the facilitated transport membrane 20a, the porous support 20b, and the carrier diffusion suppression layer 20c will be described in detail later.
  • the permeating gas channel member 26 is a member for allowing the acidic gas Gc that has reacted with the carrier and permeated through the acidic gas separation membrane 20 to flow through the through hole 12a of the central cylinder 12.
  • the stacked body 14a has the sandwiching body 36 in which the acidic gas separation membrane 20 is folded in half with the facilitated transport membrane 20a inside, and the supply gas flow path member 24 is sandwiched. By laminating the permeating gas flow path member 26 on the sandwiching body 36 and bonding them with the adhesive layer 30, one laminated body 14a is formed.
  • the permeating gas flow path member 26 functions as a spacer between the acidic gas separation membranes 20 and from the source gas G that reaches the through hole 12a of the central cylinder 12 toward the winding center (inner side) of the stacked body 14a. A flow path of the separated acid gas Gc is formed. Further, in order to properly form the flow path of the acidic gas Gc, the adhesive layer 30 described later needs to penetrate.
  • the permeating gas channel member 26 is preferably a net-like (mesh / net-like), woven fabric, non-woven fabric, porous material or the like, similar to the supply gas channel member 24. .
  • the laminated body 14a is not limited to the configuration using the sandwiching body 36 in which the supply gas flow path member 24 is sandwiched between the folded acidic gas separation membrane 20.
  • the laminated body may be configured in the same manner as the sandwiching body 36 by using the supply gas flow path member 24 attached to the surface of the acidic gas separation membrane 20.
  • polyester-based materials such as epoxy-impregnated polyester, polyolefin-based materials such as polypropylene, fluorine-based materials such as polytetrafluoroethylene, inorganic materials such as metal, glass, and ceramics are preferably exemplified.
  • a plurality of materials may be used in combination as the material for forming such a permeating gas channel member 26. Further, a plurality of the same materials may be used.
  • the thickness of the permeating gas channel member 26 may be appropriately determined according to the supply amount of the raw material gas G, the required processing capacity, and the like. Specifically, 100 to 1000 ⁇ m is preferable, 150 to 950 ⁇ m is more preferable, and 200 to 900 ⁇ m is particularly preferable.
  • the permeating gas channel member 26 is a channel for the acidic gas Gc that is separated from the source gas G and permeates the acidic gas separation membrane 20. Therefore, it is preferable that the permeating gas channel member 26 has a low resistance to the flowing gas. Specifically, it is preferable that the porosity is high, the deformation is small when pressure is applied, and the pressure loss is small.
  • the porosity of the permeating gas channel member 26 is preferably 30 to 99%, more preferably 35 to 97.5%, and particularly preferably 40 to 95%. Deformation when pressure is applied can be approximated by elongation when a tensile test is performed.
  • the permeating gas channel member 26 preferably has an elongation of 5% or less and more preferably 4% or less when a load of 10 N / 10 mm width is applied.
  • the pressure loss can be approximated by a flow rate loss of compressed air that flows at a constant flow rate.
  • the permeate gas channel member 26 has a flow rate loss of 7.5 L / min or less when air of 15 L (liter) / min is passed through the 15 cm square permeate gas channel member 26 at room temperature. Preferably, it is within 7 L / min.
  • the laminated body 14a is formed by laminating a supply gas flow path member 24, an acidic gas separation membrane 20, and a permeate gas flow path member 26.
  • the acidic gas separation membrane 20 includes the facilitated transport membrane 20a, the porous support 20b that substantially supports the facilitated transport membrane 20a, and the carrier diffusion suppression layer 20c.
  • the acidic gas separation membrane 20 has a projected area ratio (Ps) of the porous support 20b on the surface of the porous support 20b in a state excluding the facilitated transport membrane 20a.
  • the projected area ratio (Pc) of the carrier diffusion suppression layer 20c is 30% in the cross section in the thickness direction of the porous support 20b (the laminating direction of each film and layer and the flow path member). That's it.
  • 3A is a schematic sectional view of the acid gas separation membrane 20 in the thickness direction.
  • FIG. 3B is a schematic top view of the porous support 20b in a state in which the facilitated transport membrane 20a is removed from the acid gas separation membrane 20.
  • 3B is a schematic diagram of the facilitated transport film 20a formation surface (surface) of the porous support 20b in the state where the carrier diffusion suppressing layer 20c is formed and the facilitated transport film 20a is not present.
  • the facilitated transport film 20a has a function of selectively allowing the acidic gas Gc to permeate from the source gas G.
  • the facilitated transport film 20a has a function of selectively transporting the acidic gas Gc.
  • Such a facilitated transport film 20a contains at least a hydrophilic compound such as a hydrophilic polymer, a carrier that reacts with an acidic gas, water, and the like.
  • the hydrophilic compound functions as a binder, retains moisture in the facilitated transport film 20a, and exhibits a function of separating an acidic gas such as carbon dioxide by a carrier. Moreover, it is preferable that a hydrophilic compound has a crosslinked structure from a heat resistant viewpoint.
  • the hydrophilic compound can be dissolved in water to form a coating composition, and the facilitated transport film 20a preferably has high hydrophilicity (moisturizing property), those having high hydrophilicity are preferable.
  • the hydrophilic compound preferably has a hydrophilicity of 0.5 g / g or more in physiological saline, and has a hydrophilicity of 1 g / g or more in physiological saline. More preferably, the physiological saline has a hydrophilicity of 5 g / g or more, more preferably, the physiological saline has a hydrophilicity of 10 g / g or more, and the physiological saline has a hydrophilicity. Most preferably, the amount has a hydrophilicity of 20 g / g or more.
  • the weight average molecular weight of a hydrophilic compound suitably in the range which can form a stable film
  • the hydrophilic compound has a hydroxy group (—OH) as a crosslinkable group
  • the hydrophilic compound preferably has a weight average molecular weight of 30,000 or more. In this case, the weight average molecular weight is more preferably 40,000 or more, and more preferably 50,000 or more.
  • the weight average molecular weight is preferably 6,000,000 or less from the viewpoint of production suitability.
  • the hydrophilic compound preferably has a weight average molecular weight of 10,000 or more.
  • the weight average molecular weight of the hydrophilic compound is more preferably 15,000 or more, and particularly preferably 20,000 or more.
  • a weight average molecular weight is 1,000,000 or less from a viewpoint of manufacture aptitude.
  • the weight average molecular weight of various polymer materials may be measured as a molecular weight in terms of PS by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • a commercial item can also be used for a hydrophilic compound, and when using a commercial item, the molecular weight nominally mentioned by a catalog, a specification, etc. should just be used.
  • crosslinkable group forming the hydrophilic compound those capable of forming a hydrolysis-resistant crosslinked structure are preferably selected.
  • Specific examples include a hydroxy group, an amino group, a chlorine atom, a cyano group, a carboxy group, and an epoxy group.
  • an amino group and a hydroxy group are preferably exemplified.
  • a hydroxy group is illustrated from the viewpoint of affinity with a carrier and a carrier carrying effect.
  • hydrophilic compounds include those having a single crosslinkable group such as polyallylamine, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyethyleneimine, polyvinylamine, polyornithine, polylysine, Examples include polyethylene oxide, water-soluble cellulose, starch, alginic acid, chitin, polysulfonic acid, polyhydroxymethacrylate, poly-N-vinylacetamide and the like. Most preferred is polyvinyl alcohol. Moreover, as a hydrophilic compound, these copolymers are also illustrated.
  • Examples of the hydrophilic compound having a plurality of crosslinkable groups include polyvinyl alcohol-polyacrylic acid copolymers.
  • a polyvinyl alcohol-polyacrylic salt copolymer is preferable because of its high water absorption ability and high hydrogel strength even at high water absorption.
  • the content of polyacrylic acid in the polyvinyl alcohol-polyacrylic acid copolymer is, for example, 1 to 95 mol%, preferably 2 to 70 mol%, more preferably 3 to 60 mol%, particularly preferably 5 to 50 mol%. It is.
  • the content of acrylic acid can be controlled by a known synthesis method.
  • the polyacrylic acid may be a salt.
  • Examples of the polyacrylic acid salt in this case include ammonium salts and organic ammonium salts in addition to alkali metal salts such as sodium salts and potassium salts.
  • Polyvinyl alcohol is also available as a commercial product. Specific examples include PVA117 (manufactured by Kuraray Co., Ltd.), Poval (manufactured by Kuraray Co., Ltd.), polyvinyl alcohol (manufactured by Aldrich Co., Ltd.), J-Poval (manufactured by Nippon Vinebaum Poval Co., Ltd.) and the like. Various grades of molecular weight exist, but those having a weight average molecular weight of 130,000 to 300,000 are preferred.
  • a polyvinyl alcohol-polyacrylate copolymer (sodium salt) is also available as a commercial product. For example, Crustomer AP20 (made by Kuraray Co., Ltd.) is exemplified.
  • two or more hydrophilic compounds of the facilitated transport film 20a may be mixed and used.
  • the content of the hydrophilic compound is appropriately determined depending on the type of the hydrophilic composition, the carrier, and the like so that the hydrophilic compound functions as a binder and can sufficiently retain moisture. , You can set.
  • the content of the hydrophilic compound in the facilitated transport film 20a is preferably 0.5 to 50% by mass, more preferably 0.75 to 30% by mass, and particularly preferably 1 to 15% by mass.
  • the crosslinked structure of the hydrophilic compound can be formed by a known method such as thermal crosslinking, ultraviolet crosslinking, electron beam crosslinking, radiation crosslinking, or photocrosslinking. Photocrosslinking or thermal crosslinking is preferred, and thermal crosslinking is most preferred.
  • the coating composition for forming the facilitated transport film 20a preferably contains a crosslinking agent.
  • the crosslinking agent one containing a crosslinking agent that reacts with a hydrophilic compound and has two or more functional groups capable of crosslinking such as thermal crosslinking or photocrosslinking is selected.
  • the formed crosslinked structure is preferably a hydrolysis-resistant crosslinked structure.
  • an epoxy crosslinking agent a polyvalent glycidyl ether, a polyhydric alcohol, a polyvalent isocyanate, a polyvalent aziridine, a haloepoxy compound, a polyvalent aldehyde, a polyvalent amine, An organic metal type crosslinking agent etc. are illustrated suitably. More preferred are polyvalent aldehydes, organometallic crosslinking agents and epoxy crosslinking agents, and among them, polyvalent aldehydes such as glutaraldehyde and formaldehyde having two or more aldehyde groups are preferred.
  • Epoxy crosslinking agent the compound which has 2 or more of epoxy groups is illustrated, and the compound which has 4 or more is also preferable.
  • Epoxy crosslinking agents are also commercially available, for example, trimethylolpropane triglycidyl ether (manufactured by Kyoeisha Chemical Co., Epolite 100MF, etc.), Nagase ChemteX Corporation EX-411, EX-313, EX-614B, EX -810, EX-811, EX-821, EX-830, Epiol E400 manufactured by NOF Corporation, and the like.
  • an oxetane compound having a cyclic ether is also preferably used.
  • the oxetane compound is preferably a polyvalent glycidyl ether having two or more functional groups.
  • Examples of commercially available products include EX-411, EX-313, EX-614B, EX-810, EX-811, EX manufactured by Nagase ChemteX Corporation. -821, EX-830, etc.
  • polyvalent glycidyl ether examples include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, propylene Examples include glycol glycidyl ether and polypropylene glycol diglycidyl ether.
  • polyhydric alcohol examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, polyglycerin, propylene glycol, diethanolamine, triethanolamine, polyoxypropyl, oxyethyleneoxypropylene block copolymer , Pentaerythritol, sorbitol and the like.
  • Examples of the polyvalent isocyanate include 2,4-tolylene diisocyanate and hexamethylene diisocyanate.
  • Examples of the polyvalent aziridine include 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 1,6-hexamethylenediethyleneurea, diphenylmethane-bis-4,4′-N, N Examples include '-diethylene urea.
  • Examples of the haloepoxy compound include epichlorohydrin and ⁇ -methylchlorohydrin.
  • Examples of the polyvalent aldehyde include glutaraldehyde and glyoxal.
  • Examples of the polyvalent amine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and polyethyleneimine.
  • examples of the organometallic crosslinking agent include organic titanium crosslinking agents and organic zirconia crosslinking agents.
  • an epoxy crosslinking agent or glutaraldehyde is preferably used as the crosslinking agent.
  • an epoxy crosslinking agent or glutaraldehyde is preferably used as the crosslinking agent.
  • the hydrophilic compound When a polyallylamine having a weight average molecular weight of 10,000 or more is used as the hydrophilic compound, it is possible to form a crosslinked structure having good reactivity with this hydrophilic compound and excellent hydrolysis resistance.
  • the crosslinking agent an epoxy crosslinking agent, glutaraldehyde, and an organometallic crosslinking agent are preferably used.
  • an epoxy crosslinking agent is preferably used as the crosslinking agent.
  • the amount of a crosslinking agent is preferably 0.001 to 80 parts by mass, more preferably 0.01 to 60 parts by mass, and particularly preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the crosslinkable group possessed by the hydrophilic compound. preferable.
  • the content of the cross-linking agent in the above range, a facilitated transport film having good cross-linking structure formation and excellent shape maintainability can be obtained.
  • the crosslinked structure is preferably formed by reacting 0.001 to 80 mol of a crosslinking agent with respect to 100 mol of the crosslinkable group possessed by the hydrophilic compound.
  • the facilitated transport film 20a preferably contains a metal element.
  • One preferred embodiment of the facilitated transport film 20a includes an embodiment in which the facilitated transport film contains at least one metal element selected from the group consisting of Ti, Zr, Al, Si, and Zn.
  • the strength of the facilitated transport film 20a is improved.
  • the strength of the facilitated transport film 20a is further improved by forming a cross-linked structure containing the metal element, and as a result, the facilitated transport film 20a is deteriorated when wound in a spiral shape, for example. Is more suppressed.
  • the form of the facilitated transport film 20a containing such a metal element is not particularly limited, but a facilitated transport film containing a structural unit represented by the following formula (1) is preferable.
  • * represents a bonding position.
  • M- (O-*) m M represents a metal element selected from the group consisting of Ti (titanium), Zr (zirconium), Al (aluminum), Si (silicon), and Zn (zinc).
  • m represents the valence of the metal element represented by M. For example, as shown below, m represents 2 when M is Zn, m represents 3 when M is Al, and m represents 4 when M is Ti, Zr, and Si. . More specifically, structural formulas (formula (2) to formula (4)) where m is 2 to 4 are shown below.
  • the structural unit represented by the above formula (1) is, for example, by using a hydrolyzable compound in combination with a hydrophilic compound having a crosslinkable group (for example, a hydroxy group) as described below. It can be introduced into the facilitated transport film 20a. In that case, the structural unit functions as a so-called cross-linked site (cross-linked structure).
  • membrane 20a it can confirm by detecting a specific peak by IR measurement, for example. If necessary, after removing the carriers in the facilitated transport film 20a, IR measurement may be performed on the remaining film.
  • the total mass of the metal elements in the facilitated transport film 20a is not particularly limited, but the content of the metal element is 0.1 to 0.1% with respect to the total mass of the hydrophilic compound in that the strength of the facilitated transport film 20a is more excellent.
  • the content is preferably 50% by mass, more preferably 0.3 to 20% by mass, and still more preferably 0.5 to 10% by mass.
  • the measuring method of content of the said metal element is not restrict
  • Formula (5) M (X) m
  • M represents a metal element selected from the group consisting of Ti (titanium), Zr (zirconium), Al (aluminum), Si (silicon), and Zn (zinc).
  • X represents a hydrolyzable group.
  • hydrolyzable group examples include an alkoxyl group, an isocyanate group, a halogen atom such as a chlorine atom, an oxyhalogen group, an acetylacetonate group, and a hydroxy group.
  • a plurality of X may be the same or different.
  • m represents the valence of the metal element represented by M.
  • the carrier reacts with an acid gas (for example, carbon dioxide gas (CO 2 )) to transport the acid gas.
  • an acid gas for example, carbon dioxide gas (CO 2 )
  • the carrier is a water-soluble compound having affinity with acidic gas and showing basicity. Specific examples include alkali metal compounds, nitrogen-containing compounds, and sulfur oxides.
  • the carrier may react indirectly with the acid gas, or the carrier itself may react directly with the acid gas.
  • the former reacts with other gas contained in the supply gas, shows basicity, and the basic compound reacts with acidic gas. More specifically, OH react with steam (water) - was released, the OH - that reacts with CO 2, a compound can be incorporated selectively CO 2 in facilitated transport membrane 20a
  • an alkali metal compound is such that the carrier itself is basic, for example, a nitrogen-containing compound or a sulfur oxide.
  • alkali metal compound examples include alkali metal carbonate, alkali metal bicarbonate, and alkali metal hydroxide.
  • alkali metal an alkali metal element selected from cesium, rubidium, potassium, lithium, and sodium is preferably used.
  • an alkali metal compound contains the salt and its ion other than alkali metal itself.
  • Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate.
  • Examples of the alkali metal bicarbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate.
  • Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. Among these, an alkali metal carbonate is preferable, and a compound containing potassium, rubidium, and cesium having high solubility in water is preferable from the viewpoint of good affinity with acidic gas.
  • two or more kinds of carriers may be used in combination.
  • two or more types of carriers are present in the facilitated transport film 20a, different carriers can be separated from each other in the film. Thereby, due to the difference in deliquescence of a plurality of carriers, due to the water absorption of the facilitated transport film 20a, the facilitated transport films 20a or the facilitated transport film 20a and other members are adhered to each other during production. (Blocking) can be suitably suppressed.
  • the first compound having deliquescence and the specific gravity having lower deliquescence than the first compound It is preferable to contain the 2nd compound with small.
  • the first compound is exemplified by cesium carbonate
  • the second compound is exemplified by potassium carbonate.
  • Nitrogen-containing compounds include amino acids such as glycine, alanine, serine, proline, histidine, taurine, diaminopropionic acid, hetero compounds such as pyridine, histidine, piperazine, imidazole, triazine, monoethanolamine, diethanolamine, triethanolamine , Alkanolamines such as monopropanolamine, dipropanolamine and tripropanolamine, cyclic polyetheramines such as cryptand [2.1] and cryptand [2.2], cryptand [2.2.1] and cryptand [ And bicyclic polyetheramines such as 2.2.2], porphyrin, phthalocyanine, ethylenediaminetetraacetic acid and the like.
  • sulfur compounds include amino acids such as cystine and cysteine, polythiophene, dodecyl thiol and the like.
  • the amount of carriers in the facilitated transport film 20a is preferably 0.3 to 30% by mass, more preferably 0.5 to 25% by mass, and 1 to 20% by mass. Is particularly preferred.
  • the weight ratio of the hydrophilic compound to the carrier in the coating composition is preferably 1: 9 to 2: 3, more preferably 1: 4 to 2: 3, and more preferably 3: 7 to 2 in terms of the weight ratio of the hydrophilic compound to the carrier. : 3 is particularly preferable.
  • the facilitated transport film 20a may contain a thickener as necessary. That is, the coating composition for forming the facilitated-transport film
  • membrane 20a may contain a thickener as needed.
  • the thickener for example, thickening polysaccharides such as agar, carboxymethylcellulose, carrageenan, chitansan gum, guar gum and pectin are preferable.
  • carboxymethylcellulose is preferable from the viewpoints of film forming property, availability, and cost.
  • the content of the thickener is preferably as small as possible as long as it can be adjusted to the target viscosity.
  • a general index 10% by mass or less is preferable, 0.1 to 5% by mass is more preferable, and 0.1 to 2% by mass or less is more preferable.
  • the facilitated transport film 20a that is, the coating composition for forming the facilitated transport film 20a contains various components as necessary in addition to such a hydrophilic compound, a crosslinking agent and a carrier, or a thickener. May be.
  • antioxidants such as dibutylhydroxytoluene (BHT), compounds having 3 to 20 carbon atoms or fluorinated alkyl groups having 3 to 20 carbon atoms and hydrophilic groups, and siloxane structures.
  • BHT dibutylhydroxytoluene
  • Specific compounds such as compounds having a surfactant, surfactants such as sodium octoate and sodium 1-hexasulfonate, polymer particles such as polyolefin particles and polymethyl methacrylate particles, and the like.
  • a catalyst, a humectant, a hygroscopic agent, an auxiliary solvent, a film strength modifier, a defect detector, and the like may be used as necessary.
  • the thickness of the facilitated transport membrane 20a may be set as appropriate so that the desired performance can be obtained according to the composition of the facilitated transport membrane 20a. Specifically, it is preferably 3 to 1000 ⁇ m, more preferably 5 to 500 ⁇ m, and particularly preferably 5 to 100 ⁇ m.
  • membrane 20a can be measured by cross-sectional observation using a scanning electron microscope or the like.
  • the facilitated transport film 20a is shown on the porous support 20b for the sake of brevity, but in actuality, the facilitated transport film 20a is shown in FIGS. 3 (A) and 3 (B).
  • the film thickness of the facilitated transport film 20a is obtained by taking an image of a cross section with a scanning electron microscope (SEM), and taking the average of any 10 cross sections with the interface between the facilitated transport film 20a and the layer located therebelow as the lower end Calculate as The layer located under the facilitated transport film 20a is the porous support 20b or the carrier diffusion suppression layer 20c.
  • SEM scanning electron microscope
  • the porous support 20b supports the facilitated transport film 20a and the carrier diffusion suppression layer 20c, and has a permeability to an acidic gas such as carbon dioxide.
  • the porous support 20b is also referred to as the support 20b.
  • As the support 20b various known materials can be used as long as they have this function.
  • the support 20b may be a single layer.
  • the support 20b preferably has a two-layer structure in which a porous film and an auxiliary support film are stacked.
  • the porous membrane is on the facilitated transport membrane 20a side.
  • the porous membrane is preferably made of a material having heat resistance and low hydrolyzability.
  • a porous membrane include membrane filter membranes such as polysulfone (PSF), polyethersulfone, polypropylene (PP) and cellulose, interfacially polymerized thin films of polyamide and polyimide, polytetrafluoroethylene (PTFE).
  • PTFE polytetrafluoroethylene
  • a stretched porous membrane of high molecular weight polyethylene a porous film containing one or more materials selected from fluorine-containing polymers such as PTFE, high molecular weight polyethylene, PP and PSF is preferably exemplified.
  • stretched porous membranes of PTFE, high molecular weight polyethylene, and PP are preferable from the viewpoints of high porosity, small diffusion inhibition of acidic gas (especially carbon dioxide gas), and strength and manufacturability.
  • a stretched porous membrane of PTFE is preferably used in terms of heat resistance and low hydrolyzability.
  • an inorganic material or an organic-inorganic hybrid material may be used.
  • the inorganic porous support include a porous substrate mainly composed of ceramics. By using ceramics as a main component, it is excellent in heat resistance, corrosion resistance, etc., and mechanical strength can be increased. There are no particular limitations on the type of ceramic, and various commonly used ceramics can be used. Examples of the ceramic include alumina, silica, silica-alumina, mullite, cordierite, zirconia and the like. Further, a combination of two or more kinds of ceramics, a composite of ceramic and metal, or a composite of ceramic and organic compound may be used.
  • the auxiliary support membrane is provided for reinforcing the porous membrane.
  • various materials can be used as long as they satisfy the required strength, stretch resistance and gas permeability.
  • a nonwoven fabric, a woven fabric, a net, and a mesh can be appropriately selected and used.
  • the auxiliary support membrane is also preferably made of a material having heat resistance and low hydrolyzability, like the porous membrane described above.
  • the fibers constituting the nonwoven fabric, woven fabric, and knitted fabric are excellent in durability and heat resistance, polyolefin such as PP, modified polyamide such as aramid (trade name), PTFE, polyvinylidene fluoride, etc.
  • a fiber made of a fluorine-containing resin is preferable. It is preferable to use the same material as the resin material constituting the mesh.
  • a non-woven fabric made of PP that is inexpensive and has high mechanical strength is particularly preferably exemplified.
  • the support 20b has an auxiliary support film
  • the mechanical strength can be improved. Therefore, as will be described later, even when the acid gas separation membrane 20 is formed using so-called RtoR (roll-to-roll), it is possible to prevent wrinkles from being generated on the support 20b, and to improve productivity. Can also be increased.
  • RtoR roll-to-roll
  • the thickness of the support 20b is preferably 200 ⁇ m or less. Further, if the support 20b is too thin, the strength is difficult. Considering this point, the thickness of the support 20b is preferably 10 to 200 ⁇ m, more preferably 10 to 120 ⁇ m, and particularly preferably 15 to 100 ⁇ m.
  • the film thickness of the porous film is preferably 5 to 100 ⁇ m, and the film thickness of the auxiliary support film is preferably 50 to 200 ⁇ m.
  • the maximum pore diameter of the porous membrane is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less, and particularly preferably 0.3 ⁇ m or less.
  • the average pore diameter of the pores of the porous membrane is preferably 0.001 to 1 ⁇ m, and more preferably 0.001 to 0.3 ⁇ m.
  • the maximum pore size and the average pore size of the porous film are set within this range, it is possible to improve the controllability of the penetration of the carrier diffusion suppression layer 20c (coating composition to be the carrier diffusion suppression layer 20c) described later, It is possible to suitably prevent the film from obstructing the passage of the acidic gas, and when applying the coating composition that becomes the carrier diffusion suppressing layer 20c described later, the film surface becomes non-uniform due to capillary action or the like. I can prevent it.
  • the acidic gas separation membrane 20 is at least partially infiltrated into the support 20b (soaked in).
  • the carrier diffusion suppression layer 20c is formed.
  • the carrier diffusion suppression layer 20c prevents the carrier from escaping from the facilitated transport film 20a and further from the support 20b.
  • the carrier diffusion suppressing layer 20c has an effect of supporting the facilitated transport film 20a together with the support 20b.
  • the carrier diffusion suppressing layer 20c is formed entirely without gaps corresponding to the formation region of the facilitated transport film 20a, as in the case of a normal acidic gas separation module using the facilitated transport film.
  • the acidic gas separation membrane 20 is a support in a state where the facilitated transport membrane 20a is removed as conceptually shown in FIGS. 3 (A) and 3 (B).
  • the projected area ratio (Ps) of the support 20b on the surface of 20b is 50% or more.
  • the carrier diffusion suppression layer 20c is in a so-called sea island state in which it partially protrudes from the surface of the support 20b.
  • the acidic gas separation membrane 20 has a projected area of the carrier diffusion suppression layer 20c in the cross section in the thickness direction of the support 20b, as conceptually shown in FIG.
  • the rate (Pc) is 30% or more.
  • the carrier diffusion suppression layer 20c may be formed only in the porous film or formed only in the auxiliary support film. Alternatively, it may be formed across both the porous membrane and the auxiliary support membrane.
  • the carrier diffusion suppression layer 20c is usually formed on the porous film side. Therefore, in this case, the porous film on which the carrier diffusion suppressing layer 20c is formed becomes the porous support in the present invention.
  • the present invention prevents the facilitated transport film 20a from dropping off during the acidic gas separation operation, and the carrier escapes from the facilitated transport film 20a and further escapes from the support 20b. This prevents the acid gas separation module 10 having excellent durability.
  • a porous support is used to prevent carriers that have escaped from the facilitated transport membrane from exiting the porous support.
  • a carrier diffusion layer is provided on the surface, and a facilitated transport film is formed thereon.
  • the facilitated transport film is in a gel form.
  • the raw material gas G having a temperature of 100 to 130 ° C. and a humidity of about 90% is supplied at a pressure of about 1.5 MPa. For this reason, in the conventional configuration in which the facilitated transport film is formed on the carrier diffusion suppressing layer, the facilitated transport film has insufficient adhesion, and the facilitated transport film may fall off during the acid gas separation operation.
  • the acidic gas separation membrane using the facilitated transport membrane gradually loses the carrier from the facilitated transport membrane and further escapes from the support as a result of use, and the acid gas separation ability is reduced. Therefore, it cannot be said that the acid gas module using the conventional facilitated transport membrane has sufficient durability.
  • the acidic gas separation membrane 20 has a projected area ratio (Ps) of the support 20b on the surface of the support 20b of 50, excluding the facilitated transport membrane 20a. % Or more. That is, the carrier diffusion suppression layer 20c is formed in a state in which at least a part is infiltrated into the support 20b, and 50% or more of the projected area ratio is covered with the carrier diffusion suppression layer 20c on the surface of the support 20b.
  • the support 20b is bare. Therefore, as shown in FIGS. 3 (A) and 3 (B), in the separation module 10 of the present invention, the facilitated transport film 20a has 50% or more of the projected area ratio on the surface of the support 20b.
  • the acidic gas separation membrane 20 has a projected area of the carrier diffusion suppression layer 20c in the cross section in the thickness direction of the support 20b, as conceptually shown in FIG.
  • the rate (Pc) is 30% or more.
  • the acidic gas separation membrane 20 has the carrier diffusion suppression layer 20c having a sufficient thickness with respect to the thickness of the support 20b. Furthermore, it is possible to prevent the support 20b from coming off. Therefore, according to the present invention, the separation module 10 having excellent durability can be obtained.
  • the acid gas separation membrane 20 has a projected area ratio (Ps) of the support 20b of 50% or more on the surface of the support 20b in a state where the facilitated transport membrane 20a is excluded.
  • the acid gas separation membrane 20 has an area ratio of 50% or more where the support 20b is exposed on the surface of the support 20b excluding the facilitated transport membrane 20a, and the carrier diffusion suppression layer 20c is exposed.
  • the area ratio is less than 50%.
  • the projected area ratio (Ps) is less than 50%, the anchor effect due to the facilitated transport film 20a soaking into the support 20b cannot be sufficiently obtained, and the facilitated transport film 20a cannot be sufficiently prevented from falling off during the separation operation.
  • the higher the projected area ratio (Ps) the better the anchor effect.
  • the projected area ratio (Ps) is preferably 80% or more, and more preferably 85% or more.
  • the projected area ratio (Ps) of the support 20b on the surface of the support 20b excluding the facilitated transport film 20a is, for example, that the facilitated transport film 20a is not present and the carrier diffusion suppression layer 20c is formed.
  • What is necessary is just to image
  • SEM scanning electron microscope
  • the obtained SEM image is binarized between the exposed portion of the carrier diffusion suppression layer 20c and the exposed portion of the support 20b by discriminant analysis using commercially available image processing software (such as “Winroof” manufactured by Mitani Corporation). Processing is performed, and the area ratio is calculated as an average of arbitrary 10 cross sections. At this time, if there are different elements in the chemical composition of the carrier diffusion suppressing layer 20c and the support 20b, the area ratio may be calculated from SEM-EDX mapping targeting the element. Further, the projected area ratio (Ps) may be measured as it is after the formation of the carrier diffusion suppressing layer 20c and before the formation of the facilitated transport film 20a. Even after the facilitated transport film 20a is formed, the surface of the support 20b may be exposed and measured by dissolving the facilitated transport film 20a with hot water and washing it away.
  • image processing such as “Winroof” manufactured by Mitani Corporation.
  • the acidic gas separation membrane 20 has a projected area ratio (Pc) of the carrier diffusion suppression layer 20c of 30% or more in the cross section of the support 20b in the thickness direction.
  • the support 20b of the acidic gas separation membrane 20 has an area ratio at which the carrier diffusion suppression layer 20c is exposed in a cross section in the thickness direction of 30% or more, and an area ratio at which the support 20b is exposed. Is less than 70%.
  • the projected area ratio (Pc) is less than 30%, the carrier diffusion suppressing layer 20c having a sufficient thickness cannot be formed, and it is not possible to sufficiently suppress the carriers from passing through the facilitated transport film and further from the support 20b.
  • the projected area ratio (Pc) is preferably 50% or more.
  • the projected area ratio (Pc) is preferably 50 to 80%, more preferably 55 to 70%.
  • the projected area ratio (Pc) of the carrier diffusion suppression layer 20c in the cross section of the support 20b in the thickness direction is the same as the projected area ratio (Ps), and the cross section in the thickness direction of the support 20b is measured with a scanning electron microscope. Photographing and image analysis to obtain the area ratio of the carrier diffusion suppression layer 20c in this cross section may be performed in any 10 cross sections, and the average value may be set as the projected area ratio (Pc). At this time, the facilitated transport film 20a may be removed as necessary in the same manner as the projected area ratio (Ps).
  • the product “(Ps) ⁇ (Pc)” of the projected area ratio (Ps) and the projected area ratio (Pc) is preferably 2000 or more, and more preferably 2500 or more. It is particularly preferably 5000 or more.
  • the product “(Ps) ⁇ (Pc)” is basically larger, the facilitated transport film 20a is prevented from falling off and the carrier is prevented from leaving the facilitated transport film 20a and the support 20b in a well-balanced manner. Can do. Therefore, by setting the product “(Ps) ⁇ (Pc)” to 2000 or more, it is possible to obtain the separation module 10 with more excellent durability.
  • the carrier diffusion suppression layer 20c is formed above the support 20b in a so-called sea-island state in which a part protrudes from the surface of the support 20b.
  • the present invention is not limited to this. That is, the carrier diffusion suppression layer 20c may not be exposed on the surface of the support 20b, and may be entirely present inside the support 20b (projected area ratio (Ps) is 100%). May be formed at the bottom (the side opposite to the side on which the facilitated transport film 20a is formed).
  • the carrier diffusion suppression layer 20c can be formed of various materials. Specifically, the carrier diffusion suppression layer 20c preferably has a functional group that reacts with a hydroxyl group and / or a carboxyl group. More specifically, the carrier diffusion suppression layer 20c preferably contains a compound having at least one of an epoxy group, an amino group, a methoxy group, an ethoxy group, a hydroxyl group, and a carboxyl group as a main component.
  • the carrier diffusion suppressing layer 20c a layer made of a compound having a silicone bond or a silicone-containing compound having a non-crosslinkable or crosslinked structure is exemplified.
  • silicone-containing polyacetylene such as organopolysiloxane (silicone resin) or polytrimethylsilylpropyne having non-crosslinkable or crosslinked structure can be used.
  • organopolysiloxane include those represented by the following general formula.
  • the carrier diffusion suppressing layer 20c can also be used in a configuration obtained by crosslinking one represented by the following general formula. In the above general formula, n represents an integer of 1 or more.
  • n is preferably in the range of 10 to 1000000, and more preferably in the range of 100 to 100,000.
  • R 1n , R 2n , R 3 and R 4 are each selected from the group consisting of a hydrogen atom, alkyl group, vinyl group, aralkyl group, aryl group, hydroxyl group, amino group, carboxyl group and epoxy group. Indicates either. Note that n R 1n and R 2n may be the same or different. Further, the alkyl group, aralkyl group and aryl group may have a ring structure.
  • alkyl group, vinyl group, aralkyl group and aryl group may have a substituent, and the substituent in this case is, for example, an alkyl group, vinyl group, aryl group, hydroxyl group, amino group, carboxyl group. , An epoxy group and a fluorine atom. These substituents may further have a substituent, if possible.
  • the alkyl group, vinyl group, aralkyl group and aryl group selected from R 1n , R 2n , R 3 and R 4 are alkyl groups having 1 to 20 carbon atoms, vinyl groups, More preferred are an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms.
  • R 1n , R 2n , R 3 and R 4 are preferably methyl groups or epoxy-substituted alkyl groups.
  • PDMS derivatives such as epoxy-modified polydimethylsiloxane (PDMS) can be suitably used.
  • a silicone material such as poly [1- (trimethylsilyl) -1-propyne] (PTMSP), a butadiene-based / isoprene-based rubber material, a low density A layer made of polymethylpentene or the like can also be used.
  • the acidic gas separation membrane 20 preferably has a protective layer on the surface, that is, the facilitated transport membrane 20a.
  • the facilitated transport membrane 20a As described above, when the separation module 10 winds the laminate 14a in which the sandwiched body 36 formed by the acidic gas separation membrane 20 and the supply gas flow path member 24 and the permeate gas flow path member 26 are wound, The facilitated transport film 20a may be damaged by the sliding contact between the facilitated transport film 20a and the supply gas flow path member 24.
  • the facilitated transport membrane 20a is prevented by the sliding contact between the facilitated transport membrane 20a and the supply gas flow path member 24, and more acidic.
  • a separation module 10 having excellent gas separation performance can be obtained.
  • the material for forming the protective layer can be used as the material for forming the protective layer, and various compounds exemplified in the carrier diffusion suppression layer 20c described above are preferably used.
  • the PDMS derivative is preferably exemplified.
  • a protective layer suitably according to the characteristic of the facilitated-transport film
  • Such an acidic gas separation membrane 20 may be produced by various known methods. Preferably, it is produced by a coating method using RtoR.
  • RtoR means that a substrate is delivered from a roll formed by winding a long substrate (object to be processed) and conveyed in the longitudinal direction, and the coating composition is applied and dried. It is a manufacturing method which winds up the board
  • a roll formed by winding a long support 20b is loaded into a carrier diffusion suppression layer 20c forming apparatus, and the support is sent out from the roll. While transporting 20b in the longitudinal direction, a coating composition to be the carrier diffusion suppression layer 20c is applied.
  • the conveyance speed of the support 20b is preferably faster from the viewpoint of productivity.
  • the coating composition uniformly it is preferably 3 to 200 m / min, more preferably 5 to 150 m / min, and particularly preferably 10 to 120 m / min.
  • the coating composition that becomes the carrier diffusion suppressing layer 20c is composed of the monomer, dimer, trimer, oligomer, prepolymer, mixture of these compounds, the curing agent, and the curing acceleration.
  • a resin layer resin film
  • a coating method in which an agent, a crosslinking agent, a thickener, a reinforcing agent, and a filler are dissolved and / or dispersed in an organic solvent, It is a general coating composition (coating liquid / paint).
  • Such a coating composition may be prepared by a known method.
  • the support 20b is a porous body. Therefore, when the coating composition to be the carrier diffusion suppressing layer 20c is applied to the support 20b, the coating composition gradually permeates the support 20b (porous film).
  • the viscosity of the coating composition to be the carrier diffusion suppressing layer 20c, the solid content concentration of the coating composition, the coating amount of the coating composition (coating film thickness), the time from applying the coating composition to drying or curing By adjusting the maximum pore size and average pore size of the support 20b (porous membrane) over time, the penetration of the coating composition into the support 20b is controlled, and the projected area ratio of the porous support 20b on the surface ( Ps) is 50% or more, and the acidic gas separation membrane 20 in which the projected area ratio (Pc) of the carrier diffusion suppression layer 20c in the cross section in the thickness direction of the porous support 20b is 30% or more can be produced.
  • the projected area ratio (Ps) and / or the projected area ratio (Pc) can be adjusted.
  • the acidic gas separation membrane 20 having a projected area ratio (Ps) of 50% or more and a projected area ratio (Pc) of 30% or more is first coated with a low-viscosity coating composition, and then has a certain degree of high viscosity. It can also be produced by applying the coating composition to be the carrier diffusion suppressing layer 20c a plurality of times, such as by applying a coating composition. The order of applying the low-viscosity coating composition and the order of applying the high-viscosity coating composition may be reversed. Furthermore, using a coating composition that is very easily impregnated into the support 20b, a coating layer is formed on the lower surface of the support 20b (the surface opposite to the surface on which the facilitated transport film is formed) to form a coating composition.
  • the acidic gas separation membrane 20 having a projected area ratio (Ps) of 50% or more and a projected area ratio (Pc) of 30% or more may be formed by applying an object.
  • the coating composition to be the carrier diffusion suppression layer 20c has a viscosity at 25 ° C. of preferably 50 to 10,000 cp, more preferably 50 to 8000 cp, and particularly preferably 50 to 5000 cp.
  • the coating composition used as the carrier diffusion suppressing layer 20c has an acid gas separation membrane having a projected area ratio (Ps) of 50% or more and a projected area ratio (Pc) of 30% or more by setting the viscosity at 25 ° C. to 50 to 10,000 cp. 20 is preferable in that it can be stably produced.
  • the coating device for the coating composition to be the carrier diffusion suppression layer 20c various known devices corresponding to the coating composition can be used. Specifically, roll coater, direct gravure coater, offset gravure coater, 1 roll kiss coater, 3 reverse roll coater, forward rotation roll coater, curtain flow coater, extrusion die coater, air doctor coater, blade coater, rod coater And knife coaters, squeeze coaters, reverse roll coaters, bar coaters and the like.
  • a roll coater in consideration of the control of the coating composition, the coating amount of the coating composition, the penetration amount of the coating composition, etc., a roll coater, a direct gravure coater, an offset gravure coater, a single roll kiss coater, a three reverse roll coater, A rotary roll coater, a squeeze coater, a reverse roll coater and the like are preferably exemplified.
  • the coating composition to be the carrier diffusion suppressing layer 20c is applied, the coating composition is then dried.
  • the drying may be performed by a known method such as hot air drying or drying with a heater.
  • the coating composition to be the carrier diffusion suppression layer 20c is dried, the coating composition is then cured to form the carrier diffusion suppression layer 20c.
  • a method capable of curing such as heat curing, ultraviolet irradiation, electron beam irradiation, or the like, may be appropriately selected according to the material for forming the carrier diffusion suppression layer 20c.
  • curing of the coating composition by ultraviolet irradiation or short heating is preferably used. Is done.
  • curing by ultraviolet irradiation is most preferably used. That is, in the present invention, it is preferable to form the carrier diffusion suppression layer 20c with a coating composition using a monomer or the like that can be cured by irradiation with ultraviolet rays.
  • the coating composition may be dried and cured at the same time. Moreover, you may perform drying and / or hardening of a coating composition in inert atmosphere, such as nitrogen atmosphere, as needed.
  • the support 20b on which the carrier diffusion suppression layer 20c is formed is wound into a roll.
  • the protective layer formed on the facilitated transport film 20a can be basically formed in the same manner as the carrier diffusion suppression layer 20c.
  • the roll of the support 20b on which the carrier diffusion suppressing layer 20c is formed is loaded into the apparatus for forming the facilitated transport film 20a, and the composite is sent out from the roll and transported in the longitudinal direction to become the facilitated transport film 20a.
  • a coating composition is applied.
  • the support 20b on which the carrier diffusion suppression layer 20c is formed is also referred to as a composite.
  • complex at the time of forming the facilitated-transport film
  • the conveyance speed of the composite is preferably 0.5 m / min or more, more preferably 0.75 to 200 m / min, and particularly preferably 1 to 200 m / min.
  • the facilitated transport film 20a contains a hydrophilic compound such as a hydrophilic polymer, a carrier that reacts with an acidic gas, water, and the like.
  • the coating composition (coating liquid / paint) for forming such a facilitated transport film 20a includes the above-described hydrophilic compound, carrier and water, or further a necessary composition such as a crosslinking agent. It is a thing.
  • the water may be room temperature water or warm water.
  • the hydrophilic compound may be crosslinked, partially crosslinked, or uncrosslinked, or a mixture of these.
  • This coating composition may also be prepared by a known method.
  • the coating composition to be the facilitated transport film 20a preferably has a viscosity at 25 ° C. of 100 cp or more.
  • a viscosity at 25 ° C. of the coating composition By setting the viscosity at 25 ° C. of the coating composition to 100 cp or more, it is preferable from the standpoint that repelling at the time of applying the coating composition can be suppressed, and uniformity of coating of the coating composition can be improved.
  • what is necessary is just to measure a viscosity similarly to the coating composition used as the carrier diffusion suppression layer 20c.
  • the coating composition to be the facilitated transport film 20a various known materials can be used, and the same materials as those of the carrier diffusion suppression layer 20c described above are exemplified.
  • a roll coater, a bar coater, a positive rotation roll coater, a knife coater, and the like are preferably used.
  • membrane 20a is apply
  • Various known methods for drying by removing water such as warm air drying or drying by heating the support 20b, can be used as the drying method.
  • the speed of the warm air may be set as appropriate so that the coating composition can be dried quickly and the coating film (gel film) of the coating composition does not collapse. Specifically, 0.5 to 200 m / min is preferable, 0.75 to 200 m / min is more preferable, and 1 to 200 m / min is particularly preferable.
  • the temperature of the hot air may be appropriately set at a temperature at which the support 20b is not deformed and the coating composition can be dried quickly.
  • the film surface temperature is preferably 1 to 120 ° C., more preferably 2 to 115 ° C., and particularly preferably 3 to 110 ° C.
  • drying of the facilitated transport film 20a by heating the support 20b is preferably performed at a temperature of the support 20b of 60 to 120 ° C, more preferably 60 to 90 ° C, and more preferably 70 to 80 ° C. It is particularly preferable to carry out as In this case, the film surface temperature is preferably 15 to 80 ° C., more preferably 30 to 70 ° C.
  • the coating composition is dried to produce the facilitated transport membrane 20a, that is, the acidic gas separation membrane 20, the acidic gas separation membrane 20 is wound into a roll.
  • the support 20b on which the carrier diffusion suppression layer 20c is formed is temporarily wound, and the support 20b on which the carrier diffusion suppression layer 20c is formed is sent out from this roll to form the facilitated transport film 20a. is doing.
  • the support 20b on which the carrier diffusion suppressing layer 20c is formed is not wound up, but is transported in the longitudinal direction as it is to form the facilitated transport film 20a to produce the acidic gas separation film 20, May be.
  • the facilitated transport membrane 2a is formed on the support 20b on which the carrier diffusion suppressing layer 20c is formed.
  • the acid gas separation membrane has various configurations other than this. Is possible.
  • a structure in which a part or all of the facilitated transport film 20a is impregnated with a nonwoven fabric or the like can be used for the purpose of reinforcing mechanical strength such as pressure resistance.
  • a configuration in which part or all of the facilitated transport film 20a is formed inside a nonwoven fabric or the like can be used.
  • the acidic gas separation membrane has a configuration in which a nonwoven fabric impregnated with the facilitated transport membrane 20a is laminated on the support 20b on which the carrier diffusion suppression layer 20c is formed.
  • a nonwoven fabric the nonwoven fabric which consists of materials, such as PP, PPS, PET, PVA, is illustrated as an example.
  • the nonwoven fabric which consists of PP and PPS is used suitably at points, such as the decomposition
  • the support 20b a support having a two-layer structure in which a porous film and an auxiliary support film are stacked can be suitably used.
  • Such an acidic gas separation membrane having a structure in which the nonwoven fabric is impregnated with the facilitated transport film 20a produces a support 20b on which the carrier diffusion suppressing layer 20c is formed and a nonwoven fabric impregnated with the facilitated transport film 20a. And what is necessary is just to manufacture by laminating
  • the facilitated transport film 20a may be formed by laminating a nonwoven fabric on the support 20b on which the carrier diffusion suppressing layer 20c is formed and impregnating the nonwoven fabric.
  • the separation module 10 a method for producing the laminated body 14 a including the acidic gas separation membrane 20, the supply gas flow path member 24 and the permeate gas flow path member 26, and a winding method of the laminated body 14 a, that is, lamination A method for producing the wound body 14 will be described.
  • the supply gas flow path member 24 and the permeate gas flow path member 26 have end faces (end portions) in order to simplify the drawings and clearly show the configuration. Only the net is shown.
  • the extending direction of the central cylinder 12 and the short direction coincide with each other, and the fixing means 34 such as an adhesive is attached to the central cylinder 12.
  • the fixing means 34 such as an adhesive is attached to the central cylinder 12.
  • the tube wall of the center tube 12 is provided with a slit (not shown) along the axial direction.
  • a distal end portion of a permeating gas channel member 26 to be described later is inserted into the slit, and is fixed to the inner peripheral surface of the center tube 12 by fixing means.
  • the inner peripheral surface of the central tube 12 and the permeating gas channel Friction with the member 26 can prevent the permeate gas flow path member 26 from coming out of the slit, that is, the permeate gas flow path member 26 is fixed.
  • the acidic gas separation membrane 20 produced as described above is folded in half with the facilitated transport membrane 20a inside, and the supply gas flow path member 24 is sandwiched therebetween. That is, the holding body 36 is manufactured in which the supply gas flow path member 24 is held between the acidic gas separation membranes 20 folded in half.
  • the acidic gas separation membrane 20 is not equally folded in half, but is folded in half so that one is slightly longer as shown in FIG.
  • a sheet-like protective member for example, Kapton tape
  • Etc. are preferably arranged.
  • an adhesive 30a to be the adhesive layer 30 is applied to the shorter surface of the acid gas separation membrane 20 folded in half (the surface of the support 20b).
  • the adhesive 30 a extends in the vicinity of both ends in the width direction (arrow x direction) and extends in the entire winding direction (arrow y direction). Furthermore, it is applied to the entire region in the width direction in the vicinity of the end portion opposite to the folded portion, and is applied in a band shape.
  • the surface coated with the adhesive 30a is directed to the permeating gas flow path member 26, and the folded side is directed to the central cylinder 12.
  • the sandwiching body 36 is laminated on the permeate gas flow path member 26 fixed to the central cylinder 12, and the permeate gas flow path member 26 and the acidic gas separation membrane 20 (support 20b) are bonded.
  • an adhesive 30a to be the adhesive layer 30 is applied to the upper surface (the surface of the longer support 20b) of the sandwiched sandwich 36.
  • the direction opposite to the permeating gas flow path member 26 first fixed to the central cylinder 12 by the fixing means 34 is also referred to as the upper side.
  • the adhesive 30a on this surface also extends in the vicinity of both ends in the width direction and is applied in a strip shape in the vicinity of both ends in the width direction. Furthermore, it extends in the entire region in the width direction in the vicinity of the end opposite to the folded portion and is applied in a band shape.
  • the permeate gas flow path member 26 is laminated on the sandwich 36 applied with the adhesive 30a, and the acidic gas separation membrane 20 (support 20b) and the permeate gas flow are laminated.
  • the road member 26 is bonded to form the laminated body 14a. Note that a plurality of permeate gas channel members 26 may be used as necessary.
  • a sandwiching body 36 in which the supply gas flow path member 24 is sandwiched between the acidic gas separation membranes 20 is produced, and an adhesive 30 a to be the adhesive layer 30 is applied.
  • the permeated gas flow path member 26 and the sandwiching body 36 that are finally stacked are stacked and bonded with the side to which the adhesive is applied facing down.
  • an adhesive 30a is applied to the upper surface of the laminated sandwiching body 36 as shown in FIGS. 6A and 6B, and then, as shown in FIG. Then, the permeating gas flow path member 26 is laminated and bonded, and the second laminated body 14a is laminated.
  • the laminated body 14a is laminated so as to be gradually separated from the central tube 12 in the winding direction as it goes upward. Thereby, the laminated body 14a is easily wound around the central cylinder 12, and the end of the permeate gas flow path member 26 on the central cylinder 12 side or the vicinity of the end is preferably in contact with the central cylinder 12. it can.
  • the laminated body 14 a is wound around the central cylinder 12 so as to wind the laminated body 14 a.
  • the permeate gas passage member 26 on the outermost periphery is maintained for a predetermined time in a state where tension is applied in the pulling-out direction, that is, the direction of squeezing and the adhesive 30a and the like are dried.
  • the outermost permeating gas channel member 26 is the lowermost permeating gas channel member 26 fixed to the central cylinder 12 first.
  • the outermost permeate gas channel member 26 is fixed by ultrasonic welding or the like at a position where it has made one round, and the excess permeate gas channel member 26 outside the fixed position is cut.
  • the laminated body 14 is obtained by winding the laminated body 14a around the central cylinder.
  • the raw material gas G is supplied from the end of the supply gas flow path member 24, and the acidic gas Gc passes through the acidic gas separation membrane 20 by being transported in the stacking direction, and passes through the permeated gas flow. It flows into the road member 26, flows through the permeate gas flow path member 26, and reaches the central cylinder 12.
  • the adhesive 30a is applied to the support 20b, which is a porous body, and the net-like permeating gas channel member 26 is bonded to the adhesive 30a. Therefore, the adhesive 30a penetrates (impregnates) the support 20b and the permeating gas flow path member 26, and the adhesive layer 30 is formed inside of both. Further, as described above, the adhesive layer 30 (adhesive 30a) is formed in a strip shape extending in the entire vicinity in the winding direction in the vicinity of both ends in the width direction. Further, the adhesive layer 30 extends across the entire width direction in the vicinity of the end portion on the side opposite to the folded portion on the central tube 12 side so as to cross the adhesive layer 30 in the vicinity of both ends in the width direction in the width direction.
  • the adhesive layer 30 is formed so as to surround the outer peripheries of the permeating gas flow path member 26 and the support 20b by opening the central tube 12 side.
  • the permeating gas channel member 26 is sandwiched between the facilitated transport films 20a.
  • an envelope-like flow path that opens on the side of the central tube 12 is formed in the permeating gas flow path member 26 of the laminate 14a. Therefore, the acidic gas Gc that has passed through the acidic gas separation membrane 20 and has flowed into the permeate gas flow path member 26 flows through the permeate gas flow path member 26 toward the central cylinder 12 without flowing out, It flows into the center tube 12 from the through hole 12a. That is, the adhesive layer 30 acts not only for bonding but also as a sealing portion for sealing the acidic gas Gc to a predetermined channel in the permeating gas channel member 26 and the like.
  • various known adhesives can be used as long as the adhesive layer 30 (adhesive 30a) has sufficient adhesive strength, heat resistance, and moisture resistance.
  • adhesives include epoxy resins, vinyl chloride copolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinylidene chloride copolymers, vinyl chloride-acrylonitrile copolymers, butadiene-acrylonitrile copolymers, polyamide resins, polyvinyl butyral.
  • Preferred examples include polyesters, cellulose derivatives (nitrocellulose, etc.), styrene-butadiene copolymers, various synthetic rubber resins, phenol resins, urea resins, melamine resins, phenoxy resins, silicone resins, urea formamide resins, and the like. .
  • the adhesive 30a to be the adhesive layer 30 may be applied once, but preferably, an adhesive diluted with an organic solvent such as acetone is applied first, and only the adhesive is applied thereon.
  • the adhesive diluted with an organic solvent is preferably applied in a wide width, and the adhesive is preferably applied in a narrower width.
  • a telescope prevention plate (telescope prevention member) 16 is disposed at both ends of the laminated body 14 produced in this way.
  • the telescope prevention plate 16 is so-called that the laminated body 14 is pressed by the raw material gas G, the supply-side end surface is pushed in a nested manner, and the opposite-side end surface protrudes in a nested manner. It is a member for preventing the telescope phenomenon.
  • the telescope prevention plate 16 various known types used for spiral type separation modules can be used.
  • the telescope prevention plate includes an annular outer ring portion 16a, an annular inner ring portion 16b arranged in the outer ring portion 16a so as to coincide with the center, an outer ring portion 16a and an inner ring. And a rib (spoke) 16c for connecting and fixing the portion 16b.
  • the central cylinder 12 around which the laminate in which the laminate 14a is laminated is wound passes through the inner ring portion 16b.
  • the ribs 16c are provided radially at equal angular intervals from the center of the outer ring part 16a and the inner ring part 16b, and between the outer ring part 16a and the inner ring part 16b and each rib 16c. Is an opening 16d through which the source gas G or the residual gas Gr passes.
  • the telescoping prevention plate 16 may be disposed in contact with the end face of the laminated body 14. However, the telescope prevention plate 16 and the end face of the laminated body 14 have a slight gap in order to use the entire end face of the laminated body 14 for supplying the source gas and discharging the residual gas Gr. Are preferably arranged.
  • a metal material a resin material, ceramics, etc. are illustrated suitably.
  • the metal material include stainless steel (SUS), aluminum, aluminum alloy, tin, and tin alloy.
  • Examples of the resin material include polyethylene resin, polypropylene resin, aromatic polyamide resin, nylon 12, nylon 66, polysulfin resin, polytetrafluoroethylene resin, polycarbonate resin, acrylic / butadiene / styrene resin, acrylic / ethylene / styrene resin, Examples include epoxy resins, nitrile resins, polyether ether ketone resins (PEEK), polyacetal resins (POM), polyphenylene sulfide (PPS), and the like.
  • Examples of the resin material include fiber reinforced plastics of these resins. Examples of the fibers include glass fibers, carbon fibers, stainless steel fibers, and aramid fibers, and long fibers are particularly preferable. More specifically, examples of the fiber reinforced plastic include long glass fiber reinforced polypropylene and long glass fiber reinforced polyphenylene sulfide. Examples of ceramics include zeolite and alumina.
  • the covering layer 18 covers the peripheral surface of the laminated body 14 and blocks the discharge of the raw material gas G and the residual gas Gr from outside the peripheral surface, that is, the end surface of the laminated body 14. It is.
  • the covering layer 18 may be provided to cover not only the peripheral surface of the laminated body 14 but also the telescope prevention plate as necessary.
  • the covering layer 18 may be a cylindrical member or may be configured by winding a wire or a sheet-like member.
  • the FRP wire is impregnated with the adhesive used for the adhesive layer 30 described above, and the wire impregnated with the adhesive is laminated in multiple layers as necessary without gaps.
  • the coating layer 18 wound around is illustrated.
  • the fiber or matrix resin used in FRP examples include glass fiber, carbon fiber, Kevlar, Dyneema, etc. Among them, glass fiber is particularly preferable.
  • the matrix resin examples include an epoxy resin, a polyamide resin, an acrylate resin, and an unsaturated polyester resin, and an epoxy resin is preferable from the viewpoint of heat resistance and hydrolysis resistance.
  • a sheet shape such as a Kapton tape for preventing penetration of the adhesive into the laminated body 14 between the coating layer 18 and the laminated body 14.
  • a member may be provided.
  • PVA polyvinyl alcohol
  • PAA polyacrylic acid copolymer
  • a support roll formed by winding a long support 20b was prepared.
  • This support 20b is a laminate in which a porous film (porous PTFE, average pore diameter of 0.15 ⁇ m) having a thickness of 10 ⁇ m is laminated on the surface of a PP nonwoven fabric having a thickness of 200 ⁇ m.
  • a general-purpose film forming apparatus having a coating apparatus (roll coater), a drying apparatus, and an ultraviolet irradiation apparatus, which forms a film by a coating method using RtoR, is loaded with a support roll so that the porous film side becomes a surface to be coated.
  • the support 20b was inserted (paper passed) through a predetermined conveyance path, and the tip was wound around the winding shaft.
  • the coating composition used as the carrier diffusion suppression layer 20c prepared previously was filled in the material tank of the coating apparatus.
  • the coating composition that becomes the carrier diffusion suppression layer 20c is applied by the coating apparatus while the support 20b is transported in the longitudinal direction, the coating composition is dried by the drying apparatus, and the coating composition is dried by the ultraviolet irradiation apparatus.
  • coating of the coating composition was performed at normal temperature.
  • the coating amount of the coating composition was adjusted to 2.5 g / m 2 in a cured state when coated on a PET support.
  • the conveyance speed of the support 20b was 30 m / min. Irradiation with ultraviolet rays was performed so that the coating composition was cured in 10 seconds after the coating composition was applied (curing time 10 seconds).
  • the relationship between the curing time of the coating composition and the ultraviolet irradiation conditions was previously examined by experiments.
  • the surface of the support 20b (coating surface of the coating composition) is photographed with a scanning electron microscope, and image analysis is performed with commercially available image analysis software.
  • the projected area ratio (Ps) of the support 20b on the surface of the body 20b was measured. As a result, the projected area ratio (Ps) was 80%.
  • the support 20b is cut in the thickness direction, the cross section is photographed with a scanning operation type electron microscope, image analysis is performed with commercially available image analysis software, and the projected area ratio of the carrier diffusion suppression layer 20c in the cross section is determined. It was measured.
  • the measurement of the projected area ratio of the carrier diffusion suppression layer 20c in this cross section is performed in 10 arbitrary cross sections, and the average value is calculated, whereby the projected area ratio of the carrier diffusion suppression layer 20c in the cross section in the thickness direction of the support 20b. (Pc) was calculated. As a result, the projected area ratio (Pc) was 35%. Therefore, the projected area ratio (Ps) ⁇ the projected area ratio (Pc) is 2800.
  • a roll formed by winding the support roll and the support 20b on which the carrier diffusion suppression layer 20c was formed was removed from the film forming apparatus in which the carrier diffusion suppression layer 20c was formed on the support 20b.
  • a general film forming apparatus having a coating apparatus (roll coater) and a drying apparatus that forms a film by a coating method using RtoR is loaded with a roll formed by winding the support 20b on which the carrier diffusion suppression layer 20c is formed. Then, the support 20b on which the carrier diffusion suppression layer 20c was formed was inserted through a predetermined conveyance path, and the tip was wound around the winding shaft.
  • membrane 20a prepared previously was filled in the material tank of the coating device.
  • the film forming apparatus applies the coating composition by the coating apparatus while transporting the support 20b in the longitudinal direction, and the coating composition is dried by the drying apparatus, thereby promoting the carrier diffusion suppressing layer 20c.
  • an acid gas separation membrane 20 having a support 20b, a carrier diffusion suppression layer 20c, and a facilitated transport membrane 20a as shown in FIGS. 3 (A) and 3 (B) is prepared. And wound into a roll.
  • coating of the coating composition was performed so that the thickness of the facilitated-transport film
  • the relationship between the coating amount (coating film thickness) of the coating composition and the thickness of the facilitated transport film 20a to be formed was examined in advance by experiments.
  • the permeating gas flow path member 26 was fixed to the center tube 12 made of SUS.
  • a 100-mesh stainless steel wire mesh (wire diameter: 0.1 mm, aperture: 0.154 mm) was used.
  • the fixing means 34 an adhesive capable of adhering SUS was used.
  • the produced acidic gas separation membrane 20 was cut into a predetermined length and folded in half with the facilitated transport membrane 20a inside. As shown in FIG. 5, the half-folding was performed so that one acidic gas separation membrane 20 was slightly longer. Kapton tape was attached to the valley of the acid gas separation membrane 20 folded in half, and the end of the supply gas flow path member 24 was reinforced so as not to damage the valley of the facilitated transport membrane 20a. Subsequently, the supply gas flow path member 24 was sandwiched between the folded acidic gas separation membranes 20 to produce a sandwiching body 36. As the supply gas flow path member 24, a PP net having a thickness of 0.5 mm was used.
  • the entire region in the winding direction (arrow y direction) is disposed on the side of the support 20b on which the acidic gas separation membrane 20 of the sandwich 36 is shorter.
  • the adhesive 30a was applied to the entire region in the width direction in the vicinity of the end portion on the side opposite to the folded portion in the winding direction.
  • an adhesive made of an epoxy resin (E120HP manufactured by Henkel Japan) was used.
  • the sandwiching body 36 and the permeating gas flow path member 26 fixed to the central cylinder 12 are provided. Laminated and glued.
  • winding is performed on the upper surface of the acidic gas separation membrane 20 of the sandwiching body 36 laminated on the permeating gas flow path member 26 in the vicinity of both ends in the width direction.
  • the adhesive 30a was applied so as to extend over the entire region in the width direction and in the vicinity of the end portion on the opposite side of the folded portion in the winding direction.
  • a permeate gas flow path member 26 is laminated on the acidic gas separation membrane 20 coated with the adhesive 30a and bonded to form the first layered product 14a. did.
  • an adhesive 38a is applied to the peripheral surface of the central cylinder 12, as shown in FIG.
  • the adhesive 38b was applied on the permeating gas flow path member 26 between the central cylinder 12 and the lowermost layered laminate 14a.
  • the adhesives 38a and 38b were the same as the adhesive 30a.
  • the laminated body 14 a having three layers was wound around the central cylinder 12 in a multiple manner so as to be a laminated body 14.
  • the center tube 12 is inserted into the inner ring portion 16b at both ends of the laminated body 14 and shown in FIG.
  • a telescoping prevention plate 16 having a thickness of 2 cm was attached.
  • the telescope prevention plate 16 was made of PPS containing 40% by mass of glass fiber.
  • the distance between the telescope prevention plate 16 and the laminate wound product 14 was 1 mm.
  • the coating layer 18 was formed by winding the FRP resin tape around the peripheral surface of the telescope prevention plate 16 and the peripheral surface of the laminated body 14 to produce the separation module 10.
  • the membrane area of the prepared separation module 10 was 1.2 m 2 (design value) in total.
  • Example 2 As the support 20b, a laminate in which a porous film (porous PTFE, average pore diameter 0.15 ⁇ m) having a thickness of 15 ⁇ m is laminated on the surface of a 200 ⁇ m-thick PP nonwoven fabric, and the carrier diffusion suppressing layer 20c is used.
  • the acidic gas separation membrane 20 was produced in the same manner as in Example 1 except that the coating amount of the coating composition to be the carrier diffusion suppressing layer 20c was 1.5 times. Therefore, also in this example, the porous film of the laminated body which is the support 20b becomes the porous support in the present invention.
  • Example 1 the projected area ratio (Ps) of the support 20b on the surface of the support 20b and the projected area ratio (Pc) of the carrier diffusion suppression layer 20c in the cross section in the thickness direction of the support 20b are measured. did. As a result, the projected area ratio (Ps) was 90%, and the projected area ratio (Pc) was 45%. Therefore, the projected area ratio (Ps) ⁇ projected area ratio (Pc) is 4050.
  • a separation module 10 was produced in the same manner as in Example 1 except that this acidic gas separation membrane 20 was used.
  • Example 3 As the support 20b, a laminate in which a porous film (porous PTFE, average pore diameter 0.15 ⁇ m) having a thickness of 15 ⁇ m is laminated on the surface of a PP nonwoven fabric having a thickness of 200 ⁇ m, and the carrier diffusion suppressing layer 20c is used.
  • the acidic gas separation membrane 20 was produced in the same manner as in Example 1 except that the coating amount of the coating composition to be the carrier diffusion suppressing layer 20c was doubled. Therefore, also in this example, the porous film of the laminated body which is the support 20b becomes the porous support in the present invention.
  • Example 1 the projected area ratio (Ps) of the support 20b on the surface of the support 20b and the projected area ratio (Pc) of the carrier diffusion suppression layer 20c in the cross section in the thickness direction of the support 20b are measured. did. As a result, the projected area ratio (Ps) was 65%, and the projected area ratio (Pc) was 60%. Therefore, the projected area ratio (Ps) ⁇ projected area ratio (Pc) is 3900.
  • a separation module 10 was produced in the same manner as in Example 1 except that this acidic gas separation membrane 20 was used.
  • Example 4 As the support 20b, a laminate in which a porous film (porous PTFE, average pore diameter 0.15 ⁇ m) having a thickness of 15 ⁇ m is laminated on the surface of a 200 ⁇ m-thick PP nonwoven fabric, and further, the carrier diffusion suppression layer 20c is used.
  • a porous film porous PTFE, average pore diameter 0.15 ⁇ m
  • the polymerizable polydimethylsiloxane added to the coating composition to be the carrier diffusion suppression layer 20c was changed to KF-102 manufactured by Shin-Etsu Silicone, and
  • the acid gas separation membrane 20 was prepared in the same manner as in Example 1 except that the hexane solution A was diluted to 20% by mass with hexane and the curing time of the coating composition to be the carrier diffusion suppression layer 20c was changed to 5 seconds. Produced. Therefore, also in this example, the porous film of the laminated body which is the support 20b becomes the porous support in the present invention.
  • Example 1 the projected area ratio (Ps) of the support 20b on the surface of the support 20b and the projected area ratio (Pc) of the carrier diffusion suppression layer 20c in the cross section in the thickness direction of the support 20b are measured. did. As a result, the projected area ratio (Ps) was 55%, and the projected area ratio (Pc) was 35%. Therefore, the projected area ratio (Ps) ⁇ the projected area ratio (Pc) is 1925.
  • a separation module 10 was produced in the same manner as in Example 1 except that this acidic gas separation membrane 20 was used.
  • Example 5 In the formation of the carrier diffusion suppression layer 20c, the hexane solution A was diluted to 30% by mass with hexane in the preparation of the coating composition to be the carrier diffusion suppression layer 20c, and the coating amount of the coating composition to be the carrier diffusion suppression layer 20c was 2
  • the acidic gas separation membrane 20 was prepared in the same manner as in Example 4 except that the curing time of the coating composition to be the carrier diffusion suppressing layer 20c was changed to 7 seconds. Therefore, also in this example, the porous film of the laminated body which is the support 20b becomes the porous support in the present invention.
  • Example 1 the projected area ratio (Ps) of the support 20b on the surface of the support 20b and the projected area ratio (Pc) of the carrier diffusion suppression layer 20c in the cross section in the thickness direction of the support 20b are measured. did. As a result, the projected area ratio (Ps) was 65%, and the projected area ratio (Pc) was 55%. Therefore, the projected area ratio (Ps) ⁇ projected area ratio (Pc) is 3575.
  • a separation module 10 was produced in the same manner as in Example 1 except that this acidic gas separation membrane 20 was used.
  • Example 6 In the formation of the carrier diffusion suppression layer 20c, the hexane solution A was diluted to 35% by mass with hexane in the preparation of the coating composition to be the carrier diffusion suppression layer 20c, and the coating amount of the coating composition to be the carrier diffusion suppression layer 20c was 3
  • the acidic gas separation membrane 20 was produced in the same manner as in Example 4 except that the curing time of the coating composition to be the carrier diffusion suppression layer 20c was changed to 10 seconds. Therefore, also in this example, the porous film of the laminated body which is the support 20b becomes the porous support in the present invention.
  • Example 1 the projected area ratio (Ps) of the support 20b on the surface of the support 20b and the projected area ratio (Pc) of the carrier diffusion suppression layer 20c in the cross section in the thickness direction of the support 20b are measured. did. As a result, the projected area ratio (Ps) was 85%, and the projected area ratio (Pc) was 70%. Therefore, the projected area ratio (Ps) ⁇ projected area ratio (Pc) is 5950.
  • a separation module 10 was produced in the same manner as in Example 1 except that this acidic gas separation membrane 20 was used.
  • Example 7 As the support 20b, a laminate in which a porous film (porous PTFE, average pore diameter of 0.15 ⁇ m) having a thickness of 100 ⁇ m is laminated on the surface of a PP nonwoven fabric having a thickness of 200 ⁇ m, and further, the carrier diffusion suppressing layer 20c is used.
  • the coating composition to be the carrier diffusion suppression layer 20c was prepared by diluting the hexane solution A to 3% by mass with hexane to double the coating amount of the coating composition to be the carrier diffusion suppression layer 20c.
  • an acidic gas separation membrane 20 was produced.
  • the porous film of the laminated body which is the support 20b becomes the porous support in the present invention.
  • the projected area ratio (Ps) of the support 20b on the surface of the support 20b and the projected area ratio (Pc) of the carrier diffusion suppression layer 20c in the cross section in the thickness direction of the support 20b are measured. did.
  • the projected area ratio (Ps) was 90%, and the projected area ratio (Pc) was 40%. Therefore, the projected area ratio (Ps) ⁇ the projected area ratio (Pc) is 3600.
  • a separation module 10 was produced in the same manner as in Example 1 except that this acidic gas separation membrane 20 was used.
  • PVA polyvinyl alcohol
  • PAA polyacrylic acid copolymer
  • ORGATICS TC-100 manufactured by Matsumoto Fine Chemical Co., Ltd.
  • a Ti-based cross-linking agent was added so as to have a ratio of 10% by mass with respect to the PVA-PAA copolymer, and the mixture was stirred and degassed to obtain a coating composition A product was prepared.
  • the PVA-PAA copolymer was synthesized in the same manner as in Example 1.
  • An acidic gas separation membrane 20 was produced in the same manner as in Example 6 except that the facilitated transport membrane 20a was formed using this coating composition. Therefore, also in this example, the porous film of the laminated body which is the support 20b becomes the porous support in the present invention.
  • the projected area ratio (Ps) of the support 20b on the surface of the support 20b and the projected area ratio (Pc) of the carrier diffusion suppression layer 20c in the cross section in the thickness direction of the support 20b are measured. did. As a result, the projected area ratio (Ps) was 85%, and the projected area ratio (Pc) was 70%. Therefore, the projected area ratio (Ps) ⁇ projected area ratio (Pc) is 5950.
  • a separation module 10 was produced in the same manner as in Example 1 except that this acidic gas separation membrane 20 was used.
  • Example 9 ⁇ Formation of carrier diffusion suppression layer>
  • the support 20b is a laminate in which a porous membrane (porous PTFE, average pore diameter of 0.15 ⁇ m) having a thickness of 15 ⁇ m is laminated on the surface of a PP nonwoven fabric having a thickness of 200 ⁇ m. Therefore, also in this example, the porous film of the laminated body which is the support 20b becomes the porous support in the present invention.
  • a porous membrane porous PTFE, average pore diameter of 0.15 ⁇ m
  • the projected area ratio (Ps) of the support 20b on the surface of the support 20b and the projected area ratio (Pc) of the carrier diffusion suppression layer 20c in the cross section in the thickness direction of the support 20b are measured. did. As a result, the projected area ratio (Ps) was 85%, and the projected area ratio (Pc) was 70%. Therefore, the projected area ratio (Ps) ⁇ projected area ratio (Pc) is 5950.
  • a roll formed by winding a long nonwoven fabric was prepared.
  • This non-woven fabric is a PP non-woven fabric (OL-30, manufactured by Nippon Vilene Co., Ltd.) having a fiber diameter of 30 ⁇ m, a basis weight of 30 g / m 2 , and an ISO air permeability of 3.1 ⁇ m / (Pa ⁇ sec).
  • a general film forming device that has a coating device (roll coater) and a drying device and forms a film by a coating method using RtoR is loaded with a roll formed by winding this nonwoven fabric, and the nonwoven fabric is inserted into a predetermined transport path. Then, the tip was wound around the winding shaft.
  • membrane 20a same as Example 8 was filled into the material tank of the coating device.
  • the transporting film 20a is formed in a roll by applying the coating composition with a coating apparatus while drying the nonwoven fabric in the longitudinal direction with this film forming apparatus and drying the coating composition with a drying apparatus. Wound around.
  • coating of the coating composition was performed so that the thickness of the facilitated-transport film
  • the relationship between the coating amount (coating film thickness) of the coating composition and the thickness of the facilitated transport film 20a to be formed has been examined in advance by experiments. When confirmed with a cross-sectional observation image of an electron microscope, the facilitated transport film 20a was formed in a layer form in the nonwoven fabric in the entire area in the plane direction.
  • the support 20b a laminate in which a porous film (porous PTFE, average pore diameter 0.15 ⁇ m) having a thickness of 15 ⁇ m is laminated on the surface of a 200 ⁇ m-thick PP nonwoven fabric, and further, the carrier diffusion suppression layer 20c is used.
  • the coating composition to be the carrier diffusion suppression layer 20c is prepared by diluting the hexane solution A to 20% by mass with hexane in the preparation of the coating composition to be the carrier diffusion suppression layer 20c, and setting the transport speed of the support 20b to 60 m / min.
  • the acidic gas separation membrane 20 was produced in the same manner as in Example 1 except that the coating amount of the product was increased to 4 times and the curing time of the coating composition to be the carrier diffusion suppression layer 20c was changed to 3 seconds. Therefore, also in this example, the porous film of the laminated body which is the support 20b becomes the porous support in the present invention.
  • the projected area ratio (Ps) of the support 20b on the surface of the support 20b and the projected area ratio (Pc) of the carrier diffusion suppression layer 20c in the cross section in the thickness direction of the support 20b are measured. did.
  • the projected area ratio (Ps) was 4%
  • the projected area ratio (Pc) was 90%. Therefore, the projected area ratio (Ps) ⁇ projected area ratio (Pc) is 360.
  • a separation module was produced in the same manner as in Example 1 except that this acidic gas separation membrane 20 was used.
  • Example 2 As the support 20b, a laminate in which a porous film (porous PTFE, average pore diameter 0.15 ⁇ m) having a thickness of 15 ⁇ m is laminated on the surface of a 200 ⁇ m-thick PP nonwoven fabric, and further, the carrier diffusion suppression layer 20c is used.
  • the hexane solution A was diluted to 80% by mass with hexane in the preparation of the coating composition to be the carrier diffusion suppressing layer 20c
  • the conveying speed of the support 20b was 10 m / min
  • the coating composition to be the carrier diffusion suppressing layer 20c An acidic gas separation membrane 20 was produced in the same manner as in Example 1 except that the amount of the product applied was halved.
  • the porous film of the laminated body which is the support 20b becomes the porous support in the present invention.
  • the projected area ratio (Ps) of the support 20b on the surface of the support 20b and the projected area ratio (Pc) of the carrier diffusion suppression layer 20c in the cross section in the thickness direction of the support 20b are measured. did.
  • the projected area ratio (Ps) was 92%, and the projected area ratio (Pc) was 5%. Therefore, the projected area ratio (Ps) ⁇ the projected area ratio (Pc) is 460.
  • a separation module was produced in the same manner as in Example 1 except that this acidic gas separation membrane 20 was used.
  • the hexane solution A was diluted to 3% by mass with hexane in the preparation of the coating composition to be the carrier diffusion suppression layer 20c, and the conveyance speed of the support 20b was set to 60 m / min.
  • the acidic gas separation membrane 20 is produced in the same manner as in Example 4 except that the coating amount of the coating composition to be the layer 20c is halved and the curing time of the coating composition to be the carrier diffusion suppression layer 20c is changed to 3 seconds. did. Therefore, also in this example, the porous film of the laminated body which is the support 20b becomes the porous support in the present invention.
  • Example 1 the projected area ratio (Ps) of the support 20b on the surface of the support 20b and the projected area ratio (Pc) of the carrier diffusion suppression layer 20c in the cross section in the thickness direction of the support 20b are measured. did. As a result, the projected area ratio (Ps) was 32%, and the projected area ratio (Pc) was 31%. Therefore, the projected area ratio (Ps) ⁇ the projected area ratio (Pc) is 992.
  • a separation module was produced in the same manner as in Example 1 except that this acidic gas separation membrane 20 was used.
  • the source gas G was supplied to each separation module 10 under the conditions of a flow rate of 2.2 L / min, a temperature of 120 ° C., and a total pressure of 301.3 kPa.
  • a through hole for supplying a sweep gas was formed at the end of the central cylinder 12 on the raw material gas permeation side, and Ar gas having a flow rate of 0.6 L / min was supplied as a sweep gas from here.
  • Rate of change [(Value at 1 hour elapsed time-Value at 100 hour elapsed time) / Value at 1 hour elapsed time] ⁇ 100
  • the evaluation is as follows. A: Change rate between 1 hour and 100 hours is less than 5%
  • the projected area ratio (Ps) of the support 20b on the surface of the support 20b and the projected area ratio (Pc) of the carrier diffusion suppression layer 20c in the cross section in the thickness direction of the support 20b are as follows.
  • the examples that are both within the scope of the present invention are excellent in wet heat adhesion and separation performance durability, can prevent the facilitated transport film from falling off during the acidic gas separation operation, and the carrier is the facilitated transport film 20a and the support. It is a separation module excellent in durability, which is prevented from passing through 20b.
  • Examples 1 to 3 and Examples 5 and 7 in which the projected area ratio (Ps) ⁇ projected area ratio (Pc) exceeds 2500 are excellent in either wet heat adhesion or separation performance durability.
  • SYMBOLS 10 (Acid gas) separation module 12 Center tube 14 Laminated body roll 14a Laminate body 16 Telescope prevention board 16a Outer ring part 16b Inner ring part 16c Rib 16d Opening part 18 Covering layer 20 Acid gas separation membrane 20R Separation membrane roll 20A Separator Membrane Adherent 20AR Adherent Roll 20a Accelerated Transport Membrane 20b (Porous) Support 20c Carrier Diffusion Suppressing Layer 24 Supply Gas Channel Member 26 Permeate Gas Channel Member 30 Adhesive Layer 30a Adhesive 34 Fixing Means

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne un module de séparation de gaz acide qui comprend : une membrane de séparation de gaz acide qui comprend un corps de support poreux, une couche de suppression de la diffusion formant support dont au moins une partie est formée à l'intérieur du corps de support poreux, et une membrane de transport facilité qui contient un composé hydrophile et un support qui est réactif avec un gaz acide ; et un élément d'alimentation de canaux de gaz, qui sert de canal pour un gaz de départ. Le rapport de la surface projetée du corps de support poreux dans la surface en excluant la membrane de transport facilité est de 50 % ou plus, et le rapport de la surface projetée de la couche de suppression de la diffusion formant support en coupe transversale dans le sens de l'épaisseur du corps de support poreux est de 30 % ou plus. En conséquence, la présente invention prévoit un module de séparation de gaz acide qui fait preuve d'une excellente adhésion d'une membrane de transport facilité, tout en ayant une bonne durabilité.
PCT/JP2016/050329 2015-01-26 2016-01-07 Module de séparation de gaz acide WO2016121436A1 (fr)

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CN110694462B (zh) * 2019-09-30 2021-09-10 北京工业大学 一种pdms与泡沫陶瓷复合填料及其制备方法
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