JP2014065034A - Acid gas separation layer, production method and facilitated transport membrane therefor, and acidic gas separation module and acidic gas separation system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acidic gas separation layer that maintains high acidic gas separation performance and besides, exhibits superior producibility/usability by suppressing deliquescence of a facilitated transport membrane, and to provide a production method and the facilitated transport membrane for the acidic gas separation layer, and to provide an acidic gas separation module with the acidic gas separation layer, and an acidic gas separation system.SOLUTION: There is provided the production method for an acidic gas separation layer having a facilitated transport membrane on a porous support. By the method, the facilitated transport membrane is formed by applying application liquid containing a hydrophilic compound and at least two kinds of alkali metal compounds onto a porous support. There is provided the acidic gas separation layer having the facilitated transport membrane on the porous support, the facilitated transport membrane containing the hydrophilic compound and at least two kinds of alkali metal compounds, or there is provided the facilitated transport membrane of the acidic gas separation layer, and the facilitated transport membrane contains the hydrophilic compound and at least two kinds of alkali metal compounds. Also, there is provided the acidic gas separation module obtained by using the acidic gas separation layer, and the acidic gas separation system.

Description

  The present invention relates to an acidic gas separation layer, a production method thereof, an facilitated transport membrane thereof, an acidic gas separation module, and an acidic gas separation system.

  In recent years, development of a technique for selectively separating an acid gas in a raw material gas has progressed. For example, an acid gas separation module that separates an acid gas from a raw material gas by an acid gas separation membrane that selectively permeates the acid gas has been developed.

  Patent Document 1 discloses an acid gas separation module in which a laminated body including an acid gas separation membrane is wound around a permeate gas collecting pipe having a through-hole formed in a pipe wall and fixed at an adhesive portion in a state of being wound in multiple layers. Yes. In this Patent Document 1, a so-called “dissolving diffusion membrane” is used as an acidic gas separation membrane, which performs separation by utilizing the difference between the solubility of the acidic gas and the substance to be separated in the membrane and the diffusivity in the membrane. .

  Patent Documents 2 and 3 disclose an acidic gas separation module in which a laminated body including an acidic gas separation membrane is provided inside a tubular body (outer frame). In Patent Document 2, a so-called “facilitated transport membrane” is used as the acidic gas separation membrane, in which a carrier is contained in the membrane, and the acidic gas is transported to the opposite side of the membrane by the carrier.

Japanese Patent Laid-Open No. 4-215824 Japanese Patent No. 462295 JP 2009-082850 A

  However, the acid gas separation module of Patent Document 1 generally uses a dissolution diffusion membrane that has a lower solubility with respect to the separation target substance and a slower permeation rate of the acid gas than the facilitated transport membrane. The separation efficiency will be low. In particular, when an acidic gas is separated from a raw material gas containing water vapor at a high temperature of 100 ° C. or higher, the dissolution diffusion membrane and the bonded portion are deteriorated by heat and moisture, and the separation efficiency is lowered.

  Moreover, in the acidic gas separation module of patent document 2, although the facilitated-transport film | membrane is used as an acidic gas separation film | membrane, since this film | membrane is provided inside the tubular body, it is difficult to improve a membrane area. Therefore, unless the number of modules is increased, the acid gas separation efficiency is lowered.

By the way, the facilitated transport film is usually selected in the film because a carrier made of an alkali metal such as cesium carbonate present in the film reacts with water to release OH ⁻ and reacts with CO _2. Ingest CO ₂ . On the other hand, since this membrane requires the intervention of water, its deliquescence becomes a problem. Specifically, the film surface is condensed or blocking is performed at the time of roll after continuous film formation. As a result, the handling at the time of making an acidic gas separation module is poor, and the production suitability is lowered. Excessive deliquescence also becomes an impediment to gas separation operations.

  The present invention, while maintaining high acid gas separation performance, while suppressing the deliquescence of the facilitated transport membrane and exhibiting excellent production and use suitability, its production method and its facilitated transport membrane, and An object is to provide an acid gas separation module and an acid gas separation system including the acid gas separation layer.

The above-described problems of the present invention have been solved by the following means.
<1> A method for producing an acidic gas separation layer having a facilitated transport film on a porous support, wherein a coating liquid containing a hydrophilic compound and two or more alkali metal compounds is applied on the porous support. A method for producing an acidic gas separation layer as the facilitated transport membrane.

<2> The method for producing an acidic gas separation layer according to <1>, wherein one of the two or more alkali metal compounds is potassium.

<3> The method for producing an acidic gas separation layer according to <1> or <2>, wherein the two or more alkali metal compounds include potassium carbonate, potassium bicarbonate, or potassium hydroxide.

<4> Any one of <1> to <3>, wherein a mass ratio of the two or more alkali metal compounds to the total mass of the hydrophilic compound and the two or more alkali metal compounds is 25% by mass or more and 85% by mass or less. The method for producing an acidic gas separation layer according to claim 1.

<5>
The method for producing an acidic gas separation layer according to any one of <1> to <4>, wherein the hydrophilic compound is polyvinyl alcohol or a polyvinyl alcohol-polyacrylic acid copolymer.

<6>
The method for producing an acidic gas separation layer according to any one of <1> to <5>, wherein one of the two or more alkali metal compounds is unevenly distributed on the surface side of the facilitated transport membrane.

<7> The method for producing an acidic gas separation layer according to <6>, wherein the alkali metal compound unevenly distributed on the surface side of the facilitated transport membrane is a potassium salt or a potassium ion.

<8> The acidic gas separation according to <6> or <7>, wherein the alkali metal compound unevenly distributed on the surface side of the facilitated transport film is contained in an amount of 0.01% by mass to 10% by mass (compared to the total amount of solids). Layer manufacturing method.

<9>
An acidic gas separation layer having a facilitated transport membrane on a porous support, wherein the facilitated transport membrane contains a hydrophilic compound and two or more alkali metal compounds.

<10> The acidic gas separation according to <9>, wherein the mass ratio of the two or more alkali metal compounds to the total mass of the hydrophilic compound and the two or more alkali metal compounds is 25% by mass or more and 85% by mass or less. layer.

<11> The acidic gas separation layer according to <9> or <10>, wherein one of the two or more alkali metal compounds is unevenly distributed on the surface side of the facilitated transport membrane.

<12> The acidic gas separation layer according to <11>, wherein the alkali metal compound unevenly distributed on the surface side of the facilitated transport membrane is contained in an amount of 0.01% by mass to 10% by mass (compared to the total amount of solids).

<13>
<9>-<12> The acidic gas separation module which has an acidic gas separation layer of any one of <12>.

<14> An acid gas separation system comprising the acid gas separation module according to <13>.

<15> A facilitated transport film for an acidic gas separation layer, which includes a hydrophilic compound and two or more alkali metal compounds.

  According to the present invention, while maintaining high acid gas separation performance, on the other hand, suppressing the deliquescence of the facilitated transport membrane and exhibiting excellent production and use suitability, its production method and its facilitated transport membrane, In addition, an acid gas separation module and an acid gas separation system including the acid gas separation layer can be provided.

FIG. 1 is a schematic configuration diagram showing one embodiment of an acidic gas separation module and provided with a partial cutout. FIG. 2 is a cross-sectional view taken along the line AA of FIG. FIG. 3 is a view showing a state before the laminated body is wound around the permeate gas collecting pipe in the acidic gas separation module, and is a view showing an embodiment of a formation region of each bonding portion. FIG. 4A is a manufacturing process diagram of the acidic gas separation module. FIG. 4B is a manufacturing process diagram of the acidic gas separation module following FIG. 4A. FIG. 4C is a manufacturing process diagram of the acidic gas separation module following FIG. 4B. FIG. 5 is a view showing a modification of the acidic gas separation module shown in FIG. FIG. 6 is a view showing a modification of the acidic gas separation module shown in FIG. FIG. 7 is a view showing another modification of the acidic gas separation module shown in FIG. FIG. 8 is a cross-sectional view schematically showing a cross section of the acidic gas separation layer. It is an EDX measurement image which shows the electron micrograph which shows the cross section of the acidic gas separation layer sample produced by the reference example (sample 101), and element distribution.

  Hereinafter, an acidic gas separation module and a method for producing an acidic gas separation module according to an embodiment of the present invention will be specifically described with reference to the accompanying drawings. In the drawings, members (components) having the same or corresponding functions are denoted by the same reference numerals and description thereof is omitted as appropriate.

<Acid gas separation module>
FIG. 1 is a schematic configuration diagram showing one embodiment of an acidic gas separation module 10 with a partial cutout.

As shown in FIG. 1, the acidic gas separation module 10 has a basic structure in which the outermost periphery of the laminate 14 is a coating layer in a state where one or a plurality of laminates 14 are wound around the permeate gas collecting pipe 12. 16, and telescope prevention plates 18 are attached to both ends of these units.
When the source gas 20 containing an acidic gas is supplied to the laminated body 14 from the one end portion 10A side, the acidic gas separation module 10 having such a configuration converts the raw material gas 20 into the acidic gas by the configuration of the laminated body 14 to be described later. 22 and the remaining gas 24 are separated and discharged separately to the other end portion 10B side.

  The permeate gas collecting pipe 12 is a cylindrical pipe having a plurality of through holes 12A formed in the pipe wall. One end side (one end 10A side) of the permeate gas collecting pipe 12 is closed, and the other end side (the other end 10B side) of the permeate gas collecting pipe 12 is opened and passes through the laminate 14 and gathers from the through hole 12A. A discharge port 26 from which acidic gas 22 such as carbon dioxide gas is discharged is provided.

The ratio (opening ratio) of the through-holes 12A that make the surface area of the permeate gas collecting pipe 12 in a region sealed with an adhesive described later is preferably 1.5% or more and 80% or less, and preferably 3% or more and 75%. Or less, more preferably 5% or more and 70% or less. Furthermore, the aperture ratio is preferably 5% or more and 25% or less from a practical viewpoint.
By setting each lower limit value or more, the acidic gas 22 can be efficiently collected. Moreover, the intensity | strength of a pipe | tube can be raised and it can fully ensure processability by setting it as each upper limit or less.

  Although the shape of 12 A of through-holes is not specifically limited, It is preferable that the circular hole of 0.5-20 mmphi is opened. Moreover, it is preferable that the through holes 12 </ b> A are arranged uniformly with respect to the surface of the permeate gas collecting pipe 12.

  The coating layer 16 is formed of a blocking material that can block the raw material gas 20 that passes through the acidic gas separation module 10. This barrier material preferably further has heat and humidity resistance. In the present embodiment, unless otherwise specified, “heat resistance” of “heat resistance and humidity” means having heat resistance of 60 ° C. or higher. Specifically, heat resistance of 60 ° C. or higher means that the shape before storage is maintained even after 2 hours of storage at 60 ° C. or higher, and curling that can be visually confirmed by heat shrinkage or heat melting does not occur. Means that. Further, in the present embodiment, “moisture resistance” of “heat resistance and humidity resistance” means that the form before storage is maintained even after storage for 2 hours under the condition of 40 ° C. and 80% RH. This means that no curl can be confirmed.

The telescope prevention plate 18 has an outer peripheral annular portion 18A, an inner peripheral annular portion 18B, and a radial spoke portion 18C, and each is preferably formed of a heat and moisture resistant material.
Specifically, the telescope prevention plate 18 is made of a metal material (for example, SUS, aluminum, aluminum alloy, tin, tin alloy, etc.), a resin material (for example, polyethylene resin, polypropylene resin, aromatic polyamide resin, nylon 12). , Nylon 66, polysulfone resin, polytetrafluoroethylene resin, polycarbonate resin, acrylic / butadiene / styrene resin, acrylic / ethylene / styrene resin, epoxy resin, nitrile resin, polyetheretherketone resin (PEEK), polyacetal resin (POM) , Polyphenylene sulfide (PPS), and the like, and fiber reinforced plastics of these resins (for example, fibers are glass fiber, carbon fiber, stainless steel fiber, aramid fiber, etc.), and long fibers are particularly preferable. , For example long glass fiber reinforced polypropylene, long glass fiber-reinforced polyphenylene sulfide), as well as ceramics (such as zeolite, alumina, etc.) and the like.

  The laminated body 14 is sandwiched between acidic gas separation layers 32 in which a supply gas flow path member 30 is folded inward with a facilitated transport film, which will be described later, and the acidic gas separation layer 32 is used for the permeate gas flow path on the radially inner side. The member 36 is configured to be bonded via an adhesive portion 34 that has penetrated these members.

  The number of the laminated body 14 wound around the permeate gas collecting pipe 12 is not particularly limited and may be single or plural, but by increasing the number (number of laminated layers), the membrane area of the facilitated transport film 32A can be improved. Thereby, the quantity which can isolate | separate the acidic gas 22 with one module can be improved. Moreover, in order to improve a film area, you may make the length of the laminated body 14 longer.

  Moreover, when there are a plurality of laminates 14, the number is preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. When the number is less than or equal to the number, it becomes easy to wind the laminate 14 and the workability is improved.

The width of the laminate 14 is not particularly limited, but is preferably 50 mm or more and 10,000 mm or less, more preferably 60 mm or more and 9000 mm or less, and preferably 70 mm or more and 8000 mm or less. Furthermore, it is preferable that the width | variety of the laminated body 14 is 200 mm or more and 2000 mm or less from a practical viewpoint.
By setting each lower limit value or more, the effective facilitated transport film 32A film area can be ensured even when the adhesive is applied (sealed). Moreover, by setting it as each upper limit value or less, the horizontality of the winding core can be maintained and the occurrence of winding deviation can be suppressed.

  FIG. 2 is a cross-sectional view taken along the line AA of FIG.

As shown in FIG. 2, the stacked bodies 14 are bonded to each other through an adhesive portion 40 that has penetrated the acidic gas separation layer 32, and are stacked around the permeate gas collecting pipe 12.
Specifically, the laminated body 14 is formed by laminating a permeate gas flow path member 36, an acidic gas separation layer 32, a supply gas flow path member 30, and an acidic gas separation layer 32 in order from the permeate gas collecting pipe 12 side. .
By these laminations, the source gas 20 containing the acid gas 22 is supplied from the end of the supply gas flow path member 30 and permeates the acid gas separation layer 32 of the present embodiment partitioned by the coating layer 16. The separated acidic gas 22 is accumulated in the permeate gas collecting pipe 12 via the permeate gas flow path member 36 and the through hole 12 </ b> A, and is collected from the discharge port 26 connected to the permeate gas collective pipe 12. Further, the residual gas 24 separated from the acid gas 22 that has passed through the gap or the like of the supply gas flow path member 30 is supplied to the supply gas flow path on the side where the discharge port 26 is provided in the acidic gas separation module 10. It is discharged from the end portions of the member 30 and the acid gas separation layer 32.

(Supply gas channel member)
The supply gas flow path member 30 is a member to which the raw material gas 20 including the acidic gas 22 is supplied from the one end portion 10A side of the acidic gas separation module 10, and has a function as a spacer. Since it is preferable to generate a turbulent flow, a net-like member is preferably used. Since the gas flow path changes depending on the shape of the net, the shape of the unit cell of the net is selected from shapes such as rhombus and parallelogram according to the purpose. Assuming that the raw material gas 20 containing water vapor is supplied at a high temperature, it is preferable that the supply gas flow path member 30 has moisture and heat resistance similarly to the acidic gas separation layer 32 described later.

  The material of the supply gas channel member 30 is not limited in any way, but paper, fine paper, coated paper, cast coated paper, synthetic paper, cellulose, polyester, polyolefin, polyamide, polyimide, polysulfone, aramid, Examples thereof include resin materials such as polycarbonate and inorganic materials such as metal, glass and ceramics. The resin materials include polyethylene, polystyrene, polyethylene terephthalate, polytetrafluoroethylene (PTFE), polyethersulfone (PES), polyphenylene sulfide (PPS), polysulfone (PSF), polypropylene (PP), polyimide, polyetherimide, poly Suitable examples include ether ether ketone and polyvinylidene fluoride.

  In addition, preferable materials from the viewpoint of heat and humidity resistance include inorganic materials such as ceramics, glass, and metals, organic resin materials having heat resistance of 100 ° C. or higher, high molecular weight polyester, polyolefin, heat resistant polyamide, polyimide, and the like. Polysulfone, aramid, polycarbonate, metal, glass, ceramics and the like can be suitably used. More specifically, at least one selected from the group consisting of ceramics, polytetrafluoroethylene, polyvinylidene fluoride, polyethersulfone, polyphenylene sulfide, polysulfone, polyimide, polypropylene, polyetherimide, and polyetheretherketone. It is preferable that it is comprised including these materials.

  Although the thickness of the member 30 for supply gas flow paths is not specifically limited, 100 micrometers or more and 1000 micrometers or less are preferable, More preferably, they are 150 micrometers or more and 950 micrometers or less, More preferably, they are 200 micrometers or more and 900 micrometers or less.

(Acid gas separation layer)
The acidic gas separation layer 32 includes a facilitated transport film 32A provided on the supply gas flow path member 30 side, and a porous support 32B that supports the facilitated transport film 32A and is provided on the permeate gas flow path member 36 side. ,have.

(Facilitated transport membrane)
The facilitated transport film 32A contains at least a carrier that reacts with the acidic gas 22 in the raw material gas 20 that passes through the supply gas flow path member 30 and a hydrophilic compound that supports the carrier. Has a function of selectively transmitting. In the present embodiment, the facilitated transport film 32A generally has a heat resistance higher than that of the dissolution diffusion film, so that the acidic gas 22 can be selectively permeated even under a temperature condition of, for example, 100 ° C. to 200 ° C. It can be done. Further, even if the raw material gas 20 contains water vapor, the facilitated transport film 32A containing the hydrophilic compound absorbs the water vapor and retains moisture, so that the carrier is more easily transported. Therefore, the separation efficiency is increased as compared with the case where a dissolution diffusion membrane is used.

Membrane area facilitated transport membrane 32A is not particularly limited, it is preferably 0.01 m ² or more 1000 m ² or less, more preferably 0.02 m ² or more 750 meters ² or less, 0.025 m ² or more 500 meters ² Even more preferably: Furthermore, the membrane area, from a practical point of view, is preferably 1 m ² or more 100 m ² or less.
By setting each lower limit value or more, the acidic gas 22 can be efficiently separated with respect to the membrane area. Moreover, workability becomes easy by being below each upper limit.

The length (the total length before folding in half) of the facilitated transport film 32A is not particularly limited, but is preferably 100 mm or more and 10,000 mm or less, more preferably 150 mm or more and 9000 mm or less, and even more preferably 200 mm or more and 8000 mm or less. Furthermore, the length is preferably from 800 mm to 4000 mm from a practical viewpoint.
By setting each lower limit value or more, the acidic gas 22 can be efficiently separated with respect to the membrane area. Moreover, by setting it as each upper limit or less, generation | occurrence | production of winding deviation is suppressed and workability becomes easy.

  The thickness of the facilitated transport film 32A is not particularly limited, but is preferably 1 to 200 μm, and more preferably 2 to 175 μm. A thickness in such a range is preferable because sufficient gas permeability and separation selectivity can be realized.

Further, the facilitated transport film 32A preferably has a cross-linked structure from the viewpoint of heat resistance. From such a viewpoint, a preferred embodiment will be described.
The facilitated transport film 32A is formed of, for example, a single or a plurality of crosslinkable groups selected from the following group (A), and has a hydrophilic structure having a crosslinked structure including a hydrolysis-resistant bond selected from the following group (B). It is composed of an organic compound layer. In particular, from the viewpoint of excellent acid gas separation characteristics and durability, the facilitated transport membrane 32A is formed of a single crosslinkable group selected from the following group (A), and has resistance selected from the following group (B). It is preferably composed of a hydrophilic compound layer having a crosslinked structure containing a hydrolyzable bond.

(A) group: —OH, —NH ₂ , —Cl, —CN, —COOH, epoxy group (B) group: ether bond, acetal bond, —NH—CH ₂ —C (OH) —, —OM —O— (M represents Ti or Zr), —NH—M—O— (M represents Ti or Zr), urethane bond, —CH ₂ —CH (OH) —, amide bond

-Hydrophilic compound-
Examples of the hydrophilic compound include hydrophilic polymers. The hydrophilic polymer functions as a binder and retains moisture when used as an acidic gas separation layer to exert a function of separating a gas such as carbon dioxide by a carrier. The hydrophilic compound can be dissolved in water to form a coating solution, and the facilitated transport film is preferably highly hydrophilic from the viewpoint of having high hydrophilicity (moisturizing property). It preferably has a hydrophilicity of 0.5 g / g or more. Furthermore, it is more preferable to have a hydrophilicity of 1 g / g or more, more preferable to have a hydrophilicity of 5 g / g or more, more preferable to have a hydrophilicity of 10 g / g or more, and further to 20 g. Most preferably, it has a hydrophilicity of at least / g.

The weight average molecular weight of the hydrophilic compound is appropriately selected within a range where a stable film can be formed, but is preferably 20,000 to 2,000,000, more preferably 25,000 to 2,000,000, 30 2,000 to 2,000,000 is particularly preferred. If it is less than the lower limit, the film strength may not be obtained.
In particular, when the hydrophilic compound has —OH as a crosslinkable group, for example, those having a weight average molecular weight of 30,000 or more are preferable. The weight average molecular weight is more preferably 40,000 or more, and more preferably 50,000 or more. When the hydrophilic compound has —OH as a crosslinkable group, the upper limit of the weight average molecular weight is not particularly limited, but is preferably 6 million or less from the viewpoint of production suitability.
Also, when having -NH ₂ as crosslinkable groups, a weight average molecular weight of those is preferably 10,000 or more. The weight average molecular weight is more preferably 15,000 or more, and more preferably 20,000 or more. Although there is no restriction | limiting in particular in the upper limit of a weight average molecular weight, From a viewpoint of manufacturing aptitude, it is preferable that it is 1 million or less.
The weight average molecular weight of the hydrophilic compound is, for example, a value measured according to JIS K 6726 when PVA is used as the hydrophilic compound. Moreover, when using a commercial item, the molecular weight nominally used by a catalog, a specification, etc. is used.

As the crosslinkable group, a group capable of forming a hydrolysis-resistant crosslinked structure is selected, and a hydroxy group (—OH), an amino group (—NH ₂ ), a carboxy group (—COOH), an epoxy group, a chlorine atom ( -Cl), a cyano group (-CN) and the like. Among these, an amino group and a hydroxy group are preferable, and a hydroxy group is most preferable from the viewpoint of affinity with a carrier and a carrier carrying effect.

Such hydrophilic compounds having a single crosslinkable group are preferably polyallylamine, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyethyleneimine, polyvinylamine, polyornithine, polylysine, polyethylene oxide, water-soluble Cellulose cellulose, starch, alginic acid, chitin, polysulfonic acid, polyhydroxymethacrylate, poly N vinylacetamide and the like, and polyvinyl alcohol is most preferable. Moreover, these copolymers are also mentioned as a hydrophilic compound.
Examples of the hydrophilic compound having a plurality of crosslinkable groups include polyvinyl alcohol-polyacrylate copolymer. A polyvinyl alcohol-polyacrylic acid copolymer is preferable because of its high water absorption ability and high hydrogel strength even at high water absorption. The content of the polyacrylate 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%. %. The polyacrylic acid may form a salt, and examples of the polyacrylic acid salt include alkali metal salts such as sodium salt and potassium salt, ammonium salt and organic ammonium salt.

Polyvinyl alcohol is also available as a commercial product, and examples thereof include PVA117 (manufactured by Kuraray), Poval (manufactured by Kuraray), polyvinyl alcohol (manufactured by Aldrich), and J-Poval (manufactured by Nihon Vinegar & Poval) . Although there are various molecular weight grades, it is preferable to select those having a weight average molecular weight of 130,000 to 300,000 as described above.
A commercially available product of a commercially available polyvinyl alcohol-polyacrylate copolymer (sodium salt) is very available, and examples thereof include Clastomer AP20 (trade name, manufactured by Kuraray Co., Ltd.).

  Two or more hydrophilic compounds may be used as a mixture.

  The content of the hydrophilic compound is 0.5 to 50% by mass from the viewpoint of forming a film as a binder and allowing the hydrophilic compound layer to sufficiently retain moisture, although it depends on the type. More preferably, it is more preferably 0.75 to 30% by mass, and still more preferably 1 to 15% by mass.

-Crosslinking agent-
The crosslinked structure can be formed by a conventionally 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.
In forming the hydrophilic compound layer in the present embodiment, it is preferable to use a composition containing a crosslinking agent together with the hydrophilic compound. Hereinafter, the coating composition for forming a hydrophilic compound layer used for forming the hydrophilic compound layer may be simply referred to as “coating composition” or “composition”.
As the cross-linking agent, a cross-linking structure formed by selecting one containing a cross-linking agent having two or more functional groups capable of undergoing thermal cross-linking or photo-crosslinking by reacting with the hydrophilic compound having the single or plural cross-linkable groups. Requires a hydrolysis-resistant crosslinked structure selected from the group (B). From such a viewpoint, as a crosslinking agent that can be used in this embodiment, 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, Examples include organometallic crosslinking agents. Preferred are polyvalent aldehydes, organometallic crosslinking agents, and epoxy crosslinking agents, more preferred are organometallic crosslinking agents and epoxy crosslinking agents, and most preferred are glutaraldehyde and formaldehyde having two or more aldehyde groups. It is a polyvalent aldehyde.

As an 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, Kyoeisha Chemical Co., Ltd., Epolite 100MF (trimethylolpropane triglycidyl ether), Nagase ChemteX Corporation EX-411, EX-313, EX-614B, EX -810, EX-811, EX-821, EX-830, NOF Corporation Epiol E400, etc. are mentioned.
Moreover, as a compound similar to an epoxy crosslinking agent, an oxetane compound having a cyclic ether is also preferably used. The oxetane compound is preferably a polyvalent glycidyl ether having two or more functional groups, and commercially available products include, for example, EX-411, EX-313, EX-614B, EX-810, EX-811, EX manufactured by Nagase ChemteX Corporation. -821, EX-830, and the like.

Hereinafter, other crosslinking agents used for forming a crosslinked structure in the present embodiment will be described.
Examples of the polyvalent glycidyl ether 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 thereof include glycol glycidyl ether and polypropylene glycol diglycidyl ether.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, polyglycerin, propylene glycol, diethanolamine, triethanolamine, polyoxypropyl, and oxyethylene oxypropylene block copolymer. Examples thereof 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-acylidinyl) propionate], 1,6-hexamethylenediethyleneurea, diphenylmethane-bis-4,4′-. N, N′-diethylene urea and the like can be mentioned.

Examples of the haloepoxy compound include epichlorohydrin and α-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 organometallic crosslinking agents include organic titanium crosslinking agents and organic zirconia crosslinking agents.

Among the above crosslinking agents, for example, when a high molecular weight polyvinyl alcohol having a weight average molecular weight of 130,000 or more is used as the hydrophilic compound, the reactivity with the hydrophilic compound is good and the hydrolysis resistance is also excellent. Epoxy compounds and glutaraldehyde are particularly preferable because a crosslinked structure can be formed.
In addition, for example, when polyallylamine having a weight average molecular weight of 10,000 or more is used, an epoxy compound can be formed because a crosslinked structure having good reactivity with this hydrophilic compound and excellent hydrolysis resistance can be formed. , Glutaraldehyde, and organometallic crosslinkers are particularly preferred.
When polyethyleneimine or polyallylamine is used as the hydrophilic compound, an epoxy compound is particularly preferable as the crosslinking agent.

The content when the coating liquid composition contains a crosslinking agent is preferably 0.001 to 80 parts by mass, more preferably 0.01 to 100 parts by mass of the crosslinkable group possessed by the hydrophilic compound. 60 parts by mass to 60 parts by mass is preferable, and most preferably 0.1 to 50 parts by mass. When the content is in the above range, the formability of the crosslinked structure is good and the shape maintaining property of the formed gel film is excellent.
If attention is paid to the crosslinkable group possessed by the hydrophilic compound, the crosslinked structure is a crosslinked structure formed by reacting 0.001 mol to 80 mol of the crosslinking agent with respect to 100 mol of the crosslinkable group possessed by the hydrophilic compound. Is preferred.

-Career-
The carrier is a variety of water-soluble compounds that have affinity with acidic gas (for example, carbon dioxide gas) and show basicity. In this embodiment, the carrier is composed of an alkali metal compound, a nitrogen-containing compound, and a sulfur oxide. At least one selected from the group consisting of:
The carrier refers to a substance that reacts indirectly with the acid gas, or a substance that itself reacts directly with the acid gas.
Examples of the former include those that react with other gases contained in the supply gas, exhibit basicity, and react with the basic compound and acid gas. More specifically react with steam OH ^- to the release, the OH ^- refers to alkali metal compounds can be incorporated selectively CO ₂ in the film by reacting with CO ₂ .
The latter are, for example, nitrogen-containing compounds and sulfur oxides that are themselves basic.

Examples of the alkali metal compound include at least one selected from the group consisting of alkali metal carbonates, alkali metal bicarbonates, and alkali metal hydroxides. Here, as the alkali metal, an alkali metal element selected from cesium, rubidium, potassium, lithium, and sodium is preferably used.
In addition, in this specification, an alkali metal compound is used in the meaning containing 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 as an alkali metal element is preferable from the viewpoint of good affinity with an acidic gas.

  Here, in this embodiment, since the hygroscopic facilitated transport membrane 32A is used as the carbon dioxide separation membrane, the facilitated transport membrane 32A becomes a gel due to moisture absorbed at the time of manufacture, and the facilitated transport membrane 32A is formed between the films at the time of manufacture. And a phenomenon (blocking) that sticks to other members. When this blocking occurs, when the facilitated transport film 32A is peeled off, the facilitated transport film 32A may cause a defect due to the sticking, resulting in a gas leak. Therefore, in this embodiment, it is preferable to prevent blocking.

Therefore, in this embodiment, the carrier preferably contains two or more alkali metal compounds. This is because, by using two or more kinds of carriers, blocking of the same kind of carriers in the film can be created by creating a non-uniformity of blocking by separating the distances.
Furthermore, it is more preferable that the carrier contains a first alkali metal compound having deliquescence and a second alkali metal compound having a lower deliquescence and a lower specific gravity than the first alkali metal compound. Specifically, the first alkali metal compound includes cesium carbonate, and the second alkali metal compound includes potassium carbonate.
Since the carrier includes the first alkali metal compound and the second alkali metal compound, the second alkali metal compound having a small specific gravity is arranged on the film surface side of the facilitated transport film 32A (that is, the surface side of the facilitated transport film 32A (supply gas) The first alkali metal compound having a large specific gravity is disposed on the inner side of the facilitated transport film 32A (that is, unevenly distributed on the porous support 32B side of the facilitated transport film 32A). Arranged). And since the 2nd alkali metal compound arrange | positioned at the film surface side has lower deliquescence property than a 1st alkali metal compound, compared with the case where a 1st alkali metal compound is arrange | positioned at the film surface side, a film surface is sticky. Therefore, blocking can be suppressed. In addition, since the first alkali metal compound having high deliquescence is disposed inside the membrane, blocking is suppressed and the separation efficiency of carbon dioxide gas is reduced as compared with the case where the second alkali metal compound is simply disposed over the entire membrane. Can be increased.

Specifically, as shown in FIG. 8, in the acidic gas separation layer 10, when two or more kinds of alkali metal compounds (first and second alkali metal compounds) are applied as carriers, the facilitated transport film 32A is porous. It consists of a second layer 32A-2 on the surface side opposite to the support 32B (supply gas flow path member 30 side) and a first layer 32A-1 on the porous support 32B side below it. The facilitated transport film 32A is entirely composed of a hydrophilic compound (hydrophilic polymer). Among them, the second layer 32A-2 mainly includes a second alkali metal compound having low deliquescence and low specific gravity. Is contained. In the first layer 32A-1, a first alkali metal compound having mainly deliquescence exists. The thickness of the second layer 32A-2 is not particularly limited, but is preferably 0.01 to 150 μm and preferably 0.1 to 100 μm in order to exhibit a sufficient deliquescent function. More preferred.
In the facilitated transport film 32A, in the illustrated state, the second layer 32A-2 containing the second alkali metal compound is unevenly distributed on the surface side (supply gas flow path member 30 side), and the first alkali metal compound is located below the second layer 32A-2. However, the present invention is not limited to this. For example, the interface between the two layers may not be clear, and the two layers may be separated in a state in which both change in an inclined manner. Further, the interface is not constant and may be in a meandering state.

  Due to the action of the second layer 32A-2 containing the second alkali metal compound having low deliquescence and low specific gravity, the deliquescence of the film is suppressed. The reason why the second alkali metal compound is unevenly distributed is considered to be due to the difference in specific gravity between two or more alkali metals. That is, by setting one of two or more types of alkali metals to a low specific gravity, it is possible to localize a lighter specific gravity in the coating solution at the time of film formation. And while maintaining the high transport capability of carbon dioxide etc. which the 1st alkali metal compound which has the deliquescence contained in 1st layer 32A-1 inside a film has, the 2nd alkali on the film surface of 2nd layer 32A-2. Condensation and the like can be prevented by the property of the metal compound that is easier to crystallize. Thereby, while blocking can be suppressed, the separation efficiency of a carbon dioxide gas can be improved.

  Since the second alkali metal compound only needs to be on the film surface side in order to suppress blocking, the second alkali metal compound is preferably contained in a smaller amount than the first alkali metal compound. Thereby, the amount of the first alkali metal compound having high deliquescence is relatively large in the entire membrane, and the carbon dioxide separation efficiency can be further increased.

  Here, the number of types of two or more types of alkali metal compounds is determined by the type of alkali metal, and even if the counter ions are different, it is not counted as one type. That is, even if potassium carbonate and potassium hydroxide are used in combination, it is counted as one type.

As a combination of two or more kinds of alkali metal compounds, the following are preferable. In the table below, an alkali metal compound is indicated by the name of alkali metal, but it may be a salt or ion thereof.
----------------------
Combination Second alkali metal compound, first alkali metal compound ---------------------
# 1 Potassium Cesium # 2 Potassium Rubidium # 3 Potassium Cesium / Rubidium ----------------------

  The content of the entire carrier in the hydrophilic compound layer depends on the type of the carrier, but in order to prevent salting out before coating and to surely exhibit the separation function of acid gas, it is 0.3 to 30% by mass. It is preferable that it is 0.5 to 25% by mass, more preferably 1 to 20% by mass.

  When two or more kinds of alkali metal compounds are applied as the carrier, the content of the two or more kinds of alkali metal compounds is the total solid content of the hydrophilic compound and two or more kinds of alkali metal compounds that are the main components of the film. In terms of mass, the mass ratio of two or more alkali metal compounds is preferably 25% by mass or more and 85% by mass or less, and more preferably 30% by mass or more and 80% by mass or less. By setting this amount within the above range, the gas separation function can be sufficiently exhibited.

  Among the two or more types of alkali metal compounds, the second alkali metal compound (which is less deliquescence and lower in specific gravity than the first alkali metal compound) is unevenly distributed on the surface side of the facilitated transport film 32A (supply gas flow path member 30 side). The alkali metal compound) is 0.01% by mass or more with respect to the total mass (typically, the total mass of the separated layer after drying) of the solids such as the hydrophilic compound and the two or more alkali metal compounds. It is preferably 0.02% by mass or more. Although there is no upper limit in particular, it is preferable that it is 10 mass% or less, and it is more preferable that it is 7.5 mass% or less. If this amount is too small, blocking may not be prevented, and if it is too large, handling may not be possible.

The ratio of the second alkali metal compound to the first alkali metal compound is not particularly limited, but the first alkali metal compound is preferably 50 parts by mass or more and 100 parts by mass or more with respect to 100 parts by mass of the second alkali metal compound. More preferred. As an upper limit, 100000 mass parts or less are preferable, and 80000 mass parts or less are more preferable. By adjusting the ratio of the two in this range, it is possible to achieve both blocking properties and handling properties at a high level.

Examples of nitrogen-containing compounds include amino acids such as glycine, alanine, serine, proline, histidine, taurine, and diaminopropionic acid, hetero compounds such as pyridine, histidine, piperazine, imidazole, and triazine, monoethanolamine, diethanolamine, and triazine. Alkanolamines such as ethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, cyclic polyetheramines such as cryptand [2.1] and cryptand [2.2], cryptand [2.2.1] Bicyclic polyetheramines such as cryptand [2.2.2], porphyrin, phthalocyanine, ethylenediaminetetraacetic acid and the like can be used.
As the sulfur compound, for example, amino acids such as cystine and cysteine, polythiophene, dodecylthiol and the like can be used.

-Other ingredients-
In the composition used for forming the facilitated transport film 32A, various additives may be used in addition to the hydrophilic compound, the crosslinking agent, and the carbon dioxide carrier. Further, water as a solvent may be contained in a small amount that is dried during production.

-Antioxidant-
The coating liquid composition may contain an antioxidant as long as the effects of the present embodiment are not impaired. The addition of an antioxidant has the advantage of further improving wet heat resistance.
Commercially available products may be used as the antioxidant, and suitable antioxidants include, for example, dibutylhydroxytoluene (BHT), Irganox 1010, Irganox 1035FF, Irganox 565, and the like.

-Specific compounds and polymer particles-
As an additive, the composition of the facilitated transport film 32A includes (1) an alkyl group having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms as a hydrophobic portion and a hydrophilic group that is a hydrophilic portion. compounds having, (2) a compound having a siloxane structure, (3) the group average particle diameter is in and the specific gravity 0.01μm~1000μm made from three polymer particles of 0.5g ^/ cm ³ ~1.3g ^/ cm 3 You may contain the 1 type or 2 or more types selected more.
When forming the facilitated transport film 32A containing one or more of these, the specific compound and / or polymer particles are not simply present in the facilitated transport film 32A. It is made to be unevenly distributed near the film surface. At this time, it is unevenly distributed so that carbon dioxide can permeate. By doing in this way, generation | occurrence | production of the blocking at the time of continuous film forming is suppressed effectively, maintaining acidic gas separability favorably. As a result, productivity by suppressing the occurrence of film peeling can be improved. This is particularly effective when continuous film formation is performed roll-to-roll.

(Specific compounds)
The facilitated transport film 32 </ b> A does not include or includes the polymer particles described later, and also includes a compound having a C 3-20 alkyl group or a C 3-20 fluorinated alkyl group and a hydrophilic group, and a siloxane structure. 1 type or 2 types or more of compounds (specific compound) chosen from the group which consists of a compound which has.

  As content of a specific compound, 0.0001-1 mass% is preferable with respect to the total mass of the composition of the facilitated-transport film | membrane 32A, 0.0003-0.8 mass% is more preferable, 0.001-0 More preferably, 1% by mass. When the content of the specific compound is 0.0001% by mass or more, the effect of inhibiting the occurrence of blocking is excellent. In addition, when the content of the specific compound is 1% by mass or less, the separability of acidic gas such as carbon dioxide is kept good.

  A compound having an alkyl group having 3 to 20 carbon atoms or a fluoroalkyl group having 3 to 20 carbon atoms and a hydrophilic group tends to be unevenly distributed so as to cover the surface of the film when a coating film is formed by coating, It is effective in preventing the occurrence of blocking. Specifically, in the step of forming the facilitated transport film 32A containing the surfactant having the alkyl group or the fluorinated alkyl group, the compound is formed into a film due to the highly hydrophobic alkyl group or fluoroalkyl group. Blocking is effectively prevented by orienting the surface and reducing the surface energy of the film surface. Therefore, it is preferable that the compound has a higher hydrophobicity, that is, an alkyl group or fluoroalkyl group having a long carbon chain.

  As this compound, a compound having a hydrophobic part and a hydrophilic part and containing an alkyl group having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms as the hydrophobic part can be used. Specific examples include surfactants having a C3-20 alkyl group or a C3-20 fluorinated alkyl group in the hydrophobic portion.

  Examples of the alkyl group having 3 to 20 carbon atoms include groups such as propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, and eicosyl. Especially, it is preferable to have a long-chain alkyl group in terms of being easily distributed on the film surface, specifically, an alkyl group having 5 to 20 carbon atoms is more preferable, and more preferably 6 to 20 carbon atoms. It is an alkyl group. Among them, the case of having hexyl, octyl, decyl, dodecyl, and eicosyl is particularly preferable as the alkyl group.

  Examples of the fluorinated alkyl group having 3 to 20 carbon atoms include groups such as fluoropropyl, perfluorobutyl, perfluorohexyl, perfluorooctyl, and perfluorodecyl. Among them, it is preferable to have a fluoroalkyl group having a long carbon chain in terms of being easily distributed on the film surface. Specifically, a fluorinated alkyl group having 4 to 20 carbon atoms is preferable, and more preferably carbon. A fluorinated alkyl group having 5 to 20 carbon atoms, more preferably a fluorinated alkyl group having 6 to 20 carbon atoms. Among them, it is preferable that the fluoroalkyl group has perfluorohexyl, perfluorooctyl, or perfluorodecyl.

  Of the above alkyl groups and fluorinated alkyl groups, an alkyl group having no fluorine atom is preferred to a fluorinated alkyl group from the viewpoint of achieving a high level of compatibility between blocking inhibition and excellent acid gas separation. .

  Examples of the hydrophilic group include a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, an alkyleneoxy group, an amino group, and a quaternary ammonium group.

  Examples of surfactants having an alkyl group having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms include the following compounds.

[Surfactant]
-1. Anionic surfactant
(Carboxylic acid type)
・ Sodium octanoate (C ₇ H ₁₅ COONa)
・ Sodium decanoate (C ₉ H ₁₉ COONa)
・ Sodium laurate (C ₁₁ H ₂₃ COONa)
・ Myristate sodium (C ₁₃ H ₂₇ COONa)
・ Sodium palmitate (C ₁₅ H ₃₁ COONa)
・ Sodium stearate (C ₁₇ H ₃₅ COONa, w: Sodium stearate)
・ PFOA (C ₇ F ₁₅ COOH)
・ Perfluorononanoic acid (C ₈ F ₁₇ COOH, w: Perfluorononanoic acid)
· N-lauroyl sarcosine sodium _{(C 11 H 23 CON (CH} 3) CH 2 COONa, w: Sodium lauroyl sarcosinate)
・ Sodium cocoyl glutamate (HOOCCH ₂ CH ₂ CH (NHCOR) COONa [R: alkyl having 11 to 17 carbon atoms])
・ Alpha sulfo fatty acid methyl ester salt (CH ₃ (CH ₂ ) _n CH (SO ₃ Na) COOCH ₃ [n = 1-19])
(Sulfonic acid type)
・ Sodium 1-hexanesulfonate (C ₆ H ₁₃ SO ₃ Na)
・ Sodium 1-octanesulfonate (C ₈ H ₁₇ SO ₃ Na)
・ Sodium 1-decanesulfonate (C ₁₀ H ₂₁ SO ₃ Na)
・ Sodium 1-dodecanesulfonate (C ₁₂ H ₂₅ SO ₃ Na)
・ Perfluorobutanesulfonic acid (C ₄ F ₉ SO ₃ H, w: Perfluorobutanesulfonic acid)
・ Sodium linear alkylbenzenesulfonate (RC ₆ H ₄ SO ₃ Na [R: alkyl having 3 to 20 carbon atoms])
・ Sodium toluene sulfonate (CH ₃ C ₆ H ₄ SO ₃ Na)
・ Sodium cumene sulfonate (C ₃ H ₇ C ₆ H ₄ SO ₃ Na)
・ Sodium octylbenzenesulfonate (C ₈ H ₁₇ C ₆ H ₄ SO ₃ Na)
· Sodium dodecylbenzenesulfonate _{(DBS; C 12 H 25 C} 6 H 4 SO 3 Na)
・ Naphthalene sodium sulfonate (C ₁₀ H ₇ SO ₃ Na)
・ Naphthalenedisulfonic acid disodium (C ₁₀ H ₆ (SO ₃ Na) ₂ )
・ Trisodium naphthalene trisulfonate (C ₁₀ H ₅ (SO ₃ Na) ₃ )
・ Sodium butyl naphthalenesulfonate (C ₄ H ₉ C ₁₀ H ₆ SO ₃ Na)
・ Sodium di (2-ethylhexyl) sulfosuccinate (the following compound; Lapisol A-90, manufactured by NOF Corporation)

(Sulfate type)
・ Sodium lauryl sulfate (C ₁₂ H ₂₅ OSO ₃ Na)
・ Sodium myristyl sulfate (C ₁₄ H ₂₉ OSO ₃ Na)
・ Sodium laureth sulfate (C ₁₂ H ₂₅ (CH ₂ CH ₂ O) _n OSO ₃ Na, w: Sodium laureth sulfate)
・ Sodium polyoxyethylene alkylphenol sulfonate (C ₈ H ₁₇ C ₆ H ₄ O [CH ₂ CH ₂ O] ₃ SO ₃ Na)
・ Ammonium lauryl sulfate (C ₁₂ H ₂₅ OSO ₃ NH ₄ , w: Ammonium lauryl sulfate)
(Phosphate ester type)
・ Lauryl phosphate (C ₁₂ H ₂₅ OPO (OH) ₂ )
・ Sodium lauryl phosphate (C ₁₂ H ₂₅ OPOOHONa)
・ Potassium lauryl phosphate (C ₁₂ H ₂₅ OPOOHOK)

-2. Cationic surfactant
(Quaternary ammonium salt type)
· Chloride dodecyl dimethyl benzyl ammonium ^{_{(C 12 H 25 N + (}} CH 3) 2 CH 2 C 6 H 5 Cl)
・ Octyltrimethylammonium chloride (C ₈ H ₁₇ N ⁺ (CH ₃ ) ₃ Cl)
Decyltrimethylammonium chloride (C ₁₀ H ₂₁ N ⁺ (CH ₃ ) ₃ Cl)
・ Dodecyltrimethylammonium chloride (C ₁₂ H ₂₅ N ⁺ (CH ₃ ) ₃ Cl)
・ Tetradecyltrimethylammonium chloride (C ₁₄ H ₂₉ N ⁺ (CH ₃ ) ₃ Cl)
Cetyltrimethylammonium chloride (CTAC) (C ₁₆ H ₃₃ N ⁺ (CH ₃ ) ₃ Cl)
・ Stearyltrimethylammonium chloride (C ₁₈ H ₃₇ N ⁺ (CH ₃ ) ₃ Cl)
- hexadecyltrimethylammonium bromide _{(CTAB) (C 16 H 33} N + (CH 3) 3 Br)
・ Benzyltrimethylammonium chloride (C ₆ H ₅ CH ₂ N ⁺ (CH ₃ ) ₃ Cl)
・ Benzyltriethylammonium chloride (C ₆ H ₅ CH ₂ N ⁺ (C ₂ H ₅ ) ₃ Cl)
・ Benzalkonium chloride (C ₆ H ₅ CH ₂ N ⁺ (CH ₃ ) ₂ RCl [R: alkyl having 8 to 17 carbon atoms])
Benzalkonium bromide (C ₆ H ₅ CH ₂ N ⁺ (CH ₃ ) ₂ RBr [R: alkyl having 8 to 17 carbon atoms])
・ Benzethonium chloride (C ₆ H ₅ CH ₂ N ⁺ (CH ₃ ) ₂ (CH ₂ CH ₂ O) ₂ C ₆ H ₄ C ₈ H ₁₇ Cl)
・ Dialkyldimethylammonium chloride (RN ⁺ R (CH ₃ ) ₂ Cl [R: alkyl having 3 to 20 carbon atoms])
・ Didecyldimethylammonium chloride (C ₁₀ H ₂₁ N ⁺ C ₁₀ H ₂₁ (CH ₃ ) ₂ Cl)
・ Distearyldimethylammonium chloride (C ₁₈ H ₃₇ N ⁺ C ₁₈ H ₃₇ (CH ₃ ) ₂ Cl, w: Dimethyldioctadecylammonium chloride)
(Alkylamine salt type)
・ Monomethylamine hydrochloride (CH ₃ NH ₂ · HCl)
・ Dimethylamine hydrochloride ((CH ₃ ) ₂ NH · HCl)
・ Trimethylamine hydrochloride ((CH ₃ ) ₃ N · HCl)
(Substance having a pyridine ring)
・ Butylpyridinium chloride (C ₅ H ₅ N ⁺ C ₄ H ₉ Cl)
・ Dodecylpyridinium chloride (C ₅ H ₅ N ⁺ C ₁₂ H ₂₅ Cl)
・ Cetylpyridinium chloride (C ₅ H ₅ N ⁺ C ₁₆ H ₃₃ Cl)

-3. Nonionic surfactant
(Ester type)
Lauric glyceryl _{(C 11 H 23 COOCH 2 CH} (OH) CH 2 OH, w: Glyceryl laurate)
· Glyceryl monostearate _{(C 17 H 35 COOCH 2 CH} (OH) CH 2 OH)
・ Sorbitan fatty acid ester (RCOOCH ₂ CH (CHOH) ₃ CH ₂ O [R: alkyl having 3 to 20 carbon atoms])
・ Sucrose fatty acid ester (RCOOC ₁₂ H ₂₁ O ₁₀ [R: alkyl having 3 to 20 carbon atoms])
(Ether type)
・ Polyoxyethylene alkyl ether (RO (CH ₂ CH ₂ O) _n H [R: alkyl having 3 to 20 carbon atoms])
・ Pentaethylene glycol monododecyl ether (C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₅ H, w: Pentaethylene glycol monododecyl ether)
-Octaethylene glycol monododecyl ether (C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₈ H, w: Octaethylene glycol monododecyl ether)
・ Polyoxyethylene alkyl phenyl ether (RC ₆ H ₄ O (CH ₂ CH ₂ O) _n H [R: alkyl having 3 to 20 carbon atoms])
- Nonoxynol _{(C 9 H 19 C 6 H} 4 O (CH 2 CH 2 O) nH, w: Nonoxynols)
- Nonoxynol _{-9 (C 9 H 19 C 6} H 4 O (CH 2 CH 2 O) 9 H, w: Nonoxynol-9)
・ Polyoxyethylene polyoxypropylene glycol (H (OCH ₂ CH ₂ ) _l (OC ₃ H ₆ ) _m (OCH ₂ CH ₂ ) _n OH)
(Ester ether type)
・ Polyoxyethylene sorbitan fatty acid ester ・ Polyoxyethylene hexitan fatty acid ester ・ Sorbitan fatty acid ester polyethylene glycol (alkanolamide type)
・ Lauric acid diethanolamide (C ₁₁ H ₂₃ CON (C ₂ H ₄ OH) ₂ )
・ Oleic acid diethanolamide (C ₁₇ H ₃₃ CON (C ₂ H ₄ OH) ₂ )
・ Stearic acid diethanolamide (C ₁₇ H ₃₅ CON (C ₂ H ₄ OH) ₂ )
・ Cocamide DEA (CH ₃ (CH ₂ ) _n CON (C ₂ H ₄ OH) ₂ , w: Cocamide DEA)
(Alkyl glycoside)
・ Octyl glucoside (C ₈ H ₁₇ C ₆ H ₁₁ O ₆ )
Decyl glucoside (C ₁₀ H ₂₁ C ₆ H ₁₁ O ₆ , w: Decyl glucoside)
・ Lauryl glucoside (C ₁₂ H ₂₅ C ₆ H ₁₁ O ₆ , w: Lauryl glucoside)
(Higher alcohol)
・ Cetanol (C ₁₆ H ₃₃ OH, w: Cetyl alcohol)
・ Stearyl alcohol (C ₁₈ H ₃₇ OH, w: Stearyl alcohol)
・ Oleyl alcohol (CH ₃ (CH ₂ ) ₇ CH = CH (CH ₂ ) ₈ OH, w: Oleyl alcohol)

-4. Amphoteric surfactant
(Alkyl betaine type)
Lauryl betaine ^{_{(C 12 H 25 N + (}} CH 3) 2 CH 2 COO -)
Stearyl betaine ^{_{(C 18 H 37 N + (}} CH 3) 2 CH 2 COO -)
Dodecyl amino methyl dimethyl sulfopropyl betaine ^{_{(C 12 H 25 N + (}} CH 3) 2 (CH 2) 3 SO 3 -)
- octadecyl amino methyl dimethyl sulfopropyl betaine ^{_{(C 18 H 37 N + (}} CH 3) 2 (CH 2) 3 SO 3 -)
(Fatty acid amide propyl betaine type)
- cocamidopropyl betaine _{(C 11 H 23 CONH (CH} 2) 3 N + (CH 3) 2 CH 2 COO -, w: Cocamidopropyl betaine)
・ Cocamidopropyl hydroxysultain (C ₁₁ H ₂₃ CONH (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₂ CH ₂ CHOHCH ₂ SO ₃ ⁻ )
(Alkylimidazole type)
- 2-alkyl -N- carboxymethyl -N- hydroxyethyl imidazolinium betaine _{(RC 3 H 4 N 2 (} C 2 H 4 OH) CH 2 COO - [R: alkyl having 3 to 20 carbon atoms])
(Amino acid type)
・ Lauroyl glutamate sodium (C ₁₁ H ₂₃ CON (C ₂ H ₄ COOH) HCHCOONa)
- lauroyl potassium glutamate _{(C 11 H 23 CON (C} 2 H 4 COOH) HCHCOOK)
・ Lauroylmethyl-β-alanine (C ₁₁ H ₂₃ CONH (C ₂ H ₄ COOCH ₃ )
(Amine oxide type)
Lauryl dimethylamine -N- oxide ^{_{(C 12 H 25 N + (}} CH 3) 2 O -)
· Oleyl dimethylamine -N- oxide ^{_{(C 18 H 37 N + (}} CH 3) 2 O -)

  The molecular weight of the surfactant having an alkyl group having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms is preferably in the range of 60 to 2000, and more preferably in the range of 80 to 1500. When the molecular weight is 60 or more, it is advantageous in that blocking can be suppressed uniformly as a film surface. When the molecular weight is 2000 or less, it is possible to ensure acid gas separation while suppressing blocking.

  When forming the facilitated transport film 32A containing the surfactant having a C3-20 alkyl group or a C3-20 fluorinated alkyl group ", the content of the surfactant is, for example, a facilitated transport film. It is preferable that it is 0.01 mass%-10 mass% with respect to the total solid of 32A, Furthermore, it is preferable that it is 0.01-3 mass%. When the content of the “surfactant having an alkyl group having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms” is 0.01% by mass or more, the effect of inhibiting generation of blocking is excellent. Further, when the content of the surfactant is 10% by mass or less, the separability of acidic gas such as carbon dioxide is kept good.

[Compound having a siloxane structure]
The compound having a siloxane structure tends to be unevenly distributed so as to cover the surface of the film when the facilitated transport film 32A is formed by coating, and is effective in suppressing the occurrence of blocking. The siloxane structure is not particularly limited as long as it has a siloxane skeleton represented by “—Si—O—Si—” as a partial structure.

  As the compound having a siloxane structure, a compound containing a structural unit having a siloxane structure in the side chain is preferable from the viewpoint of enhancing the surface segregation property when the facilitated transport film 32A is formed by coating.

Siloxane compounds useful for introducing a siloxane structure into the molecule can be obtained from commercially available products such as X-22-173DX and X-22-173BX manufactured by Shin-Etsu Chemical Co., Ltd. One terminal reactive silicone is mentioned.
Such a compound can be synthesized by reacting a siloxane having a reactive end with a compound having a cationic polymerizable group. For example, it can be synthesized from a compound having a hydroxyl group at one end, such as Jira's Silaplane series FM-0411, FM-0421, FM-0425, etc., and epichlorohydrin, as disclosed in JP-A-11-80315. It can be synthesized by the method described.

  When forming the facilitated-transport film | membrane 32A containing the compound which has a siloxane structure, it is 0.01 mass%-10 mass% with respect to the total solid of the facilitated-transport film | membrane 32A as content of the compound which has a siloxane structure. It is preferable that it is 0.01-3 mass% further. When the content of the compound having a siloxane structure is 0.01% by mass or more, the effect of inhibiting the occurrence of blocking is excellent. In addition, when the content of the specific compound is 10% by mass or less, the separability of an acidic gas such as carbon dioxide is kept good.

(Polymer particles)
As polymer particles, for example, particles of polyolefin (eg, polyethylene, polypropylene, polymethylpentene, etc.), polymethyl methacrylate, polystyrene, thermoplastic elastomer, silicone, etc. are preferably mentioned. Among these, polyolefin particles are preferable in that blocking can be uniformly suppressed.

The average particle diameter of the polymer particles is in the range of 0.01 μm to 1000 μm. When the particle diameter of the polymer particles is less than 0.01 μm, the particles are too densely packed, and thus the area occupied on the film surface when the coating film is formed cannot be ensured without reducing the separation performance. On the other hand, if the average particle diameter of the polymer particles exceeds 1000 μm, too much polymer is present on the film surface when the coating film is formed, and the carbon dioxide permeability is lowered and the polymer particles may fall off. Especially, as an average particle diameter of a polymer particle, the range of 0.02 micrometer-750 micrometers is more preferable, More preferably, it is the range of 0.03 micrometer-500 micrometers, Most preferably, it is the range of 0.1 micrometer-50 micrometers.
The particle diameter of the polymer particles is a value measured using FPAR1000 manufactured by Otsuka Electronics Co., Ltd.

The specific gravity of the polymer ^particles, in the range of ^{0.5g / cm 3 ~1.3g / cm 3} . If the specific gravity of the polymer particles is less than 0.5 g / cm ³ and is too small, the membrane surface tends to be clogged, and rather the carbon dioxide permeability is impaired. In addition, when the specific gravity of the polymer particles exceeds 1.3 g / cm ³ , it becomes easy to settle in the coating solution, and it becomes difficult for the polymer to exist on the film surface when the coating film is formed, so that the blocking inhibition effect is lowered. . Among these, as the specific gravity of the polymer ^particles, more preferably in the range of ^{0.52g / cm 3 ~1.28g / cm 3} , more preferably in the range of from ^{0.55g / cm 3 ~1.27g / cm 3} .

  The polymer particles can be used, for example, in the form of an emulsion (emulsion) in which a polymer is dispersed in a liquid state in an aqueous medium and a dispersion (suspension) in which a polymer is dispersed in a solid state in an aqueous medium. .

  As the polymer particles, commercially available products may be used. For example, Chemipearl w-308, w-400, w-100, wp-100, A-100 and the like manufactured by Mitsui Chemicals, Inc. may be used. Can be used.

When the facilitated transport film 32A contains polymer particles, the total content in the facilitated transport film 32A is preferably such that the area occupied by the polymer particles on the surface of the facilitated transport film 32A is 0.1% to 60%. When the occupied area by the polymer particles is 0.1% or more, the effect of inhibiting the occurrence of blocking is excellent. Further, when the area occupied by the polymer particles is 60% or less, the acid gas separability can be kept good while blocking is suppressed. The occupied area of the polymer particles is more preferably 0.5% to 30%, and still more preferably 1% to 10%.
The occupied area is determined by image analysis of the particle coverage per unit area using a scanning electron microscope (JSM6610, manufactured by JEOL).

When the facilitated transport film 32A is formed by coating using polymer particles, the polymer particles have a low specific gravity. Therefore, in the process of forming the facilitated transport film 32A using a coating solution containing polymer particles and drying, the polymer is applied to the coating film surface. Particles are unevenly distributed. Thereby, the polymer particles are unevenly distributed on the surface to prevent blocking without performing a special treatment such as applying only to the surface.
Further, the facilitated transport film 32A is prepared on the porous support 32B by preparing a first coating solution containing polymer particles and the specific compound and a second coating solution not containing the polymer particles and the specific compound, respectively. By applying the second coating liquid and the first coating liquid so as to be in the multilayer order, it is possible to form a layer in which polymer particles and a specific compound are unevenly distributed on the film surface.
Since these compounds and polymer particles are not compatible with other components constituting the hydrophilic compound layer, they do not impair the separability inherent in the hydrophilic compound layer.

  Other components other than the above include a catalyst, a moisturizing (water absorbing) agent, an auxiliary solvent, a film strength adjusting agent, and a defect detecting agent.

(Porous support)
The porous support 32B that constitutes the acidic gas separation layer 32 together with the facilitated transport film 32A has heat resistance, like the facilitated transport film 32A.
As the material of the porous support 32B, a woven fabric, a nonwoven fabric, a porous membrane, or the like can be adopted as the form of the porous support, and the same material as the supply gas flow path member 30 may be used. .
As a material of the porous support 32B, a porous support having a high self-supporting property and a high porosity can be preferably used. Polysulfone, cellulose membrane filter membrane, polyamide, polyimide interfacially polymerized thin film, polytetrafluoroethylene, high molecular weight polyethylene stretched porous membrane has high porosity, low diffusion inhibition of separation gases such as carbon dioxide, strength, manufacturing It is preferable from the viewpoint of aptitude and the like. Among these, a stretched film of polytetrafluoroethylene (PTFE) is particularly preferable.
These porous supports can be used alone, but a composite membrane integrated with a reinforcing porous support can also be suitably used.

  As the porous support 32B, an inorganic material or an organic-inorganic hybrid material may be used in addition to the organic material described above. Examples of the inorganic porous support include a porous substrate mainly composed of ceramics. By using ceramics as a main component, it is excellent in heat resistance, corrosion resistance, etc., and mechanical strength can be increased. The type of ceramic is not particularly limited, and any commonly used ceramic can be used. Examples thereof include alumina, silica, silica-alumina, mullite, cordierite, zirconia and the like. Moreover, you may adjust by compounding 2 or more types of ceramics, or ceramics and a metal, or compounding ceramics and an organic compound.

If the porous support 32B is too thick, the gas permeability decreases, and if it is too thin, the strength is difficult. Therefore, the thickness of the support is preferably 30 μm or more and 500 μm or less, more preferably 50 μm or more and 450 μm or less, further preferably 50 μm or more and 400 μm or less, and particularly preferably 50 to 300 μm.
Further, the average pore diameter of the pores of the porous support 32B is 0.001 μm or more from the viewpoint that the adhesive application region is sufficiently impregnated with the adhesive and the gas passage region does not hinder gas passage. It is preferably 10 μm or less, more preferably 0.002 μm or more and 5 μm or less, and particularly preferably 0.005 μm or more and 1 μm or less.
In addition, in the manufacturing method of the acidic gas separation layer 32 mentioned later, when employ | adopting the continuous process using the sheet | seat fabric of the porous support body 32B, distortion and a fracture | rupture of a porous support body are produced in Roll-to-Roll manufacture. For example, the strength of the porous support 32B is preferably 10 N / 10 mm or more (tensile speed: 10 mm / min) so as not to occur.

(Method for producing acid gas separation layer)
Here, a method for producing the acid gas separation layer 32 (hereinafter simply referred to as a method for producing the acid gas separation layer 32) will be described.

For example, the acidic gas separation layer 32 is produced by applying a coating liquid (composition for forming a facilitated transport film) containing a hydrophilic compound and an alkali metal compound on the porous support 32B to form the facilitated transport film 32A. It is a method to do.
In the formation of the facilitated transport film 32A, a coating liquid (dope) that forms the facilitated transport film 32B is applied (in this specification, the term “apply” includes an aspect of being attached to the surface by dipping), and an arbitrary method. It is preferable to cure.
The term “on the porous support 32B” means that another layer may be interposed between the porous support 32B and the facilitated transport film 32A. As for the upper and lower expressions, unless otherwise specified, the direction in which the gas to be separated is supplied (the direction on the supply gas flow path member 30 side) is “up” and the separated gas is emitted ( The direction of the permeate gas flow path member 36 side) is “down”.

Preparation of coating liquid (composition for forming facilitated transport film) for forming facilitated transport film 32A includes a hydrophilic compound (hydrophilic polymer), a carrier (alkali metal compound), and other components as necessary. Each is added to water (room temperature water or warm water) in an appropriate amount and stirred sufficiently, and dissolution is promoted by heating with stirring as necessary. In addition, after adding a hydrophilic compound to water and making it melt | dissolve, precipitation (salting out) of a hydrophilic compound can be effectively prevented by adding a carrier (alkali metal compound) gradually and stirring.
Here, the solvent used for the coating liquid (composition for forming a facilitated transport film) is not particularly limited, and examples thereof include an aqueous medium (water or an aqueous solution in which water-soluble components are dissolved), and water is particularly preferable. . However, water may contain components that are inevitably dissolved. Examples of the water-soluble component include alcohol.

  Moreover, the preferable apparatus used for the manufacturing method of the acidic gas separation layer 32 is a composition on the feed roll which sends out the sheet | seat opposite (henceforth porous support opposite) of the strip | belt-shaped porous support 32B, and a porous support opposite. Is provided with a coater for coating the film, a drying section for drying the gel film, and a winding roll for winding up the obtained acid gas separation layer. In addition, a transport roll for transporting an in-process sheet fabric is disposed in each unit. By using an apparatus having such a configuration, a roll-to-roll film can be formed, and the reaction of the acidic gas separation layer 32 having excellent gas separation characteristics can be continuously performed by performing a crosslinking step. It can be manufactured efficiently.

  Hereinafter, the detail of the manufacturing method of the acidic gas separation layer 32 is demonstrated according to process.

-Application process-
In the method for producing the acidic gas separation layer 32, first, a composition for forming an facilitated transport film (coating liquid) is prepared, and then the belt-like porous support is fed from a feeding roll and conveyed to a coating section (coater). The composition (coating liquid) is applied onto a porous support to provide a coating film.

  When an inorganic material is employed as the material opposite to the porous support, the coating liquid may be applied and dried by individual conveyance instead of the illustrated continuous process. Processing by such individual conveyance may be performed by a regular method, and coating, drying, heating, and the like can be performed in the same manner as described in the present embodiment.

  Although the transport speed of the porous support is dependent on the type and the viscosity of the coating solution, if the transport speed of the porous support is too high, the film thickness uniformity of the coating film in the coating process may be reduced. Yes, if it is too late, productivity will decrease. The conveyance speed of the porous support may be determined according to the type of the porous support, the viscosity of the coating solution, etc. in consideration of the above points, but is preferably 0.5 m / min or more, and more preferably 0. .75 to 200 m / min is more preferable, and 1 to 200 m / min is particularly preferable.

  As a method for applying the coating solution, a conventionally known method can be employed. Examples include curtain flow coaters, extrusion die coaters, air doctor coaters, blade coaters, rod coaters, knife coaters, squeeze coaters, reverse roll coaters, and bar coaters. In particular, a blade coater and an extrusion die coater are preferable from the viewpoints of film thickness uniformity and coating amount.

  The coating amount of the coating liquid depends on the composition and concentration of the coating liquid, but if the coating amount per unit area is too small, pores are formed in the film during the drying process, or the strength as the facilitated transport film 32A is insufficient. There is a risk of becoming. On the other hand, if the coating amount of the coating solution is too large, the variation in the film thickness may increase, or the film thickness of the obtained facilitated transport film 32A may become too large and the permeability of the separation gas may decrease. From these viewpoints, the thickness of the gel film (facilitated transport film 32A) is 1 μm or more, more preferably 5 μm or more, and particularly preferably 10 μm or more. From the viewpoint of avoiding a decrease in the permeability of the separation gas, the thickness of the gel membrane (facilitated transport membrane 32A) is preferably 1000 μm or less.

  Thus, since the coating liquid can be applied to the porous substrate oppositely to provide the coating film and then the gel film can be obtained, the film thickness can be accurately controlled. Therefore, an acidic gas separation layer having a large thickness and a uniform thickness can be formed. The acidic gas separation layer having high gas separation characteristics can be produced with high productivity by cutting this into a predetermined length and forming it if necessary.

-Drying process-
The gel film is dried to obtain a dry film (facilitated transport film 32A). The gel film conveyed to the heating unit is dried by applying warm air. The wind speed is preferably such that the gel film can be dried quickly and the gel film does not collapse, for example, 0.5 to 200 m / min, more preferably 0.75 to 200 m / min, and further 1 Particularly preferred is ~ 200 m / min. The temperature of the wind is preferably 1 to 120 ° C., more preferably 2 to 115 ° C. so that the deformation of the porous support does not occur and the gel membrane can be quickly dried. More preferably, 3 to 110 ° C is particularly preferable.

Through the above steps, the acid gas separation layer 32 is obtained by forming into a desired size and shape as necessary.
In addition, after forming the acidic gas separation layer 32, a carrier elution prevention layer may be provided on the acidic gas separation layer 32 (the facilitated transport film 32A) in order to prevent elution of the carrier (alkali metal compound) as necessary. Good. The carrier elution prevention layer preferably has a property of allowing gas such as carbon dioxide and water vapor to pass therethrough but not passing water or the like, and is preferably a hydrophobic porous film. A film having such properties may be applied on the film surface, or a film prepared separately may be laminated.

(Permeate gas channel member)
The permeating gas flow path member 36 that constitutes the laminate 14 together with the acidic gas separation layer 32 is a member that reacts with the carrier and the acidic gas 22 that has permeated the acidic gas separation layer 32 flows toward the through hole 12A. The permeate gas flow path member 36 has a function as a spacer, and has a function of flowing the permeated acidic gas 22 to the inside of the permeate gas flow path member 36. Further, adhesive portions 34 and 40 described later are provided. Like the supply gas flow path member 30, the permeate gas flow path member 36 is preferably a net-like member so as to have a permeating function. The material of the permeating gas flow path member 36 can be the same as that of the supply gas flow path member 30. Assuming that the raw material gas 20 containing water vapor is allowed to flow at a high temperature, it is preferable that the permeate gas flow path member 36 has a heat and moisture resistance like the acidic gas separation layer 32.

  Specific materials used for the permeating gas flow path member 36 are preferably polyesters such as epoxy-impregnated polyester, polyolefins such as polypropylene, and fluorines such as polytetrafluoroethylene.

  The thickness of the permeating gas channel member 36 is not particularly limited, but is preferably 100 μm or more and 1000 μm or less, more preferably 150 μm or more and 950 μm or less, and further preferably 200 μm or more and 900 μm or less.

  The permeating gas flow path member 36 is a flow path of the acidic gas 22 that has permeated the acidic gas separation layer 32, so that it is preferable that the resistance is low. Specifically, the permeating gas flow path member 36 has a high porosity and is pressurized. For example, the deformation is small and the pressure loss is small.

The porosity is preferably 30% to 99%, more preferably 35% to 97.5%, and even more preferably 40% to 95%. In addition, the measurement of a porosity can be performed as follows. First, water is sufficiently infiltrated into the gap portion of the permeating gas channel member 36 by using ultrasonic waves, etc., and after removing excess moisture on the surface, the weight per unit area is measured. The value obtained by subtracting the weight from the dry weight is the volume of the water that has entered the gap of the permeating gas flow path member 36, and can be converted by the density of the water to measure the void amount and thus the void ratio.
At this time, if water is not sufficiently infiltrated, the measurement can be performed using a solvent having a low surface tension such as an alcohol.

  The deformation when the pressure is applied can be approximated by the elongation when the tensile test is performed, and the elongation when a load of 10 N / 10 mm width is applied is preferably within 5%, and is within 4%. It is more preferable.

  In addition, the pressure loss can be approximated to the flow loss of the compressed air that flows at a constant flow rate, and the loss within 7.5 L / min when flowing through the 15 cm square permeating gas channel member 36 at room temperature for 15 L / min. It is preferable that the loss is within 7 L / min.

(Adhesive part)
The bonding part 34 and the bonding part 40 are heat and humidity resistant adhesives.
In the present embodiment, “heat resistance” of “heat resistance and humidity” of the bonding portion 34 and the bonding portion 40 means that the glass transition temperature Tg after curing is 40 ° C. or higher, particularly 60 ° C. or higher. Preferably there is. In the present embodiment, the “moisture resistance” of the “heat resistance and moisture resistance” of the adhesive portion 34 and the adhesive portion 40 means that the adhesive strength is not halved even after being stored at 80 ° C. and 80% RH for 2 hours. To do. In order to improve the heat and moisture resistance, the viscosity is obtained by changing the material (main component) of the bonding portion 34 and the bonding portion 40 or dissolving 1 to 50 parts by weight of a filler such as polystyrene, liquid paraffin, or silica in the main component. This can be achieved by increasing

  The material of the bonding part 34 and the bonding part 40 is not particularly limited as long as it has heat and humidity resistance. For example, epoxy resin, vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride. Copolymer, vinyl chloride-acrylonitrile copolymer, butadiene-acrylonitrile copolymer, polyamide resin, polyvinyl butyral, polyester, cellulose derivative (nitrocellulose, etc.), styrene-butadiene copolymer, various synthetic rubber resins, phenol Examples include resins, urea resins, melamine resins, phenoxy resins, silicon resins, urea formamide resins, and the like.

  FIG. 3 is a view showing a state before the laminated body 14 is wound around the permeate gas collecting pipe 12 in the acidic gas separation module 10, and a view showing an embodiment of the formation region of the bonding portion 34 and the bonding portion 40. It is.

  As shown in FIG. 3, the adhesive portion 40 covers the through-hole 12A with a permeate gas flow path member 36, and the acidic gas separation is performed with the laminate 14 wound around the permeate gas collecting pipe 12 in the direction of arrow R in the figure. The layer 32 and the permeating gas channel member 36 are bonded. On the other hand, the bonding portion 34 bonds the acidic gas separation layer 32 and the permeate gas flow path member 36 before the laminate 14 is wound around the permeate gas collecting pipe 12.

  Both the adhesion part 34 and the adhesion part 40 are circumferential adhesion parts 34A and 40A for adhering both side ends of the acidic gas separation layer 32 and the permeate gas flow path member 36 along the circumferential direction of the permeate gas collecting pipe 12. It has the axial direction adhesion parts 34B and 40B which adhere | attach the said edge part of the said circumferential direction of the acidic gas separation layer 32 and the member 36 for permeate gas flow paths.

The circumferential adhesive portion 34A and the axial adhesive portion 34B are connected, and the adhesive portion 34 as a whole has an envelope shape in which the circumferential end between the acid gas separation layer 32 and the permeating gas flow path member 36 at the beginning of winding is opened. It has become. And between the circumferential direction adhesion part 34A and the axial direction adhesion part 34B, the flow path P1 in which the acidic gas 22 which permeate | transmitted the acidic gas separation layer 32 flows to 12 A of through-holes is formed.
Similarly, the circumferential adhesive portion 40A and the axial adhesive portion 40B are connected, and the circumferential end portion between the acid gas separation layer 32 and the permeate gas flow path member 36 at the beginning of the winding as the entire adhesive portion 40 is opened. It is a so-called “envelope shape”. And between the circumferential direction adhesive part 40A and the axial direction adhesive part 40B, the flow path P2 through which the acidic gas 22 which permeate | transmitted the acidic gas separation layer 32 flows to 12 A of through-holes is formed.

  In the present embodiment, since the facilitated transport membrane 32A is used as the acidic gas separation membrane, the moisture contained in the membrane oozes out into the porous support 32B and increases the wettability of the porous support 32B. By pulling in the adhesive with the surface tension, the adhesive of the adhesive part 34 and the adhesive part 40 can easily permeate into the hole of the porous support 32B through the permeating gas flow path member 36. Even if the circumferential adhesive portions 34A and 40A are not formed by the potting method, the adhesive force between the adhesive portion 34 and the adhesive portion 40 is strengthened by a normal coating method, and as a result, gas leakage can be suppressed.

<Method for producing acid gas separation module>
Next, a method for manufacturing the acid gas separation module 10 having the above-described configuration will be described.
4A to 4C are manufacturing process diagrams of the acid gas separation module 10.

In the method of manufacturing the acidic gas separation module 10 of the present embodiment, first, as shown in FIG. 4A, the distal end portion of the elongate permeated gas flow path member 36 is permeated by a fixing member 50 such as Kapton tape or adhesive. The gas collecting pipe 12 is fixed to the pipe wall (outer peripheral surface).
Here, it is preferable that the tube wall is provided with a slit (not shown) along the axial direction. In this case, the distal end portion of the permeate gas flow path member 36 is inserted into the slit, and fixed to the inner peripheral surface of the permeate gas collecting pipe 12 by the fixing member 50. According to this configuration, even when the laminate 14 including the permeate gas flow path member 36 is wound around the permeate gas collecting pipe 12, the inner circumferential surface of the permeate gas collecting pipe 12 can be The permeate gas flow path member 36 does not come out of the slit due to friction with the permeate gas flow path member 36, that is, the permeate gas flow path member 36 is fixed.

  Next, as shown in FIG. 4B, the long supply gas flow path member 30 is sandwiched between the long acidic gas separation layers 32 in which the facilitated transport film 32A is folded inward. When the facilitated transport film 32A is folded in half, the facilitated transport film 32A may be divided into two parts, but may be folded and shifted.

Next, the adhesive 52 is applied to one end in the width direction and one end in the longitudinal direction of one of the outer surfaces of the folded facilitated transport film 32A (the surface of the porous support 32B). (Apply in an envelope). Thereby, the adhesion part 34, ie, the circumferential direction adhesion part 34A and the axial direction adhesion part 34B, are formed. Moreover, in order to improve applicability | paintability, you may include various solvents and surfactant in the adhesive agent for forming the adhesion part 34. FIG.
In order to suppress gas leakage, it is preferable to fill 10% or more, particularly 30%, of the holes of the porous support 32B with the bonding portion 34. As a means for filling in this way, for example, JP-A-3-68428 can be used.

  Next, as shown in FIG. 4C, the acidic gas separation layer in which the supply gas flow path member 30 is sandwiched between the surface of the permeate gas flow path member 36 fixed to the permeate gas collecting pipe 12 via the adhesive portion 34. 32 is pasted. In addition, when the acidic gas separation layer 32 is pasted, it is pasted so that the axial direction adhesive portion 34 </ b> B is separated from the permeate gas collecting pipe 12. As a result, the circumferential portion between the acid gas separation layer 32 and the permeate gas flow path member 36 at the beginning of the winding as the entire bonding portion 34 is opened, and the circumferential bonding portion 34A and the axial bonding portion 34B are opened. In the meantime, a flow path P1 in which the acidic gas 22 that has passed through the acidic gas separation layer 32 flows to the through hole 12A is formed.

  Next, with respect to the surface of the acidic gas separation layer 32 attached to the permeate gas flow path member 36 (the surface opposite to the attached surface), the adhesive 54 is attached to both ends in the width direction and one end in the longitudinal direction of the membrane. Apply. Thereby, the adhesion part 40, ie, the circumferential direction adhesion part 40A and the axial direction adhesion part 40B, are formed, and the laminated body 14 is formed.

  Next, the laminate 14 is wrapped around the permeate gas collecting pipe 12 in the direction of arrow R so as to cover the through hole 12A with the permeate gas flow path member 36. At this time, it is preferable to wind the laminate 14 while applying tension. As a result, the adhesives 52 and 54 of the adhesive portions 34 and 40, in particular, the adhesive 54 of the adhesive portion 40 can easily penetrate into the holes of the porous support 32B, and gas leakage can be suppressed. Further, in order to apply tension, as described above, it is preferable that the permeate gas channel member 36 is inserted and fixed in the slit so that the permeate gas channel member 36 is not fixed. .

  By obtaining the above steps, the acidic gas separation module 10 shown in FIG. 1 is obtained.

<Modification>
Although the present invention has been described in detail with respect to specific embodiments, the present invention is not limited to such embodiments, and various other embodiments are possible within the scope of the present invention. It will be apparent to those skilled in the art, and for example, the following modifications may be appropriately combined with the above-described embodiment, and the above-described embodiment may be replaced with the following modification.

  For example, in the above-described embodiment, when the source gas 20 containing the acid gas is supplied from the one end 10 </ b> A side to the laminate 14, the acid gas separation module 10 converts the source gas 20 into the acid gas 22 and the remaining gas 24. The case where it is the structure which isolate | separates and discharges separately to the other end part 10B side was demonstrated. However, in the acidic gas separation module 10, the raw material gas 20 containing acidic gas is supplied from the other end 10 </ b> B side to the laminated body 14, and the raw material gas 20 is separated into the acidic gas 22 and the remaining gas 24. Alternatively, it may be configured to discharge separately.

  In the above embodiment, the case where the supply gas flow path member 30 is sandwiched between the two folded acid gas separation layers 32 has been described. However, the acid gas separation layer 32 and the supply gas flow path member 30 are simply stacked. There may be. In this case, the laminated body 14 includes, for example, in order from the permeate gas collecting pipe 12 side, a permeate gas flow path member 36, an adhesive portion 34, an acidic gas separation layer 32, a supply gas flow path member 30, and an adhesive portion 40 (both surfaces). Tape).

  Further, the acid gas separation module 10 may be reinforced with FRP (Fiber Reinforced Plastics) in order to improve the strength of the acid gas separation module 10 and fix the telescope prevention plate 18. The type of fiber or matrix resin used in FRP is not limited, and examples of the fiber include glass fiber, carbon fiber, Kevlar, Dyneema, etc. Among them, glass fiber is particularly preferable. Examples of the matrix resin include an epoxy resin, a polyamide resin, an acrylate resin, and an unsaturated polyester resin. From the viewpoint of heat resistance and hydrolysis resistance, an epoxy resin is preferable.

The container for storing the acidic gas separation module 10 is not particularly limited, but there are two or more inlets of the raw material gas 20 on the diagonal line, or a manifold provided so that the gas uniformly hits the end surface of the acidic gas separation module. In this case, the separation efficiency is further improved.
Further, a plurality of acid gas separation modules 10 may be arranged in parallel in a container in order to adjust the flow rate and flow rate of the gas flowing in per module of the acid gas separation module 10 and to control the pressure loss. Moreover, you may connect the some acidic gas separation module 10 in series in a container.

In the above embodiment, the case where the one end portion side of the permeate gas collecting pipe 12 is closed has been described. However, an opening and a sweep gas selected from an inert gas or the like may be supplied from the opening. .
In this case, it is preferable to use an acidic gas separation module 100 as shown in FIG. FIG. 5 is a view showing a modification of the acidic gas separation module 10 shown in FIG.

  As shown in FIG. 5, the acid gas separation module 100 is configured by multiple layers 14 wound around the permeate gas collecting pipe 12, as with the acid gas separation module 10. However, in the acidic gas separation module 100, the permeate gas collecting pipe 12 is provided at one end of the pipe and the discharge port 26 through which the acidic gas 22 collected from the through hole 12A is discharged, and the sweep gas provided at the other end of the pipe is provided. And a supply port 60 to be supplied. Further, the permeate gas collecting pipe 12 has a blocking member 62 provided at the center of the pipe and blocking the inside of the pipe. The permeate gas collecting pipe 12 is not limited to the central portion of the pipe, but may be provided between the discharge port 26 and the supply port 60.

Further, in the acidic gas separation module 100, the partition adhesive portion 64 is formed between the circumferential adhesive portions 34A and on the outer peripheral side of the blocking member 62 along the circumferential direction (the length direction of the laminate 14 before winding). ing. The partition bonding portion 64 is not in contact with the axial direction bonding portion 34B, and forms a flow path P3 through which the sweep gas flows between the circumferential direction bonding portion 34A and the axial direction bonding portion 34B.
Similarly, in the acidic gas separation module 100, partition adhesive portions 66 are formed along the circumferential direction (the length direction of the laminate 14 before winding) between the circumferential adhesive portions 40A and on the outer peripheral side of the blocking member 62. Has been. The partition bonding portion 66 is not in contact with the axial direction bonding portion 40B, and forms a flow path P4 through which sweep gas flows between the circumferential direction bonding portion 40A and the axial direction bonding portion 40B.

Since the flow paths P3 and P4 through which the sweep gas flows are formed in this manner, the acid gas flows toward the through hole 12A without staying between the bonding portions 34 and 40, and thus gas leakage occurs. It is suppressed and the separation efficiency of acid gas is increased.
Since the partition bonding portions 64 and 66 are only provided for forming the flow paths P3 and P4, it is preferable that the width is narrower than the circumferential bonding portions 34A and 40A. This is because the acid gas is less likely to permeate from the acid gas separation layer 32 as much as the partition bonding portions 64 and 66 are present, so that it is better to make the width as narrow as possible.

  Further, the position of the blocking member 62 shown in FIG. 5 is not limited to the central portion of the pipe, and may be on one end side of the pipe. In this case, the positions of the partition bonding portions 64 and 66 are also matched with the position of the blocking member 62. Further, the number of the blocking members 62 is not limited to one and may be plural.

  As shown in FIG. 6, the blocking member 62 may be formed obliquely with respect to the sweep gas flow in order to reduce pressure loss.

  Further, the number and shape of the partition bonding portions 66 are not particularly limited, and the partition bonding portions 66 include a substantially L-shaped outer partition bonding portion 66A and a substantially L-shaped inner partition as shown in FIG. And an adhesive portion 66B. The number and shape of the partition bonding portions 64 are not limited.

(Acid gas separation system)
The acidic gas separation system of the present invention includes the acidic gas separation module 10 of the present invention. In the acidic gas separation system of the invention, when a plurality of acidic gas separation modules 10 are provided, they may be provided in parallel or connected in series. In addition, a plurality of acid gas separation modules 10 connected in series may be connected in parallel.

  In addition, the acid gas separation system of the present invention may be a system in which the acid gas separation layer 32 is installed as a flat membrane, or a pleated type using the acid gas separation layer 32 is arranged. It may be a system.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited and interpreted by these Examples at all.

<Reference Example 1>
In Reference Example 1, 1M hydrochloric acid was added to an aqueous solution containing Clastomer AP-20 (manufactured by Kuraray): 2.4% by weight, 25% glutaraldehyde aqueous solution (manufactured by Wako): 0.01% by weight until pH 1 was reached. Then, after crosslinking, a 40% cesium carbonate (rare metal) aqueous solution as a carrier was added so that the concentration of cesium carbonate was 6.0% by weight. Further, 1% Lapisol A-90 [manufactured by NOF Corporation; surfactant represented by the above structural formula (sodium di (2-ethylhexyl) sulfosuccinate, molecular weight = 445; specific compound)] is 0.003% by weight After the temperature was raised, a separately prepared agar aqueous solution was added to obtain a coating composition.
By applying and drying this coating composition using PTFE / PP nonwoven fabric (manufactured by GE) as a porous support, an acidic gas separation layer composed of an facilitated transport membrane and a porous support was produced.

Next, the produced acidic gas separation layer was folded in half with the facilitated transport membrane inside. Kapton tape was applied to the valley part folded in half, and the end part of the supply gas flow path member was reinforced so as not to damage the surface shape of the film valley part. And the polypropylene net | network of thickness 0.5mm was inserted | pinched between the acidic gas separation layer folded in half as a member for supply gas flow paths. Apply an adhesive (Henkel Japan) E120HP made of epoxy resin with high viscosity (about 40 Pa · s) on the porous support side of this unit so that it becomes an envelope shape (see Fig. 3), and then a tricot knitted epoxy Impregnated polyester permeation gas flow path members were stacked and wound around the permeation gas collecting pipe in multiple layers.
Thereby, the acidic gas separation module according to Reference Example 1 was produced. The membrane area of such a module was 0.025 m ² .

  Here, in the production of the acid gas separation module according to Reference Example 1, the adhesive was applied to the porous support so that 14% of the holes of the porous support were filled with the adhesive ( Hereinafter, the ratio of the adhesive embedded in the pores of the porous support is referred to as “adhesive penetration rate.” When the porous support uses two or more kinds of porous, the membrane side The ratio of the pores of the permeate gas channel member completely buried in the pores of the porous support located at 1.

The penetration rate of the adhesive was measured as follows.
After disassembling the produced module and cutting out the adhesive-applied portion, the frozen and cleaved section is observed with an SEM. From the observed image, image analysis is performed to determine how much of the pore portion of the porous support is filled with the adhesive.
Then, the area (A) of the pores of the porous support soaked with the adhesive and the area (B) of the holes not soaked with the adhesive are measured, and the “adhesion penetration rate” is calculated from the following calculation formula. Calculation formula: Adhesive penetration rate = A ÷ (A + B) × 100
From the above, the case where the hole is completely filled with the adhesive is 100%.

<Reference Example 2>
An acidic gas separation module according to Reference Example 2 was produced in the same manner as Reference Example 1 except that the penetration rate of the adhesive into the pores of the porous support was 86%. The membrane area of such a module was 0.025 m ² .

<Reference Example 3>
Change the permeate gas collecting tube to one having a blocking member at the center of the tube, and form a partition bonding portion to provide a flow path through which the sweep gas flows (see FIG. 5). An acidic gas separation module according to Reference Example 3 was produced in the same manner as Reference Example 1 except that the penetration rate was 91%. The membrane area of such a module was 0.025 m ² .

<Example 4>
Clastomer AP-20 (manufactured by Kuraray Co., Ltd .; polyvinyl alcohol-polyacrylate copolymer (hydrophilic polymer)) 2.4 mass% and 25 mass% glutaraldehyde aqueous solution (manufactured by Wako; cross-linking agent) 0.01 mass 1M hydrochloric acid was added to an aqueous solution containing 1% until the pH reached 1, and crosslinking was performed. Thereafter, an aqueous solution of 40% by mass of cesium carbonate (manufactured by Rare Metal Co., Ltd .; alkali metal salt) was added so that the cesium carbonate concentration was 3.66% by mass. Subsequently, 40 mass% potassium carbonate (Wako company make; alkali metal salt) aqueous solution was added so that potassium carbonate concentration might be 0.61 mass%. Further, 1% by mass of Lapisol A-90 was added so as to have a concentration of 0.003% by mass, and the temperature was raised. Then, the agar aqueous solution prepared separately was added to this, and it was set as the coating liquid (coating liquid for acidic gas separation layer formation).
PTFE / PP non-woven fabric (manufactured by GE) is prepared as a porous support, and the coating liquid obtained on this non-woven fabric is applied and dried to separate the acidic gas comprising the facilitated transport membrane and the porous support. A layer was made. In addition, content of surfactant was 0.05 mass% with respect to the total solid of a facilitated-transport film | membrane.
Next, an acidic gas separation module according to Example 4 was produced in the same manner as in Reference Example 1 using the produced acidic gas separation layer. However, the penetration rate of the adhesive into the pores of the porous support was 92%. The membrane area of such a module was 0.025 m ² .

<Example 5>
The acidic gas separation module according to Example 5 was changed in the same manner as in Example 4 except that the permeate gas flow path member was made of polypropylene and the penetration rate of the adhesive into the pores of the porous support was 93%. Produced. The membrane area of such a module was 0.025 m ² .

<Reference Example 6>
An acidic gas separation module according to Reference Example 6 was produced in the same manner as Reference Example 1 except that the penetration rate of the adhesive into the pores of the porous support was 9.1%. The membrane area of such a module was 0.025 m ² .

<Comparative Example 1>
Comparative Example 1 was the same as Reference Example 1 except that a dissolution and diffusion membrane composed of triacetylcellulose was used instead of the facilitated transport membrane, and the penetration rate of the adhesive into the pores of the porous support was 88%. Thus, an acidic gas separation module according to Comparative Example 1 was produced. The membrane area of such a module was 0.025 m ² .

<Gas separation evaluation>
The acidic gas separation performance was evaluated under the following condition 1 using the acidic gas separation module according to each of Examples, Reference Examples, and Comparative Examples. Further, for Reference Example 3 and Examples 4 to 5, measurement under Condition 2 was also performed.

-Condition 1-
A source gas (flow rate: 2.2 L / min) of H ₂ : CO ₂ : H ₂ O = 45: 5: 50 as a test gas is supplied to each acid gas separation module at a temperature of 130 ° C. and a total pressure of 301.3 kPa, Ar gas (flow rate 0.6 L / min) was flowed to the permeate side. The permeated gas was analyzed with a gas chromatograph, and the CO ₂ permeation rate (P (CO ₂ )) and the CO ₂ / H ₂ separation factor (α) were calculated. The calculation results of P (CO ₂ ) and α are summarized in Table 1.

-Condition 2-
A source gas (flow rate: 2.2 L / min) of H ₂ : CO ₂ : H ₂ O = 45: 5: 50 as a test gas is supplied to each acid gas separation module at a temperature of 130 ° C. and a total pressure of 301.3 kPa, A mixed gas of H ₂ O: Ar = 50: 50 (flow rate: 0.6 L / min) was allowed to flow on the permeate side. The permeated gas was analyzed with a gas chromatograph, and the CO ₂ permeation rate (P (CO ₂ )) and the CO ₂ / H ₂ separation factor (α) were calculated. The calculation results of P (CO ₂ ) and α are summarized in Table 1.

As shown in Condition 1 of Table 1, the acidic gas separation modules of Reference Examples 1 to 3, Examples 4 to 5, and Reference Example 6 have higher α values than Comparative Example 1, respectively. It can be seen that the separation efficiency of the acidic gas is high even when the acidic gas (CO ₂ ) is separated. Further, among Reference Examples 1 to 3, Examples 4 to 5, and Reference Example 6, it can be seen that Reference Examples 2 to 3 and Examples 4 to 5 have higher separation efficiency.

  As shown in Condition 2 in Table 1, the acidic gas separation modules of Reference Example 3 and Examples 4 to 5 have higher α values than Comparative Example 1, respectively. It can be seen that the separation efficiency of the acidic gas is high even when the gas is separated.

<Module defect evaluation>
Defect evaluation of each produced acid gas separation module was evaluated by sealing the gas after filling the supply side with He gas and measuring the time during which the pressure decreased from 0.34 MPa to 0.3 MPa. Table 2 shows the evaluation results of the defects.

  As shown in Table 2, it can be seen that Reference Examples 1 to 3, Examples 4 to 5, and Reference Example 6 have a longer pressure reduction time and fewer defects than Comparative Example 1. Among them, it can be seen that Reference Examples 1 to 3 and Examples 4 to 5 have a longer pressure reduction time and fewer defects than Reference Example 6. Further, it can be seen that Reference Example 3 and Examples 4 to 5 have a longer pressure reduction time and fewer defects than Reference Examples 1 and 6.

<Example 101 to Example 109, Reference Examples 11 to 14>
(Preparation of acid gas separation layer sample)
As carriers of the coating liquid composition for forming the facilitated transport film of Reference Example 1, the first alkali metal compound 1 [cesium carbonate (manufactured by Wako)] and the second alkali metal compound [potassium carbonate (manufactured by Wako)] are used. A coating composition was prepared in the same manner as in Reference Example 1 except that these alkali metal compounds had a composition with a solid content ratio shown in Table 3. The composition was coated and dried using a hydrophobic PTFE porous membrane (Fluoropore FP010, manufactured by Sumitomo Electric Industries) as a porous support, and the acid gas separation layer of Example 101 having the thickness shown in Table 3 for each layer. Sample 101 was produced.
And except having changed into the conditions shown in Table 3, it carried out similarly to the acidic gas separation layer sample 101, and produced the acidic gas separation layer samples 102-109 and C11-C14 of Examples 102-109 and Reference Examples 11-14. did. However, C14 did not add lapizol A-90.

Note that * 1 and * 2 in Table 3 are as follows.
* 1: References start with “C” * 2: Thickness was determined by analysis of SEM image of film cross section (average of 10 points)

-Gas separation evaluation-
The separation performance of carbon dioxide gas was evaluated as follows using each acid gas separation layer sample.
The porous support was cut to a diameter of 47 mm and sandwiched between PTFE membrane filters to prepare a permeation test sample. As a test gas, a mixed gas of H ₂ : CO ₂ = 9: 1 (flow rate 500 mL / min) at a relative humidity of 70%, a temperature of 130 ° C., a total pressure of 301.3 kPa, and each of the above samples (effective area 2.40 cm ² ) And Ar gas (flow rate 90 mL / min) was allowed to flow on the permeate side. Table 4 shows values obtained by analyzing the permeated gas with a gas chromatograph and calculating the CO ₂ permeation rate (P (CO ₂ )) and the CO ₂ / H ₂ separation factor (α).

-Blocking evaluation-
The coated film was wound around a paper tube so as to make five turns, and then placed for 1 day under conditions of 25 ° C. and 50%. One day later, when the coating film was peeled from the paper tube, it was evaluated whether or not there was adhesion peeling on the coated surface, and the results are shown in Table 4.
A indicates that there is no peeling, B indicates that there is no peeling, but indicates that there is some sticking when unwinding, and C indicates that some peeling has occurred,
D 1 shows a state in which the film is broken although there is no peeling.

Regarding Example 101 to Example 109 (Samples 101 to 109), it can be seen that P (CO ₂ ) is 30 GPU or more and α is 100 or more. Also in the blocking evaluation, good results were obtained, and a good composite film without peeling was formed. On the other hand, in Reference Example 11 (Sample C11), in the facilitated transport film, the solid content ratio was high and cracking was confirmed. Further, in Reference Example 12 (Sample C12), in the facilitated transport film, the cesium concentration of the first layer (cesium layer) is low and the gas permeation / separation property is inferior. confirmed. Further, in Reference Example 14 (Sample C14), since no Lapisol A-90 was added, partial peeling was detected.

  FIG. 9 shows an electron micrograph and an EDX image obtained by observing a cross section of the acidic gas separation layer sample of Example 101 (sample 101). As can be seen from this observation result, it is understood that potassium carbonate is unevenly distributed in the second layer on the surface side with respect to cesium carbonate constituting the first layer in the facilitated transport film.

10,100 Acid gas separation module 12 Permeate gas collecting pipe 12A Through hole 14 Laminate 20 Raw material gas 22 Acid gas 26 Discharge port 30 Supply gas flow path member 32 Acid gas separation layer 32A Promoted transport membrane 32B Porous support 34B, 40B Axial direction adhesive portion 34A, 40A Circumferential direction adhesive portion 34, 40 Adhesive portion 36 Permeate gas flow path member 50 Fixing member 52, 54 Adhesive 60 Supply port 62 Blocking member 64, 66 Partition adhesive portion P3 Flow path P4 Flow path

Claims (15)

  A method for producing an acidic gas separation layer having a facilitated transport film on a porous support, wherein the promotion is performed by applying a coating liquid containing a hydrophilic compound and two or more alkali metal compounds on the porous support. A method for producing an acidic gas separation layer as a transport membrane.   The method for producing an acidic gas separation layer according to claim 1, wherein one of the two or more alkali metal compounds is potassium.   The method for producing an acidic gas separation layer according to claim 1 or 2, wherein the two or more alkali metal compounds contain potassium carbonate, potassium bicarbonate, or potassium hydroxide.   The mass ratio of two or more types of alkali metal compounds to the total mass of the hydrophilic compound and two or more types of alkali metal compounds is 25% by mass or more and 85% by mass or less. The manufacturing method of the acidic gas separation layer of description.   The method for producing an acidic gas separation layer according to any one of claims 1 to 4, wherein the hydrophilic compound is polyvinyl alcohol or a polyvinyl alcohol-polyacrylic acid copolymer.   The method for producing an acidic gas separation layer according to any one of claims 1 to 5, wherein one of the two or more alkali metal compounds is unevenly distributed on a surface side of the facilitated transport membrane.   The method for producing an acidic gas separation layer according to claim 6, wherein the alkali metal compound unevenly distributed on the surface side of the facilitated transport membrane is a potassium salt or a potassium ion.   The production of the acidic gas separation layer according to claim 6 or 7, wherein the alkali metal compound unevenly distributed on the surface side of the facilitated transport membrane is contained in an amount of 0.01% by mass to 10% by mass (compared to the total amount of solids). Method.   An acidic gas separation layer having a facilitated transport membrane on a porous support, wherein the facilitated transport membrane contains a hydrophilic compound and two or more alkali metal compounds.   The acidic gas separation layer according to claim 9, wherein a mass ratio of the two or more alkali metal compounds to the total mass of the hydrophilic compound and the two or more alkali metal compounds is 25 mass% or more and 85 mass% or less.   The acidic gas separation layer according to claim 9 or 10, wherein one of the two or more alkali metal compounds is unevenly distributed on the surface side of the facilitated transport membrane.   The acidic gas separation layer according to claim 11, wherein an alkali metal compound unevenly distributed on the surface side of the facilitated transport membrane is contained in an amount of 0.01% by mass to 10% by mass (compared to the total amount of solids).   The acidic gas separation module which has an acidic gas separation layer of any one of Claims 9-12.   An acid gas separation system comprising the acid gas separation module according to claim 13.   A facilitated transport membrane for an acidic gas separation layer, comprising a hydrophilic compound and two or more alkali metal compounds.