WO2015029884A1 - Procédé de production d'un film de séparation de gaz acide - Google Patents

Procédé de production d'un film de séparation de gaz acide Download PDF

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Publication number
WO2015029884A1
WO2015029884A1 PCT/JP2014/071937 JP2014071937W WO2015029884A1 WO 2015029884 A1 WO2015029884 A1 WO 2015029884A1 JP 2014071937 W JP2014071937 W JP 2014071937W WO 2015029884 A1 WO2015029884 A1 WO 2015029884A1
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Prior art keywords
coating composition
facilitated transport
transport film
film
roll
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PCT/JP2014/071937
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English (en)
Japanese (ja)
Inventor
吉宏 油屋
米山　聡
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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    • 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
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B01D67/00793—Dispersing a component, e.g. as particles or powder, in another component
    • 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
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • 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
    • 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
    • B01D69/1218—Layers having the same chemical composition, but different properties, e.g. pore size, molecular weight or porosity
    • 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
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
    • 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
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/142—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers"
    • 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
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • B01D71/381—Polyvinylalcohol
    • 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
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/401—Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
    • 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
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/401—Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
    • B01D71/4011—Polymethylmethacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/022—Asymmetric membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • 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
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/36—Polytetrafluoroethene
    • 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
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • 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

Definitions

  • the present invention relates to a method for producing an acidic gas separation membrane that selectively separates acidic gas from raw material gas. Specifically, the present invention relates to a method for producing an acid gas separation membrane capable of appropriately forming a facilitated transport membrane on the facilitated transport membrane in an acidic gas separation membrane having a multilayer facilitated transport membrane.
  • 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 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.
  • Patent Document 2 a coating composition (coating solution) containing a water-absorbing polymer, a carbon dioxide carrier, and a gelling agent and prepared at 50 ° C. or higher is applied to a support.
  • An apparatus for producing an acidic gas separation membrane is described in which the coating film formed in the above is cooled to 12 ° C. or less to form a gel membrane, and this gel membrane is dried with warm air to form a carbon dioxide separation membrane.
  • the acid gas separation membrane shown in Patent Document 1 and Patent Document 2 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. .
  • the thickness of the facilitated transport film is about 1 to 200 ⁇ m.
  • a coating composition to be a facilitated transport film is applied at 1 mm or less, and this coated film is gel-dried to form a facilitated transport film having a thickness of about 5 to 50 ⁇ m. Yes.
  • the facilitated transport film when carbon dioxide is separated from a mixed gas of carbon dioxide and hydrogen, the facilitated transport film actively permeates carbon dioxide by the chemical reaction of the carrier. At the same time, hydrogen also dissolves and diffuses on the film surface. Through. For this reason, it is advantageous that the facilitated transport film is thicker in terms of lowering the hydrogen permeability.
  • a facilitated transport film when a facilitated transport film is formed by applying a coating composition on a support and drying it, if the coating composition is thin, it will be mixed into foreign matter or coating on the support surface. Due to the bubbles, defects such as pinholes may occur in the formed facilitated transport film.
  • the object of the present invention is to solve such problems of the prior art, and by forming the facilitated transport film a plurality of times, it is possible to form the intended thick facilitated transport film,
  • An object of the present invention is to provide a method for producing an acidic gas separation membrane capable of forming a uniform facilitated transport membrane free from membrane defects and the like with all facilitated transport membranes.
  • the first aspect of the method for producing an acidic gas separation membrane of the present invention includes a carrier that reacts with an acidic gas on the surface of a porous support, and a hydrophilic property for supporting the carrier.
  • a coating composition containing a carrier that reacts with an acidic gas and a hydrophilic compound for supporting the carrier is applied to the surface of the previously formed facilitated transport film, and the applied coating composition is dried and accelerated.
  • the temperature and humidity of the space to which the facilitated transport film formed in the previous step is exposed before the coating composition is applied are measured.
  • a method for producing an acid gas separation membrane characterized in that the temperature and humidity of a space are controlled so as to be 10 to 50% RH.
  • the workpiece is sent out from a workpiece roll formed by winding a long workpiece and conveyed in the longitudinal direction. It is preferable to use a roll-to-roll method in which processing is performed and a processed object is wound into a roll shape to form a processed roll.
  • the porous support is sent out from a support roll formed by winding the porous support, and the porous support is transported in the longitudinal direction, and the initial film forming process or one or more laminated film forming processes are performed.
  • the processed object to be processed is wound into a roll to form a processed roll, and then the processed object to be processed is sent out from this processed roll to perform a laminated film forming process.
  • the space in which the processed roll for supplying the processed object is present, and the facilitated transport film until the coating composition is applied It is preferable to manage temperature and humidity in the space where the water is exposed. Further, in the initial film forming step and the laminated film forming step, the temperature and humidity of the space to which the formed facilitated transport film is exposed from the drying of the coating composition to the winding of the processed object to be processed in a roll shape. It is preferable to measure and control the temperature and humidity of the space so that the temperature and humidity are in a predetermined range.
  • the coating composition preferably has a temperature of 15 to 35 ° C. and a viscosity of 0.1 to 5 Pa ⁇ sec.
  • the coating composition in an initial stage film formation process and the coating composition in at least 1 time of laminated film formation process are the same compositions. Moreover, it is preferable that the coating composition in an initial stage film formation process and the coating composition in at least 1 time of laminated film formation process are different compositions. Further, it is preferable that the coating composition contains cesium carbonate as a carrier, polyvinyl alcohol-polyacrylic acid copolymer as a hydrophilic compound, and further contains a crosslinking agent.
  • the second aspect of the method for producing an acidic gas separation membrane of the present invention is a coating composition containing a carrier that reacts with an acidic gas and a hydrophilic compound for supporting the carrier on the surface of the porous support.
  • a coating composition containing a carrier that reacts with an acidic gas and a hydrophilic compound for supporting the carrier is applied to the surface of the previously formed facilitated transport film, and the applied coating composition is dried and accelerated.
  • the acidic gas is characterized in that the coating composition is applied under a condition that the weight increase rate due to water absorption of the facilitated transport film formed in the previous step is 40% by mass or less.
  • a method for producing a separation membrane is provided.
  • the workpiece is sent out from a workpiece roll formed by winding a long workpiece and conveyed in the longitudinal direction. It is preferable to use a roll-to-roll method in which processing is performed and a processed object is wound into a roll shape to form a processed roll.
  • the coating composition preferably has a temperature of 15 to 35 ° C. and a viscosity of 0.1 to 5 Pa ⁇ sec. Moreover, it is preferable that the coating composition in an initial stage film formation process and the coating composition in at least 1 time of laminated film formation process are the same compositions.
  • the coating composition is applied under the condition that is 40% by mass or less.
  • the coating composition preferably contains cesium carbonate as a carrier, polyvinyl alcohol-polyacrylic acid copolymer as a hydrophilic compound, and further contains a crosslinking agent.
  • the temperature and humidity of the space to which the formed facilitated transport film is exposed from the drying of the coating composition to the winding of the processed object to be rolled are changed. It is preferable to measure and control the temperature and humidity of the space so that the temperature and humidity are in a predetermined range.
  • the uniform coating composition is formed on the entire surface without causing repelling.
  • a coating film liquid film
  • all facilitated transports are formed when forming the facilitated transport film of the target thick film by forming the facilitated transport film several times by overlapping and forming the facilitated transport film.
  • a uniform facilitated transport film having no film defects or the like can be formed.
  • FIG. 1 conceptually shows an example of an acidic gas separation membrane manufacturing apparatus for carrying out the acidic gas separation membrane manufacturing method of the present invention.
  • a manufacturing apparatus 10 shown in FIG. 1 manufactures an acidic gas separation membrane 50 according to the manufacturing method of the present invention as conceptually shown in FIG. 2 by a so-called roll-to-roll method (hereinafter also referred to as RtoR). It is.
  • RtoR roll-to-roll method
  • RtoR is a process of drawing or drying a coating composition while pulling out a workpiece from a roll wound with a long workpiece and transporting the workpiece in the longitudinal direction. It is a manufacturing method which goes and rolls the processed to-be-processed object in roll shape. That is, the manufacturing apparatus 10 sends out the porous support 52 from a support roll 52R formed by winding the long porous support 52 into a roll shape, and transports the porous support 52 in the longitudinal direction.
  • the first facilitated transport film 54a is formed on the surface of the porous support 52, and the porous support 52 (hereinafter referred to as the treated support 56 for convenience) formed with the facilitated transport film 54a is wound in a roll shape.
  • the manufacturing apparatus 10 feeds the processed support 56 from the processed support roll 56R and transports it in the longitudinal direction while forming a second facilitated transport film 54b on the facilitated transport film 54a.
  • the acidic gas separation membrane 50 according to the manufacturing method of the present invention is used, and the acidic gas separation membrane 50 is wound into a roll to obtain a separation membrane roll 50R.
  • Such a manufacturing apparatus 10 basically includes a supply unit 12, a coating unit 14, a drying unit 18, and a winding unit 20.
  • the manufacturing apparatus 10 manufactures a functional film (functional film) using RtoR, such as a pass roller (guide roller), a pair of conveyance rollers, a conveyance guide, and various sensors as necessary. You may have various members provided in the apparatus to do.
  • the space including the supply unit 12 and the application unit 14 is a substantially closed space by the housing 26. Furthermore, a temperature / humidity measuring means 28 for measuring the temperature and humidity in the housing 26 and a temperature / humidity adjusting means 30 for adjusting the temperature and humidity in the housing 26 are provided inside the housing 26.
  • the manufacturing apparatus 10 for carrying out the manufacturing method of the present invention determines the temperature and humidity of the temperature / humidity measuring means 28.
  • the temperature and humidity adjusting means 30 adjusts the temperature in the housing 26 to 10 to 40 ° C. and adjusts the humidity in the housing 26 to 10 to 50% RH. This will be described in detail later.
  • the rotating shaft 34 is loaded with a support roll 52R formed by winding a long porous support 52 in a roll shape. That is, it is a part which sends out the porous support body 52 by rotating the support body roll 52R.
  • the supply unit 12 is loaded with a processed support roll 56R formed by winding the processed support 56 in a roll shape on the rotating shaft 34, It is also a part which sends out the processed support body 56 by rotating the rotating shaft 34, that is, the processed support roll 56R.
  • what is necessary is just to perform sending out and conveyance of such a porous support body 52 and the processed support body 56 by a well-known method.
  • the porous support 52 (hereinafter also referred to as the support 52) is permeable to an acidic gas such as carbon dioxide, and can be applied with a coating composition for forming the facilitated transport film 54a (coating film). Can be supported).
  • the support 52 supports the formed facilitated transport film 54a and facilitated transport film 54b. In the following description, when it is not necessary to distinguish the facilitated transport film 54a and the facilitated transport film 54b, only the facilitated transport film 54a is described as a representative of both.
  • As the forming material of the support 52 various known materials can be used as long as they can exhibit this function.
  • the support body 52 may be a single layer, but as shown in FIG. 2, it has a two-layer structure including a porous film 52a and an auxiliary support film 52b. preferable.
  • the support 52 more reliably expresses the functions of acid gas permeability, application of the coating composition to be the facilitated transport film 54, and support of the facilitated transport film 54a.
  • various materials exemplified below as the porous film 52a and the auxiliary support film 52b can be used as the forming material.
  • the porous membrane 52a is on the facilitated transport membrane 54a side.
  • the porous membrane 52a is preferably made of a material having heat resistance and low hydrolyzability.
  • Specific examples of the porous membrane 52a include membrane filter membranes such as polysulfone, polyethersulfone, polypropylene and cellulose, interfacial polymerized thin films of polyamide and polyimide, polytetrafluoroethylene (PTFE) and high molecular weight polyethylene.
  • PTFE polytetrafluoroethylene
  • An example is a stretched porous membrane.
  • a stretched porous membrane of PTFE or high molecular weight polyethylene has a high porosity, is small in inhibition of diffusion of acidic gas (especially carbon dioxide gas), and is preferable from the viewpoints of strength and manufacturing suitability.
  • a stretched porous membrane of PTFE is preferably used in terms of heat resistance and low hydrolyzability.
  • the porous membrane 52a is hydrophobic so that the facilitated transport membrane 54a containing moisture can easily penetrate into the porous portion in the usage environment and does not cause deterioration in film thickness distribution or performance over time. Is preferred. The same applies to the case where the support has a single layer structure.
  • the porous membrane 52a preferably has a maximum pore diameter of 1 ⁇ m or less. Further, the average pore diameter of the pores of the porous membrane 52a is preferably 0.001 to 10 ⁇ m, more preferably 0.002 to 5 ⁇ m, and particularly preferably 0.005 to 1 ⁇ m.
  • the adhesive application region described later sufficiently infiltrates the adhesive and that the porous membrane 52a prevents the passage of the acid gas. Further, when the coating composition described later is applied, it is possible to prevent the film surface from becoming non-uniform due to capillary action or the like.
  • the auxiliary support film 52b is provided to reinforce the porous film 52a.
  • Various materials can be used as the porous membrane 52a as long as it satisfies the required strength, stretch resistance and gas permeability.
  • a nonwoven fabric, a woven fabric, a net, and a mesh having an average pore diameter of 0.001 to 10 ⁇ m can be appropriately selected and used.
  • the auxiliary support film 52b is also preferably made of a material having heat resistance and low hydrolyzability, like the porous film 52a described above.
  • the fibers constituting the nonwoven fabric, woven fabric, and knitted fabric are excellent in durability and heat resistance, polyolefin such as polypropylene (PP), modified polyamide such as aramid (trade name), polytetrafluoro Fibers made of fluorine-containing resins such as ethylene and polyvinylidene fluoride are preferred. 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 body 52 has the auxiliary support film 52b, the mechanical strength can be improved. Therefore, even in the manufacturing method using RtoR in the illustrated example, wrinkles on the support 52 can be prevented and productivity can be increased.
  • the porous membrane 52a has a thickness of 5 to 100 ⁇ m
  • the auxiliary support membrane 52b has a thickness of 50 to 300 ⁇ m.
  • the thickness of the support body 52 is preferably 30 to 500 ⁇ m.
  • the support body 52 sent out from the support body roll 52R and the processed support body 56 sent out from the processed support body roll 56R are transported in the longitudinal direction and then transported to the coating unit 14 to facilitate transport film.
  • the coating composition to be 54a and the facilitated transport film 54b is applied.
  • only the support body 52 will be described as a representative of both when the support body 52 and the processed support body 56 need not be distinguished from each other.
  • the conveying speed of the support 52 may be appropriately set according to the type of the support 52 and the viscosity of the coating composition.
  • the conveyance speed of the support 52 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 54a (and the facilitated transport film 54b) contains a hydrophilic compound such as a hydrophilic polymer, a carrier that reacts with an acidic gas, water, and the like. Therefore, the coating composition for forming such a facilitated transport film 54a is a composition containing a hydrophilic compound, a carrier and water (room temperature water or warm water), or further a necessary component such as a crosslinking agent ( Paint / coating liquid).
  • the hydrophilic compound may be crosslinked, partially crosslinked, or uncrosslinked, or a mixture of these.
  • the hydrophilic compound functions as a binder, retains moisture in the facilitated transport film 54a, and exerts a function of separating a gas such as carbon dioxide by the 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 solution, and the facilitated transport film 54a 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, more preferably 1 g / g or more, more preferably 5 g / g of the physiological saline. More preferably, it has a hydrophilicity of g or more, particularly preferably has a hydrophilicity of 10 g / g or more, and most preferably 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 weight average molecular weight of the hydrophilic compound By setting the weight average molecular weight of the hydrophilic compound to 20,000 or more, the facilitated transport film 54 having a sufficient film strength can be obtained stably.
  • the hydrophilic compound when the hydrophilic compound has a hydroxy group 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 the hydrophilic compound may be a value measured according to JIS K 6726.
  • JIS K 6726 the weight average molecular weight of the hydrophilic compound
  • 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.
  • hydrophilic compounds 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.
  • 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. Specifically, PVA117 (manufactured by Kuraray Co., Ltd.), poval (manufactured by Kuraray Co., Ltd.), polyvinyl alcohol (manufactured by Aldrich Co., Ltd.), J-poval (manufactured by Nihon Ventures & Poval Co., Ltd.) and the like are exemplified. 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 may be mixed and used.
  • the content of the hydrophilic compound in the coating composition is such that the hydrophilic compound functions as a binder and can sufficiently retain moisture in the formed facilitated transport film 54a, depending on the type of the hydrophilic composition or carrier. Accordingly, it may be set appropriately.
  • the amount in the facilitated transport film 54 is preferably 0.5 to 50% by mass, more preferably 0.75 to 30% by mass, and 1 to 15% by mass. Particularly preferred.
  • 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.
  • a coating composition 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.
  • polyvalent aldehydes such as glutaraldehyde and formaldehyde having two or more aldehyde groups are preferred.
  • Epoxy crosslinking agent it is a compound which has 2 or more of epoxy groups, and the compound which has 4 or more is also preferable.
  • Epoxy crosslinking agents are also available as commercial products, for example, trimethylolpropane triglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., Epolite 100MF, etc.), Nagase ChemteX Corporation EX-411, EX-313, EX-614B, Examples include EX-810, EX-811, EX-821, EX-830, and Epiol E400 manufactured by NOF Corporation.
  • the oxetane compound which has cyclic ether as a compound similar to an epoxy crosslinking agent is also used preferably.
  • 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, and oxyethylene oxypropylene block copolymer.
  • examples include coalescence, pentaerythritol, and sobitol.
  • Examples of the polyvalent isocyanate include 2,4-toluylene diisocyanate and hexamethylene diisocyanate.
  • Examples of the polyvalent aziridine include 2,2-bishydroxymethylbutanol-tris [3- (1-acyridinyl) 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.
  • polyvinyl alcohol having a weight average molecular weight of 130,000 or more when polyvinyl alcohol having a weight average molecular weight of 130,000 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. Therefore, an epoxy crosslinking agent and glutaraldehyde are preferably used. Further, when a polyvinyl alcohol-polyacrylic acid copolymer is used as the hydrophilic compound, an epoxy crosslinking agent or glutaraldehyde is preferably used. In addition, 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 that has good reactivity with the hydrophilic compound and excellent hydrolysis resistance.
  • an epoxy crosslinking agent glutaraldehyde, and an organometallic crosslinking agent are preferably used. Further, when polyethyleneimine or polyallylamine is used as the hydrophilic compound, an epoxy crosslinking agent is preferably used.
  • the quantity of a crosslinking agent suitably according to the kind of hydrophilic compound and crosslinking agent which are added to a coating composition.
  • the amount 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 crosslinked structure is 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. preferable.
  • 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 54a
  • 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 kinds of carriers are present in the facilitated transport film 54, different carriers can be separated from each other in the film.
  • the facilitated transport film 54 or the facilitated transport film 54 and other members are adhered to each other due to the water absorption of the facilitated transport film 54 at the time of manufacture. (Blocking) can be suitably suppressed.
  • the deliquescence property is more excellent than the first compound having deliquescence and the first compound.
  • a second compound having a low specific gravity As an example, the first compound is exemplified by cesium carbonate, and 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.
  • examples of the sulfur compound include amino acids such as cystine and cysteine, polythiophene, dodecylthiol and the like.
  • the amount of carriers in the facilitated transport film 54 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 amount ratio of the hydrophilic compound to the carrier in the coating composition is preferably 1: 9 to 2: 3 or less, more preferably 1: 4 to 2: 3 or less, as a mass ratio of the hydrophilic compound to the carrier. : 7 to 2: 3 is particularly preferable.
  • the coating composition may contain a thickener as necessary.
  • a 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 in the coating composition is preferably as small as possible as long as the content of the thickener in the composition (coating liquid) 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 coating composition (facilitated transport film 54) may contain various components as necessary in addition to such a hydrophilic compound, a crosslinking agent and a carrier, or a thickener.
  • 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 moisturizing (moisture absorbing) agent, an auxiliary solvent, a film strength adjusting agent, a defect detecting agent, and the like may be used as necessary.
  • the facilitated transport film 54 is obtained by adding a hydrophilic compound, a carrier, and various components to be added as necessary to water (room temperature water or warm water) in appropriate amounts, and stirring sufficiently.
  • a coating composition is prepared.
  • dissolution of each component may be promoted by heating with stirring.
  • precipitation (salting out) of a hydrophilic compound can be effectively prevented by adding a carrier gradually and stirring.
  • the coating composition to be the facilitated transport film 54a and the facilitated transport film 54b preferably has a temperature of 15 to 35 ° C. and a viscosity of 0.1 to 5 Pa ⁇ sec at the time of coating.
  • a viscosity is a viscosity measured value in rotation speed 60rpm by a B type viscosity system.
  • the coating composition has a viscosity of 0.1 to 5 Pa ⁇ sec at a rotation speed of 60 rpm by the B-type viscosity system at 15 to 35 ° C. That is, the prepared coating composition is put into a stainless steel container (for example, an inner diameter of 4 cm and a height of 12 cm) so that the viscometer cylinder (rotor) is sufficiently immersed in the coating composition.
  • this stainless steel container is dipped in a temperature-controllable water tank, and while adjusting the temperature of the applied coating composition in the range of 15 ° C. to 35 ° C., a B-type viscometer (for example, BL21 ⁇ 100,000 mPa ⁇ s / KN3312481) is operated, the value for each temperature at a rotational speed of 60 rpm is read, and the viscosity of the coating solution is measured according to JIS Z8803.
  • a B-type viscometer for example, BL21 ⁇ 100,000 mPa ⁇ s / KN3312481
  • the coating composition for forming the first facilitated transport film 54a and the coating composition to be formed for the second facilitated transport film 54b may be the same, or may contain the composition.
  • the type and number of components, pH, concentration of each component contained, viscosity, and the like may be different from each other. That is, in the present invention, the first facilitated transport film 54a and the second facilitated transport film 54b may be films having the same composition or different compositions.
  • all facilitated transport films may be formed of the same coating composition, or all facilitated transport films may be formed of different coating compositions.
  • the second and subsequent facilitated transport films may be formed of the same coating composition and only the first facilitated transport film 54a may be formed of a different coating composition, or the first facilitated transport film 54a and two layers may be formed.
  • One or more facilitated transport films after the first may be formed of the same coating composition, and other facilitated transport films may be formed of coating compositions having different compositions (compositions may be the same or different). Good.
  • a coating composition for forming the first facilitated transport film 54a (initial film forming process) and a coating composition for forming at least one facilitated transport film thereafter (laminated film forming process)
  • the same coating composition or different coating compositions may be used.
  • the application unit 14 is a part that applies such a coating composition to the support 52 (processed support 56) conveyed in the longitudinal direction.
  • the coating unit 14 includes a coating device 36 and a backup roller 38. That is, the support body 52 is conveyed while being kept at a predetermined application position by the backup roller 38, and the application composition is applied by the application device 36 to form a coating film (liquid film) of the application composition.
  • the coating device 36 various known devices can be used. Specifically, roll coater, direct gravure coater, offset gravure coater, single 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.
  • roll coater direct gravure coater, offset gravure coater, single 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, a bar coater, a normal rotation roll coater, a knife coater, and the like are preferably used.
  • the coating device 36 when the first facilitated transport film 54a is formed (initial film forming process), the coating device 36 is set so that the thickness of the coating film becomes 0.01 to 3 mm. Then, the coating composition is applied to the support 52. In other words, the thickness of the coating film is the thickness of the coating composition applied to the support 52.
  • the thickness of the coating film is preferably 0.01 to 3 mm.
  • the facilitated transport film forming process in which the facilitated transport film is formed in the lower layer and the facilitated transport film is further formed in the upper layer is a laminated film formation. It is preferable to satisfy the conditions of the coating film thickness in the initial film forming process while satisfying the process conditions.
  • the thickness of the coating film of the coating composition in the first facilitated transport film 54a is preferably 0.05 to 2.5 mm, and more preferably 0.1 to 2 mm.
  • the initial facilitated transport film 54a formed by drying the coating composition to be described later has a thickness that can achieve the desired performance depending on the composition of the facilitated transport film 54a and the like. May be set as appropriate. Specifically, 1 to 100 ⁇ m is preferable, and 10 to 80 ⁇ m is more preferable. That is, in the production method of the present invention, when the first facilitated transport film 54a is formed, the coating composition is formed so that the facilitated transport film 54a having the above thickness is obtained with a coating thickness of 0.01 to 3 mm. Is preferably prepared.
  • the coating film thickness of the coating composition when forming the second layer (second and subsequent layers) facilitated transport film 54b is the concentration of the hydrophilic compound or carrier in the coating composition, the purpose What is necessary is just to determine suitably according to the film thickness etc. of the facilitated-transport film
  • the coating thickness when forming the facilitated transport film 54b is preferably 0.05 to 2.5 mm, and more preferably 0.1 to 2 mm.
  • the coating thickness when forming the facilitated transport film other than the lowermost layer and the uppermost layer is 0.01 to 3 mm as described above. Is preferable, 0.05 to 2.5 mm is more preferable, and 0.1 to 2 mm is particularly preferable.
  • the thickness of the facilitated transport film 54b of the second layer (second and subsequent layers) formed by drying the coating composition described later is the composition of the facilitated transport film 54b and the intended facilitated transport. What is necessary is just to set suitably the film thickness from which the target thickness and performance are obtained according to the thickness of the film
  • the thicknesses of the first facilitated transport film 54a and the second facilitated transport film 54b (and the third and subsequent facilitated mail films) may be the same or different. In the case of having three or more facilitated transport films, the thickness of the second and subsequent facilitated transport films may be the same or different.
  • the total film thickness of the first facilitated transport film 54a and the second facilitated transport film 54b is preferably 2 to 200 ⁇ m, preferably 20 to 160 ⁇ m. Is more preferable.
  • the supply unit 12 and the application unit 14 are disposed in the housing 26. Further, a temperature / humidity measuring means 28 and a temperature / humidity adjusting means 30 are arranged in the housing 26.
  • the temperature / humidity measuring means 28 measures the temperature and humidity in the housing 26.
  • the temperature / humidity measuring means 28 may be configured using a known temperature sensor or humidity sensor.
  • the temperature / humidity adjusting means 30 adjusts the temperature and humidity in the housing 26 according to the measurement result of the temperature and humidity in the housing 26 by the temperature / humidity measuring means 28.
  • the temperature / humidity adjusting means 30 may also be configured using a known dehumidifying means, humidifying means, heating device, or cooling device.
  • the manufacturing apparatus 10 measures the temperature and humidity in the housing 26 by the temperature / humidity measuring means, and the measurement result Accordingly, the temperature / humidity adjusting means 30 adjusts the temperature and humidity in the housing 26 to manage the temperature in the housing 26 to 10 to 40 ° C. and the humidity to 2 to 50% RH. This will be described in detail later.
  • the support 52 (treated support 56) coated with the coating composition in the coating unit 14 is guided by the pass roller 40a that contacts the back surface (the surface opposite to the coating surface of the coating composition) and conveyed to the drying unit 18. Is done.
  • the drying unit 18 removes at least a part of water from the coating composition applied to the support 52 and dries, thereby forming the first facilitated transport film 54a and the treated support 56. To do. Further, the drying unit 18 removes at least a part of water from the coating composition applied to the treated support 56 and dries to form a second facilitated transport film 54b to separate the acidic gas. A film 50 is produced.
  • crosslinking of a hydrophilic compound may be performed as needed, and the facilitated-transport film
  • the drying method various known methods for drying by removing water, such as hot air drying or a drying method by heating the support 52, can be used.
  • 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.
  • 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 warm air may be appropriately set to a temperature at which the support 52 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.
  • the temperature at which the support 52 is not deformed and the coating composition can be dried quickly may be set as appropriate. Moreover, you may use blowing of a dry wind for heating of the support body 52 together.
  • the temperature of the support 52 is preferably 60 to 120 ° C., more preferably 60 to 90 ° C., and particularly preferably 70 to 80 ° C.
  • the film surface temperature is preferably 15 to 80 ° C., more preferably 30 to 70 ° C.
  • the support 52 that is, the processed support 56 having the coating composition dried in the drying unit 18, is guided by the pass roller 40 a and then conveyed to the winding unit 20.
  • the treated support 56 that is, the acidic gas separation membrane 50 obtained by drying the coating film of the coating composition in the drying unit 18 is also guided by the pass roller 40 a and then conveyed to the winding unit 20.
  • the winding unit 20 winds the processed support 56 around the winding shaft 42 to obtain a processed support roll 56R.
  • the winding unit 20 winds the acidic gas separation membrane 50 around the winding shaft 42 to obtain a separation membrane roll 50R.
  • the winding unit 20 includes the above-described winding shaft 42 and three pass rollers 40c to 40e.
  • the processed support 56 is guided along a predetermined transport station path by the pass rollers 40c to 40e, and is taken up by the winding shaft 42 (processed support roll 56R) to be a processed support roll 56R.
  • the acidic gas separation membrane 50 is guided along a predetermined transport station path by the pass rollers 40c to 40e, and taken up by the take-up shaft 42 (separation membrane roll 50R) to form the separation membrane roll 50R.
  • the three pass rollers 40c to 40e also act as tension cutters, and guide the processed support 56 and the like to meander.
  • the support roll 52R is mounted on the rotating shaft 34 of the supply unit 12, and the rotating shaft 34 is rotated to feed the support 52 from the support roll 52R.
  • the support 52 sent out from the support roll 52R passes through the coating unit 14 (backup roller 38), the pass roller 40a, the drying unit 18, the pass roller 40b, and the pass rollers 40c to 40e, and reaches a take-up shaft 42.
  • the tip of the support body 52 is wound around the take-up shaft 42.
  • the coating device 36 is filled with a necessary amount of the coating composition.
  • the rotary shaft 34, the winding shaft 42, the backup roller 38, etc. are driven in synchronism with each other. Start conveyance.
  • the temperature and humidity of the housing 26 housing the supply unit 12 and the application unit 14 are controlled within a predetermined range by the temperature / humidity measuring unit 28 and the temperature / humidity adjusting unit 30 as necessary. Also good.
  • the support body 52 sent out from the support body roll 52R is first transported while being supported at a predetermined application position by the backup roller 38 in the coating unit 14 while being transported in the longitudinal direction.
  • the coating composition to be the facilitated transport film 54a is applied so as to have a predetermined coating thickness (coating amount).
  • the coating composition is applied so that the thickness of the coating film is 0.01 to 3 mm as described above.
  • the coating composition at the time of coating preferably has a temperature of 15 to 35 ° C. and a viscosity of 0.1 to 5 Pa ⁇ sec.
  • the support 52 coated with the coating composition to be the first facilitated transport film 54a is then guided by the pass roller 40a to reach the drying unit 18, where the coating composition is dried,
  • the treated support 56 is provided with the facilitated transport film 54a.
  • the processed support 56 is guided by the pass roller 40b, conveyed to the winding unit 20, guided along a predetermined conveyance path by the pass rollers 40c to 40e, and wound around the winding shaft 42, and processed support roll 56R.
  • the conveyance of the support 52 is stopped.
  • the processed support 56 is cut downstream of the drying unit 18, wound around the processed support roll 56 ⁇ / b> R, and the processed support roll 56 ⁇ / b> R is removed from the manufacturing apparatus 10. Further, the support roll 52R is removed from the rotating shaft 34, and the remaining support 52 is removed.
  • the temperature and humidity of the housing 26 that accommodates the supply unit 12 and the coating unit 14 are measured by the temperature / humidity measuring unit 28, and the temperature and humidity in the housing 26 are adjusted by the temperature / humidity adjusting unit 30 according to the measurement result.
  • the temperature inside the housing 26 is controlled within a range of 10 to 40 ° C.
  • the humidity is controlled within a range of 10 to 50% RH.
  • the processed support roll 56R is mounted on the rotating shaft 34 of the supply unit 12, and the processed support 56 is fed from the processed support roll 56R by rotating the rotating shaft 34.
  • the processed support 56 sent out from the processed support roll 56R is passed through a predetermined transport path from the coating unit 14 to the winding shaft 42 in the same manner as described above, and the tip of the processed support 56 is wound up. Wrap around the shaft 42.
  • the coating device 36 is filled with a necessary amount of the coating composition. As described above, this coating composition may be the same as or different from the coating composition on which the first facilitated transport film 54a is formed.
  • the processed support 56 is passed through a predetermined transport path, and the coating device 36 is filled with the coating composition, the rotating shaft 34, the winding shaft 42, Then, the backup roller 38 and the like are driven synchronously, and the conveyance of the support 52 is started.
  • the processed support 56 sent out from the processed support roll 56R is transported while being supported in a predetermined application position by the backup roller 38 in the coating unit 14 while being transported in the longitudinal direction, as before.
  • the coating composition that forms the second facilitated transport film 54b is applied by the coating device 36 so as to have a predetermined coating thickness (coating amount).
  • the temperature and humidity of the housing 26 that accommodates the supply unit 12 and the application unit 14 are measured, and the temperature and humidity in the housing 26 are adjusted according to the measurement result, and the housing Since the internal temperature is controlled to 10 to 40 ° C. and the same humidity is controlled to 10 to 50% RH, the coating composition to be the facilitated transport film 54b of the second layer is uniformly distributed over the entire surface. Can be applied.
  • the first facilitated transport film 54a is hydrophilic.
  • membrane 54b contains many waters. Therefore, when considered normally, when the coating composition is applied on the first facilitated transport film 54a, it should be possible to apply the coating composition with very good coating properties (coating).
  • coating composition when a coating composition to be a facilitated transport film is applied on the facilitated transport film, the coating composition is repelled, and the portion where the coating composition is not applied is pinhole-shaped. In many cases, it may occur.
  • the facilitated transport film has a high water absorption
  • the second facilitated transport film laminated film forming step
  • the second facilitated transport film By applying the humidity and temperature of the space to which the first facilitated transport film 54a (previously formed facilitated transport film) is exposed to the above range until the coating composition to be 54b is applied, this problem of flipping is reduced. I found it possible to solve it.
  • an acid gas separation membrane using a facilitated transport membrane is often used in a gas environment having a water vapor partial pressure.
  • an acid gas separation membrane having a facilitated transport membrane tends to have a higher acid gas separation rate (permeation rate) as the facilitated transport membrane has higher water absorption. Therefore, the facilitated transport film has a configuration in which a hydrophilic compound having high water absorption such as a super water absorbent resin is used as a binder and carriers are dispersed in the binder. Many carriers also have high water absorption.
  • a highly water-absorbing additive added to the facilitated transport film as necessary. Therefore, the facilitated transport film has very high water absorption.
  • the first facilitated transport film 54a is fed from the treated support roll 56R when the second facilitated transport film 54b is formed, and the coating composition 14 is coated with the coating composition.
  • moisture in the air is absorbed, and moisture adheres to the surface, resulting in a large number of water droplets.
  • RtoR since the coating composition is applied while the treated support 56 is being conveyed, a shearing force is applied to the coating film when the coating film thickness is adjusted.
  • the water droplets that have not been diffused into the coating composition act like a lubricant, and the coating composition applied onto the water droplets slips and moves so as to be repelled from above. A part where the coating composition is not applied is generated.
  • the coating film of the coating composition formed on the first facilitated transport film 54a is in a state in which a large number of pinholes are scattered. Even if such a coating film is dried to form the second facilitated transport film 54b, the formed facilitated transport film 54b has a thin portion or a defective portion where the film is not formed. End up.
  • the first facilitated transport film 54a is exposed in the housing 26 (before the coating composition is applied) in forming the second facilitated transport film 54b.
  • the temperature and humidity of the space are controlled to 10 to 40 ° C. and 10 to 50% RH. Therefore, it is possible to prevent moisture from adhering to the surface of the first facilitated transport film 54a, and uniformly apply the coating composition that forms the second facilitated transport film 54b on the entire surface of the first facilitated transport film 54a. By coating, a uniform facilitated transport film 54b having no defects can be formed on the entire surface.
  • the temperature in the housing 26 is lower than 10 ° C., there arises a disadvantage that the initial facilitated transport film 54a is cracked.
  • the temperature in the housing exceeds 40 ° C., the absolute amount of moisture is large even in a proper humidity range, so that it is not possible to sufficiently prevent moisture from adhering to the surface of the first facilitated transport film 54a. This will cause the film to be repelled.
  • the temperature in the housing 26 is preferably 15 to 35 ° C.
  • the humidity in the housing 26 is less than 10% RH, inconveniences such as film breakage occur in the first facilitated transport film 54a.
  • the humidity in the housing 26 exceeds 50% RH, moisture cannot be sufficiently prevented from adhering to the surface of the first facilitated transport film 54a, and the coating film of the coating composition is repelled.
  • the humidity in the housing 26 is preferably 20 to 45% RH, and more preferably 20 to 40% RH.
  • the coating composition to be the second facilitated transport film preferably has a contact angle with respect to the first facilitated transport film 54a of less than 90 °. That is, it is preferable to adjust the composition of the facilitated transport film, that is, the coating composition, so that the contact angle of the coating composition to be the second facilitated transport film with respect to the first facilitated transport film 54a is less than 90 °.
  • the temperature and humidity in the housing 26 are managed as described above, and the contact angle of the coating composition to be the second facilitated transport film with respect to the first facilitated transport film 54a is less than 90 °. By doing so, it is possible to form a coating film of a coating composition having a more uniform and good surface shape and to form a second layer of facilitated transport film 54b of higher quality.
  • the coating composition at the time of coating preferably has a temperature of 15 to 35 ° C. and a viscosity of 0.1 to 5 Pa ⁇ sec as described above. is there.
  • the treated support 56 coated with the coating composition to be the second layer facilitated transport film 54b is then guided by the pass roller 40a to reach the drying unit 18, where the coating composition is dried.
  • the acidic gas separation membrane 50 in which the second facilitated transport membrane 54b is formed in addition to the first facilitated transport membrane 54a is obtained.
  • the acidic gas separation membrane 50 has a uniform facilitated transport membrane 54b formed of a coating composition uniformly applied to the entire surface and having no defects.
  • the acidic gas separation membrane 50 is guided by the pass roller 40b, conveyed to the winding unit 20, guided along a predetermined conveyance path by the pass rollers 40c to 40e, and taken up by the take-up shaft 42, and separated from the separation membrane roll 50R. Is done.
  • a housing 26 is formed so as to surround the supply unit 12 and the coating unit 14, and the temperature and humidity inside the housing 26 are managed within a predetermined range.
  • the temperature and humidity of the space to which the first facilitated transport film 54a is exposed are controlled within a predetermined range before the coating composition is applied. do it. Therefore, for example, in the illustrated example, the space downstream of the position where the coating composition is applied by the coating device 36 need not be managed for temperature and humidity.
  • the coated film is wound after being dried regardless of the first facilitated transport film 54a (initial film forming process) and the second facilitated transport film 54b (laminated film forming process). Even in a space where the facilitated transport film is exposed, that is, a space where the facilitated transport films 54a and 54b are exposed from the outlet of the drying unit 18 to the winding unit 20, the temperature and humidity are controlled within a predetermined range. Is preferred.
  • the humidity of the space where the facilitated transport film is exposed from the outlet of the drying unit 18 to the winding unit 20 is preferably managed at 10 to 60% RH, and is preferably managed at 10 to 40% RH. Is more preferable.
  • the temperature of the space where the facilitated transport film is exposed from the outlet of the drying unit 18 to the winding unit 20 is preferably managed at 15 to 35 ° C, more preferably 20 to 30 ° C.
  • Such management of the temperature and humidity from the outlet of the drying unit 18 to the winding unit 20 may be basically performed in the same manner as the space in which the facilitated transport film 54a exists before the coating composition is applied.
  • the acidic gas separation membrane 50 and the transport path of the treated support 56 from the outlet of the drying unit 18 to the winding unit 20 and the winding unit 20 are surrounded by a housing, and the temperature and humidity in the housing are known.
  • the temperature and humidity in the housing may be measured by the means and managed by a known means so as to achieve the target values.
  • the first facilitated transport film 54a and the second facilitated transport film 54b are formed to form the acidic gas separation membrane 50 having the facilitated transport film having a two-layer structure.
  • an acidic gas separation membrane having three or more facilitated transport membranes is formed by repeatedly performing the same operation (laminated film forming step) as the formation of the second facilitated transport membrane 54b. Also good.
  • the number of repetitions of the facilitated transport film formation process may be determined as appropriate according to the composition of the facilitated transport film, the target film thickness, etc., but productivity, film thickness, film quality of the facilitated transport film, etc. In consideration of the above, it is usually about 2 times (2 layers as in the illustrated example) to about 3 times.
  • the manufacturing apparatus 10 in the illustrated example has only one coating unit 14 and drying unit 18, that is, an apparatus that can form only one layer of a facilitated transport film. 54a and the second facilitated transport film 54b are formed. However, in the manufacturing method of the present invention, as schematically shown in FIG. 3, a manufacturing apparatus having two (or three or more) coating units 14a and drying units 18a, and coating units 14b and drying units 18b is used.
  • the acidic gas separation membrane 50 may be manufactured by forming the first facilitated transport membrane 54a and the second facilitated transport membrane 54b.
  • the temperature and humidity are 10 to 40 ° C.
  • the first facilitated transport film 54a is formed in the upstream coating unit 14a and the drying unit 18a
  • the second facilitated transport film 54b is formed in the downstream coating unit 14b and the drying unit 18b. do it.
  • the first facilitated transport film 54a and the second facilitated transport film 54b are formed by the first operation as before.
  • the wound roll is mounted on the supply side, and the temperature and humidity are controlled at 10 to 40 ° C. and 10 to 50% RH in the space 48 including the roll and the upstream application unit 14a, and the second time.
  • a third facilitated transport film may be formed by the operation.
  • the first operation only the first facilitated transport film 54a is formed, the wound roll is mounted on the supply side, and the temperature and humidity are set to 10 to 40 ° C. in both the space 48 and the space 46.
  • the second layer and the third layer facilitated transport film may be formed by the second operation under the control of 10 to 50% RH.
  • an acidic gas separation membrane having four or more layers of facilitated transport membranes may be formed by repeating the above operation.
  • the first aspect of the present invention described above adjusts the temperature and humidity of the space to which the first facilitated transport film 54a is exposed until the coating composition is applied in the formation process of the second facilitated transport film 54b.
  • the coating composition to be the facilitated transport film 54b of the second layer is uniformly applied without causing repellency to form a uniform facilitated transport film 54b free from defects.
  • the weight increase rate due to water absorption of the first facilitated transport film 54a is 40% by mass or less.
  • the coating composition is applied under the following conditions.
  • the facilitated transport film 54a of the treated support 56 wound around the treated support roll 56R is exposed to the outside air (when the facilitated transport film 54a is exposed to the outside air for application).
  • the coating composition for the transport film 54b is applied.
  • the temperature and humidity of the space to which the first facilitated transport film 54a is exposed are managed to suppress water absorption of the first facilitated transport film 54a. .
  • the application of the second facilitated transport film 54b (current facilitated transport film) is started after the drying of the first facilitated transport film 54a (previous facilitated transport film) is completed.
  • the weight increase rate of the first facilitated transport film 54a due to water absorption is 40% by mass or less.
  • the conveyance path from the outlet of the drying unit 18 to the winding unit 20 and the winding unit 20 are surrounded by a housing, and the temperature and humidity in the housing are measured and managed, so that after drying The first facilitated transport film 54a is suppressed in water absorption to obtain a treated support roll 56R around which the treated support 56 is wound.
  • the rate of weight increase due to water absorption of the first facilitated transport film 54a is 40% or less by the time when the coating composition for the second facilitated transport film 54b is applied.
  • the coating composition can be applied uniformly to form a uniform second facilitated transport film 54b free from defects.
  • the coating composition that becomes the second facilitated transport film 54b when the coating composition that becomes the second facilitated transport film 54b is applied under the condition that the weight increase rate due to water absorption of the first facilitated transport film 54a exceeds 40% by mass, Similarly to the above, it is not possible to sufficiently prevent moisture from adhering to the surface of the first facilitated transport film 54a, and the coating film of the coating composition is repelled to form a uniform second facilitated transport film 54b. Can not. Moreover, under the condition that the weight increase rate due to water absorption of the first facilitated transport film 54a is 30% or less in terms of more suitably preventing moisture from adhering to the surface of the first facilitated transport film 54a. It is preferable to apply a coating composition that becomes the second facilitated transport film 54b.
  • Various methods can be used as the method of applying the coating composition under the condition that the weight increase rate due to water absorption of the first facilitated transport film 54a is 40% by mass or less.
  • the temperature and / or humidity of the space to which the first facilitated transport film 54a is exposed until the coating composition is applied to the first facilitated transport film 54a. is adjusted so that the rate of weight increase due to water absorption of the first facilitated transport film 54a is 40% by mass or less. That is, the temperature and / or humidity of the housing 26 in FIG. 1 and the space 46 and the space 48 in FIG. 3 are controlled so that the weight increase rate due to water absorption of the first facilitated transport film 54a is 40% by mass or less.
  • a heating means between the supply part 12 and the application part 14 in the manufacturing apparatus 10 shown in FIG. 1, the upstream of the application part 14 in FIG. 3, and between the drying part 18a and the application part 14b, a heating means, a wind, etc.
  • Water removal means (wiping means), suction means for sucking moisture, means for dehumidifying moisture, etc. are provided, and coating is performed under the condition that the weight increase rate due to water absorption of the first facilitated transport film 54a is 40% or less.
  • a method of applying the composition can also be used. Further, after the first facilitated transport film 54a is applied and dried, the film surface is protected with a protective film or the like, and the protective film or the like is peeled off immediately before the second facilitated transport film 54b is applied. A method of applying the coating composition under conditions where the weight increase rate of the film 54a due to water absorption is 40% or less can also be used.
  • the above example is the example which performed the manufacturing method of the acidic gas separation membrane of this invention using RtoR
  • this invention can utilize various manufacturing methods besides this.
  • the first facilitated transport membrane 54a and the second facilitated transport membrane 54b are produced in the same manner while conveying the cut sheet-shaped support instead of the long support 52, and the acidic gas separation membrane is formed. It may be produced.
  • the first facilitated transport membrane 54a and the second facilitated transport membrane 54b are formed by a so-called batch-type (single-wafer) process without transporting the support to produce an acid gas separation membrane. May be. Even in the batch-type treatment, for example, when the coating film thickness of the coating composition is adjusted, a shearing force is applied to the coating film, so that the same coating composition may be repelled. However, when forming the facilitated transport film 54b of the second layer (second layer or later), the temperature and humidity of the space to which the first coating composition is exposed are measured until the coating composition is applied. By applying the coating composition under management, or by applying the coating composition under the condition that the weight increase rate due to water absorption of the first facilitated transport film 54a is 40% by mass or less, the coating composition is properly applied, A uniform facilitated transport film 54b can be formed.
  • an acid gas separation membrane is manufactured using RtoR as shown in FIGS. 1 and 3 in that high productivity can be obtained and a uniform facilitated transport membrane can be formed. Is preferred.
  • Example 1 ⁇ Preparation of coating composition> A polyvinyl alcohol-polyacrylic acid copolymer (Kuraray Co., Ltd., Clastomer AP-20, 2.4% by mass) and a crosslinking agent (Wako Pure Chemical Industries, Ltd., 25% by mass glutaraldehyde aqueous solution), 0.01% by mass, are prepared. To this aqueous solution, 1M hydrochloric acid was added until the pH reached 1.7 to cause crosslinking. After crosslinking, a 40% aqueous cesium carbonate solution (manufactured by Rare Metal Co., Ltd.) was added so that the concentration of cesium carbonate was 6.0% by weight.
  • cesium carbonate serves as a carrier for the facilitated transport film 54. Furthermore, a coating composition was prepared by adding 0.003% by mass of a surfactant (1% by mass of Lapisol A-90 manufactured by NOF Corporation). ⁇ Production of acid gas separation membrane>
  • a long (porous) support 52 having a width of 500 mm and a thickness of 200 ⁇ m (a laminate (manufactured by GE Corp.) obtained by laminating porous PTFE on the surface of a PP nonwoven fabric) is wound into a roll shape.
  • a support roll 52R was prepared.
  • the support roll 52R was mounted on the rotating shaft 34 of the supply unit 12 of the manufacturing apparatus 10 shown in FIG. 1 so that the coating composition was applied to the porous PTFE side. Subsequently, the support body 52 is sent out from the support body roll 52R, and as described above, the support body 52 passes through the coating unit 14 and the drying unit 18 through a predetermined conveyance path to the winding unit 20 to wind up the tip of the support body 52. It was wound around the shaft 42. On the other hand, a necessary amount of the prepared coating composition was filled in the coating device 36 of the coating unit 14.
  • the support 52 is started to be transported, and as described above, the coating composition is applied to the surface of the support 52 in the coating unit 14, and the coating composition is dried in the drying unit 18. Then, the first facilitated transport film 54a is formed as the treated support 56, and the prepared treated support 56 is wound around the take-up shaft 42 to obtain a treated support roll 56R.
  • the temperature / humidity measuring means 28 and the temperature / humidity adjusting means 30 are not activated.
  • the conveyance speed of the support body 52 was 3 m / min.
  • the coating composition was applied so that the coating thickness was 1 mm.
  • the thickness of the coating composition is such that the facilitated transport film formed by drying has a thickness of 0.03 mm.
  • drying in the drying unit 18 was performed using a warm air drying furnace at multi-stage heating temperatures of 70 ° C., 80 ° C., 90 ° C., 100 ° C., 110 ° C., and 120 ° C.
  • the conveyance of the support 52 was stopped, and the processed support 56 was cut immediately downstream of the pass roller 40b.
  • the processed support 56 was wound up to the end, and the processed support roll 56 ⁇ / b> R was removed from the winding shaft 42. Further, the support roll 52R and the support 52 remaining in the manufacturing apparatus 10 were also removed from the apparatus.
  • the temperature / humidity measuring means 28 and the temperature / humidity adjusting means 30 are operated, and the temperature and humidity inside the housing 26 are measured by the temperature / humidity measuring means 28, According to the measurement result, the temperature and humidity were adjusted by the temperature / humidity adjusting means 30, and the temperature inside the housing 26 was controlled to 22 ° C. ⁇ 3 ° C., and the humidity was controlled to 30% RH ⁇ 5% RH.
  • the treated support roll 56R removed from the winding shaft 42 was mounted on the rotating shaft 34 of the supply unit 12 of the manufacturing apparatus 10 so that the coating composition was applied to the first facilitated transport film 54a side.
  • the processed support 56 was pulled out from the processed support roll 56 ⁇ / b> R, passed through the winding unit 20, and the tip was wound around the winding shaft 42. Furthermore, a necessary amount of the prepared coating composition was filled in the coating device 36 of the coating unit 14.
  • the second facilitated transport film 54b is formed in the same manner as the first facilitated transport film 54a (that is, the coating thickness of the coating composition of the second layer is 1 mm, and drying is performed).
  • the subsequent film thickness was 0.03 mm
  • the acidic gas separation membrane 50 was produced, wound around the take-up shaft 42, and the separation membrane roll 50R formed by winding the acidic gas separation membrane 50 of 60 m was produced. That is, the acidic gas separation membrane 50 has a total thickness of 0.03 mm for the first (first layer) facilitated transport membrane 54a and 0.03 mm for the second facilitated transport membrane 54b. It has a facilitated transport membrane of 0.06 mm.
  • Example 2 except that the temperature inside the housing 26 was controlled to 25 ° C. ⁇ 3 ° C. and the humidity was controlled to 40% RH ⁇ 5% RH in the formation of the second layer facilitated transport film 54b (Example 2);
  • Example 2 except that the temperature inside the housing 26 was controlled to 18 ° C. ⁇ 3 ° C. and the humidity was controlled to 45% RH ⁇ 5% RH in the formation of the second layer facilitated transport film 54b (Example 3);
  • the temperature inside the housing 26 is controlled to 30 ° C. ⁇ 3 ° C.
  • Example 4 Except for controlling the temperature inside the housing 26 to 15 ° C. ⁇ 3 ° C. and the same humidity to 25% RH ⁇ 5% RH in the formation of the second layer facilitated transport film 54b (Example 5); Similarly, a separation membrane roll 50R was produced.
  • a separation membrane roll 50R was produced in the same manner as in Example 1 except that the temperature and humidity in the housing 26 were not managed when forming the second facilitated transport membrane 54b.
  • the temperature inside the housing 26 was 23 to 30 ° C., and the humidity was 50 to 60% RH.
  • a separation membrane roll 50R was produced in the same manner as in Example 1 except that the coating thickness of the coating composition was 0.005 mm.
  • the thickness of this coating composition is such that the facilitated transport film formed by drying has a thickness of 0.00015 mm. That is, the acidic gas separation membrane 50 has a total thickness of 0.00015 mm for the first (first layer) facilitated transport membrane 54 a and 0.03 mm for the second facilitated transport membrane 54 b. It has a facilitated transport membrane of 0.03015 mm.
  • a separation membrane roll 50R was produced in the same manner as in Example 1 except that the coating thickness of the coating composition was 4 mm.
  • the thickness of the coating composition is such that the facilitated transport film formed by drying has a thickness of 0.120 m. That is, the acid gas separation membrane 50 has a total thickness of 0.120 mm for the first (first layer) facilitated transport membrane 54 a and 0.03 mm for the second facilitated transport membrane 54 b. It has a facilitated transport membrane of 0.150 mm.
  • Example 4 Separation in the same manner as in Example 1 except that the temperature inside the housing 26 is controlled to 5 ° C. ⁇ 3 ° C. and the humidity is controlled to 20% RH ⁇ 5% RH in the formation of the second layer facilitated transport film 54b. A film roll 50R was produced.
  • Example 6 In the formation of the first facilitated transport film 54a, the amount of cesium carbonate as a carrier contained in the coating composition is changed from 6.0% by mass to 1.0% by mass, and the second facilitated transport film 54b is formed.
  • a separation membrane roll 50R was produced in the same manner as in Example 1 except that the temperature inside the housing 26 was controlled at 25 ° C. ⁇ 3 ° C. and the same humidity was controlled at 55-60% RH. Under these conditions, the weight increase rate due to water absorption of the first facilitated transport film 54a from the treated support roll 56R to the application of the coating composition of the second facilitated transport film 54b was measured. %Met.
  • the acidic gas separation membrane 50 was pulled out from each separation membrane roll 50R and cut out at an arbitrary position to produce a circular acidic gas separation membrane 50 having a diameter of 47 mm.
  • the circular acidic gas separation membrane 50 was sampled at four locations at intervals of 100 mm with respect to 500 mm in the width direction.
  • a permeation test sample (effective area 2.40 cm 2 ) was prepared using two PTFE membrane filters (pore size 0.10 ⁇ m, manufactured by ADVANTEC) and sandwiching a cut-out circular acidic gas separation membrane 50 from both sides of the membrane.
  • a mixed gas of CO 2 / H 2 : 10/90 (volume ratio) was used as a test gas.
  • This mixed gas was supplied to each produced permeation test sample under the conditions of a relative humidity of 70%, a flow rate of 100 ml / min, a temperature of 130 ° C., and a total pressure of 3 atm.
  • Ar gas flow rate 90 ml / min
  • the permeated gas was analyzed with a gas chromatograph, and the separation factor ⁇ was calculated from the ratio of the H 2 permeation rate and the CO 2 permeation rate, and evaluated as follows.
  • C ⁇ ⁇ 10 is included even at one location. The results are shown in the table below.
  • the coating thickness of the coating composition in the formation of the first facilitated transport film 54a is 0.01 to 3 mm, and in the formation of the second facilitated transport film 54b, the temperature in the housing is changed.
  • Examples 1 to 5 in which the humidity is controlled to 10 to 40 ° C. and the humidity is 10 to 50% RH
  • Example 6 in which the weight increase rate due to water absorption of the first facilitated transport film 54a is 20% by mass, Also achieves a good separation factor.
  • Examples 1 to 3 in which both the temperature and humidity in the housing 26 are controlled within a preferable range realize an excellent carbon dioxide separation performance with a separation factor of 80 or more in all respects.
  • Comparative Example 1 and Comparative Example 4 in which either the temperature or humidity in the housing 26 exceeds the temperature of 10 to 40 ° C. and the humidity of 10 to 50% RH are the formation of the second layer facilitated transport film 54b.
  • the first facilitated transport film 54a absorbs moisture, and this causes the coating composition of the second facilitated transport film 54b to be repelled, so that an appropriate facilitated transport film cannot be formed and the separation factor is increased. It is thought that it became low.
  • Comparative Example 2 in which the thickness of the coating film is less than 0.01 mm cannot form the first facilitated transport film 54a that expresses the intended function.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

Selon l'invention, lorsqu'un film de transport facilité est formé sur un film de transport facilité, une composition de revêtement qui devient le film de transport facilité supérieur est appliquée dans des conditions telles que l'atmosphère à laquelle le film de transport facilité sous-jacent est exposé est régulée de manière à présenter une température de 10-40°C et une humidité de 10-50 % d'HR ou que le film de transport facilité sous-jacent présente une augmentation de poids par absorption d'eau de 40 % en masse ou moins. De ce fait, lorsqu'un film de séparation de gaz acide comprenant une pluralité de films de transport facilité est produit, un film de transport facilité est formé correctement sur un autre film de transport facilité.
PCT/JP2014/071937 2013-09-02 2014-08-21 Procédé de production d'un film de séparation de gaz acide WO2015029884A1 (fr)

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EP2979744A4 (fr) * 2013-03-29 2016-07-27 Fujifilm Corp Procédé et dispositif de production d'un complexe de séparation de gaz acide
CN111356517A (zh) * 2017-11-15 2020-06-30 住友化学株式会社 酸性气体分离膜片的制造方法和制造装置
WO2021018971A1 (fr) * 2019-07-30 2021-02-04 Sartorius Stedim Biotech Gmbh Membrane d'ultrafiltration mécaniquement stable et son procédé de production
US11642629B2 (en) 2020-03-20 2023-05-09 Saudi Arabian Oil Company Multi-layer composite gas separation membranes, methods for preparation, and use

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WO2011099587A1 (fr) * 2010-02-10 2011-08-18 富士フイルム株式会社 Membrane de séparation des gaz, procédé de production associé, et procédé de séparation des gaz, module et appareil de séparation utilisant chacun la membrane de séparation des gaz
JP2011161387A (ja) * 2010-02-10 2011-08-25 Fujifilm Corp ガス分離膜その製造方法、それらを用いたガス混合物の分離方法、ガス分離膜モジュール、気体分離装置
WO2012096055A1 (fr) * 2011-01-12 2012-07-19 富士フイルム株式会社 Composition pour formation de membrane de séparation de dioxyde de carbone, membrane de séparation de dioxyde de carbone ainsi que procédé de fabrication de celle-ci, et dispositif de séparation de dioxyde de carbone

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WO2011099587A1 (fr) * 2010-02-10 2011-08-18 富士フイルム株式会社 Membrane de séparation des gaz, procédé de production associé, et procédé de séparation des gaz, module et appareil de séparation utilisant chacun la membrane de séparation des gaz
JP2011161387A (ja) * 2010-02-10 2011-08-25 Fujifilm Corp ガス分離膜その製造方法、それらを用いたガス混合物の分離方法、ガス分離膜モジュール、気体分離装置
WO2012096055A1 (fr) * 2011-01-12 2012-07-19 富士フイルム株式会社 Composition pour formation de membrane de séparation de dioxyde de carbone, membrane de séparation de dioxyde de carbone ainsi que procédé de fabrication de celle-ci, et dispositif de séparation de dioxyde de carbone

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EP2979744A4 (fr) * 2013-03-29 2016-07-27 Fujifilm Corp Procédé et dispositif de production d'un complexe de séparation de gaz acide
US10022675B2 (en) 2013-03-29 2018-07-17 Fujifilm Corporation Method of producing composite for acid gas separation and apparatus for producing same
CN111356517A (zh) * 2017-11-15 2020-06-30 住友化学株式会社 酸性气体分离膜片的制造方法和制造装置
WO2021018971A1 (fr) * 2019-07-30 2021-02-04 Sartorius Stedim Biotech Gmbh Membrane d'ultrafiltration mécaniquement stable et son procédé de production
US11642629B2 (en) 2020-03-20 2023-05-09 Saudi Arabian Oil Company Multi-layer composite gas separation membranes, methods for preparation, and use

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