JP2016041415A - Acidic gas separation module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acidic gas separation module capable of, in an acidic gas separation module using a facilitated transport membrane, preventing carriers for the facilitated transport membrane from penetrating a porous support.SOLUTION: An acidic gas separation module has a layered body formed from a member for a supply gas flow path, a porous support, an intermediate layer a part of which is soaked into the porous support, and a facilitated transport membrane on the intermediate layer. The ratio between the thickness of the intermediate layer on the porous support and the thickness of the same soaked into the porous support is 0.1 to 100. The gas permeability of the intermediate layer is 500 Barrer or greater.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an acidic gas separation module that separates an acidic gas from a raw material gas using a facilitated transport membrane. More specifically, the present invention relates to an acidic gas separation module that can prevent the carrier of the facilitated transport membrane from coming off the support that supports the facilitated transport membrane.

  In recent years, development of technology for selectively separating an acid gas from a source gas (a gas to be treated) has been advanced. For example, an acidic gas separation module that separates an acidic gas from a raw material gas using an acidic gas separation membrane that selectively permeates the acidic gas has been developed.

As an example, Patent Document 1 includes a carbon dioxide carrier on a carbon dioxide permeable support as an acidic gas separation membrane (carbon dioxide separation gel membrane) for separating carbon dioxide (carbon dioxide) from a raw material gas. An acidic gas separation membrane is disclosed in which a hydrogel membrane formed by absorbing an aqueous solution into a vinyl alcohol-acrylate copolymer having a crosslinked structure is formed.
Patent Document 1 discloses, as a method for producing this acidic gas separation membrane, an uncrosslinked vinyl alcohol-acrylate copolymer aqueous solution is applied in a film form on a carbon dioxide permeable support, A method for producing an acidic gas separation membrane is also disclosed in which an aqueous solution is heated and cross-linked to insolubilize water, and the water-insolubilized material absorbs a carbon dioxide carrier aqueous solution and gels.

  The acidic gas separation membrane shown in Patent Document 1 is an acidic gas separation membrane using a so-called facilitated transport membrane. The facilitated transport membrane has a carrier that reacts with an acidic gas such as the above-mentioned carbon dioxide carrier in the membrane, and the acidic gas is separated from the source gas by transporting the acidic gas to the opposite side of the membrane by this carrier. .

  Such an acid gas separation membrane usually has a configuration in which a facilitated transport membrane is formed on a porous support such as a nonwoven fabric or a porous membrane.

Here, the facilitated transport film needs to retain a large amount of moisture in the film in order to sufficiently function the carrier. Therefore, a polymer having extremely high water absorption and water retention is used for the facilitated transport film. In addition, in the facilitated transport membrane, as the content of a carrier such as a metal carbonate increases, the water absorption increases and the separation performance of the acid gas improves. That is, the facilitated transport film is often a very soft (low viscosity), gel film.
In addition, in the acidic gas separation membrane using the facilitated transport membrane, the raw material gas having a temperature of 100 to 130 ° C. and a humidity of about 90% is supplied at a pressure of about 1.5 MPa when the acidic gas is separated.

Therefore, when an acid gas separation membrane using a facilitated transport membrane is used, the carrier gradually reaches the support from the facilitated transport membrane and permeates the support.
If the facilitated transport membrane or the carrier flows out, the acid gas separation performance is lowered accordingly. Therefore, the acid gas module using the facilitated transport membrane cannot be said to have sufficient durability.

In order to solve such problems, Patent Document 2 discloses that a facilitated transport film (polymer compound layer) is formed on a hydrophobic support (porous film) having a heat resistance of 100 ° C. or higher. In the acidic gas separation membrane, a carrier diffusion suppression layer is provided between the support and the facilitated transport membrane.
Examples of the carrier diffusion suppressing layer include siloxane, silicone rubber, polybutadiene, ethylcellulose, polyvinylidene fluoride, polypropylene, polysulfone, polyetherimide, polyethersulfite, polyacrylic acid, and polyvinyl alcohol. Moreover, 0.01-100 micrometers is illustrated as thickness of a carrier diffusion suppression layer.

Japanese Patent Publication No. 7-102310 JP 2013-27841 A

As shown in Patent Document 2, by providing a carrier diffusion suppression layer on the surface of the support, it is possible to suppress the carriers that have escaped from the facilitated transport film from reaching the support and permeate the support.
However, in recent years, the durability required for the acid gas separation module has become more severe, and the number of carriers passing through the support through the facilitated transport membrane is further reduced, and the acid gas module having higher durability can be reduced. Appearance is desired.

  An object of the present invention is to solve such a problem of the prior art, and is an acid gas separation module using an acid gas separation membrane having a facilitated transport membrane, which passes through the support through the facilitated transport membrane. It is an object of the present invention to provide an acidic gas separation module with excellent durability, capable of greatly reducing the number of carriers to be prevented and preventing performance deterioration due to carrier slippage.

In order to achieve this object, the acidic gas separation module of the present invention comprises a porous support, an intermediate layer formed on the porous support, and an acid gas and reaction formed on the intermediate layer. An acidic gas separation membrane having a facilitated transport membrane containing a carrier and a hydrophilic compound for supporting the carrier, and a member for a supply gas flow path serving as a flow path for the source gas,
The intermediate layer has a support upper region located on the porous support, and a permeation region inside the porous support, the thickness Ta of the support upper region, and the thickness of the permeation region. Provided is an acid gas separation module characterized in that the ratio “Tb / Ta” to Tb is 0.1 to 100 and the gas permeability is 500 Barrer or more.

In such an acidic gas separation module of the present invention, the ratio “Tc / (Ta + Tb)” between the thickness Tc of the facilitated transport film and the thickness “Ta + Tb” of the intermediate layer is preferably 0.3 to 500. .
Moreover, it is preferable that it is a spiral type formed by winding the laminated body containing an acidic gas separation membrane and the member for supply gas flow paths.
Moreover, it is preferable that it is a flat plate type which maintains the laminated body containing an acidic gas separation membrane and the member for supply gas flow paths in flat plate shape.
Moreover, it is preferable that an intermediate | middle layer has as a main component the compound which has at least 1 of an epoxy group, an amino group, a methoxy group, an ethoxy group, a hydroxyl group, and a carboxyl group.
The intermediate layer is preferably a polydimethylsiloxane derivative.
Moreover, it is preferable to have a protective layer on the facilitated-transport film | membrane.
The protective layer is preferably a polydimethylsiloxane derivative.
The facilitated transport film preferably contains at least one metal element selected from the group consisting of Ti, Zr, Al, Si, and Zn.
Moreover, it is preferable that content of the metal element in a facilitated-transport film | membrane is 0.1-50 mass% with respect to the hydrophilic compound total mass.
Furthermore, it is preferable that a facilitated-transport film | membrane contains the structural unit represented by Formula (1).
Formula (1) M- (O- *) _m
M represents a metal element selected from the group consisting of Ti, Zr, Al, Si, and Zn. m represents the valence of the metal element represented by M. * Represents a binding position.

According to the present invention, since the acidic gas separation membrane has a predetermined intermediate layer under the support and the facilitated transport membrane, carriers are discharged from the facilitated transport membrane and permeate the porous support. Can be prevented.
Therefore, according to the present invention, it is possible to obtain an acidic gas separation module excellent in durability while suppressing a decrease in the acidic gas separation performance of the facilitated transport membrane caused by the carrier permeating the support.

It is a schematic perspective view which partially cuts off and shows an example of the acidic gas separation module of this invention. It is a schematic sectional drawing of a part of laminated body of the acidic gas separation module shown in FIG. It is a schematic sectional drawing of a part of acidic gas separation membrane of the acidic gas separation module shown in FIG. (A) And (B) is a conceptual diagram for demonstrating another example of the acidic gas separation module of this invention. (A) And (B) is a conceptual diagram for demonstrating the preparation methods of the acidic gas separation module shown in FIG. It is a conceptual diagram for demonstrating the production method of the acidic gas separation module shown in FIG. (A) And (B) is a conceptual diagram for demonstrating the preparation methods of the acidic gas separation module shown in FIG. It is a conceptual diagram for demonstrating the production method of the acidic gas separation module shown in FIG. It is a conceptual diagram for demonstrating the production method of the acidic gas separation module shown in FIG.

  Hereinafter, the acidic gas separation module of the present invention will be described in detail based on a preferred embodiment shown in the accompanying drawings.

FIG. 1 is a partially cutaway schematic perspective view of an example of the acid gas separation module of the present invention. In the following description, the acid gas separation module is also simply referred to as a separation module.
As shown in FIG. 1, the separation module 10 basically includes a central cylinder 12, a laminate wound product 14 obtained by winding a laminate 14 a having an acidic gas separation membrane 20, a telescope prevention plate 16, and the like. It is comprised. The laminated body 14 a is a laminated body including the acidic gas separation membrane 20, the supply gas flow path member 24, and the permeate gas flow path member 26.
As an example, the separation module 10 separates carbon dioxide as an acidic gas Gc from a raw material gas G containing carbon monoxide, carbon dioxide (CO ₂ ), water (water vapor), and hydrogen.

The separation module 10 in the illustrated example is a so-called spiral type separation module. That is, the separation module 10 stacks a plurality of sheet-like laminates 14a, which will be described later, and winds the laminate around the central cylinder 12 to form a laminate wound product 14, whereby the laminate wound product 14 is obtained. The telescoping prevention plate 16 is provided through the central tube 12 on both end surfaces of the lens. That is, the laminate wound product 14 is a substantially cylindrical product formed by the laminate 14a that is laminated and wound.
The outermost peripheral surface of the wound laminate 14 a is covered with a gas impermeable coating layer 18.

  The separation module of the present invention is not limited to the spiral type as shown in the illustrated example, and may be a so-called flat plate type in which the sheet-like laminate 14a is maintained in a flat plate shape.

In such a separation module 10, the raw material gas G from which the acidic gas is separated passes through the opening 16 d of the telescope prevention plate 16 on the back side in FIG. It is supplied to the inside of the body 14a.
The source gas G supplied to the stacked body 14a is separated from the acidic gas Gc while flowing in the stacked body 14a.
The acidic gas Gc separated from the raw material gas G by the laminated body 14a is discharged from the central cylinder 12, and the raw material gas G from which the acidic gas has been separated (hereinafter referred to as residual gas Gr for convenience) It is discharged from the end surface opposite to the supply side of the wound product 14, and discharged to the outside of the separation module 10 through the opening 16 d of the telescope prevention plate 16.

The central cylinder (permeate gas collecting pipe) 12 is a cylindrical pipe whose end face on the source gas G supply side is closed, and a plurality of through holes 12a are formed on the peripheral surface (tube wall).
The acidic gas Gc separated from the raw material gas G passes through a permeating gas passage member 26 described later, reaches the inside of the central cylinder 12 from the through hole 12a, and is discharged from the open end 12b of the central cylinder 12.

In the center tube 12, the aperture ratio is preferably 1 to 80%, more preferably 1 to 75%, and further preferably 1.5 to 70%. Among these, from the practical viewpoint, the opening ratio of the center tube 12 is particularly preferably 1.5 to 25%. Specifically, the opening ratio of the central cylinder 12 is an area ratio of the through-holes 12 a occupying the outer peripheral surface of the central cylinder 12 in the formation region of the through-holes 12 a in the length direction of the central cylinder 12.
By setting the aperture ratio of the center tube 12 within the above range, the acid gas Gc can be efficiently collected, and the strength of the center tube 12 can be increased to ensure sufficient processability.

  The through hole 12a is preferably a circular hole having a diameter of 0.5 to 20 mm. Furthermore, it is preferable that the through holes 12 a are formed uniformly on the peripheral wall of the central cylinder 12.

The center tube 12 may be provided with a supply port (supply unit) for supplying a gas (sweep gas) for flowing the separated acidic gas Gc to the open end 12b side as necessary.
Furthermore, it is preferable that a slit (not shown) is provided in the tube wall of the central cylinder 12 along the axial direction. This slit will be described in detail later.

As described above, the laminate 14a is formed by laminating the acidic gas separation membrane 20, the supply gas flow path member 24, and the permeate gas flow path member 26.
In addition, the code | symbol 30 of FIG. 1 adhere | attaches the acidic gas separation membrane 20 and the member 26 for permeate gas flow paths, and also adhere | attaches the laminated bodies 14a, and the acid gas Gc in the member 26 for permeate gas flow paths. This is an adhesive layer 30 in which the flow path is in an envelope shape opened on the center tube 12 side.

As described above, the separation module 10 in the illustrated example is formed by stacking a plurality of the laminates 14 a and winding the laminate of the laminates 14 a around the central cylinder 12. 14
Hereinafter, for convenience, a direction corresponding to the winding of the laminated body 14a indicated by an arrow y in the drawing is a winding direction, and a direction orthogonal to the winding direction indicated by an arrow x in the drawing is a width direction.

In the separation module 10, the laminate 14a constituting the laminate wound product 14 may be one. However, by laminating and winding a plurality of laminated bodies 14a, the membrane area of the acidic gas separation membrane 20 can be increased, and the amount of acidic gas Gc separated by one separation module can be improved.
The number of stacked layers 14a may be appropriately set according to the processing speed and processing amount required for the separation module 10, the size of the separation module 10, and the like. Here, the number of laminated bodies 14a to be laminated is preferably 50 or less, more preferably 45 or less, and particularly preferably 40 or less. By setting the number of laminated bodies 14a to be this number, winding of the laminated body 14a around the central cylinder 12 becomes easy, and the workability can be improved.

In FIG. 2, the fragmentary sectional view of the laminated body 14a is shown. As described above, the arrow x is the width direction, and the arrow y is the winding direction.
In the illustrated example, as shown in FIG. 6 to be described later, the laminated body 14a has a supply gas flow path member 24 sandwiched between two folded acidic gas separation membranes 20 to form a sandwiching body 36. In addition, the permeate gas flow path member 26 is laminated. This configuration will be described in detail later.

As described above, in the separation module 10, the raw material gas G is supplied from one end face of the stacked body roll 14 through the opening 16 d of the telescope prevention plate 16. That is, the source gas G is supplied to the end portion (end surface) in the width direction (arrow x direction) of each stacked body 14a.
As conceptually shown in FIG. 2, the source gas G supplied to the end face in the width direction of the stacked body 14 a flows in the width direction through the supply gas flow path member 24. In this flow, the acidic gas Gc in contact with the acidic gas separation membrane 20 (facilitated transport membrane 20a) is separated from the source gas G by the carrier of the facilitated transport membrane 20a and transported in the stacking direction, and the acidic gas separation membrane. 20 passes in the stacking direction of the stacked body 14 a and flows into the permeating gas flow path member 26.
The acidic gas Gc that has flowed into the permeate gas flow path member 26 flows in the permeate gas flow path member 26 in the winding direction (the direction of the arrow y), reaches the central cylinder 12, and is centered from the through hole 12 a of the central cylinder 12. It flows into the cylinder 12. The acidic gas Gc that has flowed into the center tube 12 flows through the center tube 12 in the width direction and is discharged from the open end 12b.
Further, the residual gas Gr from which the acidic gas Gc has been removed flows in the width direction of the supply gas flow path member 24 and is discharged from the opposite end face of the laminate wound body 14. It is discharged to the outside of the separation module 10 through the part 16d.

The supply gas flow path member 24 is supplied with the source gas G from the end in the width direction, and brings the source gas G flowing in the member into contact with the acidic gas separation membrane 20.
Such a supply gas flow path member 24 functions as a spacer of the acid gas separation membrane 20 folded in half as described above, and constitutes a flow path for the source gas G. Further, the supply gas flow path member 24 preferably makes the source gas G turbulent. Considering this point, the supply gas flow path member 24 is preferably a member having a net shape (mesh shape / mesh structure), a woven fabric shape, a nonwoven fabric shape, a porous shape, or the like.

As a material for forming the supply gas flow path member 24, various materials can be used as long as they have sufficient heat resistance and moisture resistance.
Examples include paper materials such as paper, fine paper, coated paper, cast coated paper, and synthetic paper, resin materials such as cellulose, polyester, polyolefin, polyamide, polyimide, polysulfone, aramid, and polycarbonate, and inorganic materials such as metal, glass, and ceramics. A material etc. are illustrated suitably.
Specific examples of the resin material include polyethylene, polystyrene, polyethylene terephthalate, polytetrafluoroethylene (PTFE), polyethersulfone (PES), polyphenylene sulfide (PPS), polysulfone (PSF), polypropylene (PP), polyimide, Preferred examples include polyetherimide, polyetheretherketone, and polyvinylidene fluoride. A plurality of materials may be used in combination as the material for forming such a supply gas flow path member 24.

The thickness of the supply gas flow path member 24 may be appropriately determined according to the supply amount of the source gas G, the required processing capacity, and the like.
Specifically, 100 to 1000 μm is preferable, 150 to 950 μm is more preferable, and 200 to 900 μm is particularly preferable.

  In the separation module 10 of the present invention, the acidic gas separation membrane 20 includes a facilitated transport membrane 20a and a porous support 20b that supports the facilitated transport membrane 20a. Further, in the separation module 10 of the present invention, the acidic gas separation membrane 20 includes an intermediate layer 20c between the facilitated transport membrane 20a and the porous support 20b, a part of which is located in the porous support 20b. Have. In other words, the intermediate layer 20c is partially infiltrated into the porous support 20b.

The facilitated transport film 20a contains at least a carrier that reacts with the acidic gas Gc contained in the source gas G flowing through the supply gas flow path member 24, and a hydrophilic compound that supports the carrier. Such a facilitated transport film 20a has a function of selectively allowing the acidic gas Gc to permeate from the source gas G.
The porous support 20b substantially supports the facilitated transport film 20a.
The intermediate layer 20c is a layer for preventing carriers of the facilitated transport film 20a from being discharged from the facilitated transport film 20a and permeating through the porous support 20b.
The acidic gas separation membrane 20 including the facilitated transport membrane 20a, the porous support 20b, and the intermediate layer 20c will be described in detail later.

The permeating gas channel member 26 is a member for allowing the acidic gas Gc that has reacted with the carrier and permeated through the acidic gas separation membrane 20 to flow through the through hole 12a of the central cylinder 12.
As described above, in the illustrated example, the stacked body 14a has the sandwiching body 36 in which the acidic gas separation membrane 20 is folded in half with the facilitated transport membrane 20a inside, and the supply gas flow path member 24 is sandwiched.
By laminating the permeating gas flow path member 26 on the sandwiching body 36 and bonding them with the adhesive layer 30, one laminated body 14a is formed.
The permeating gas flow path member 26 functions as a spacer between the stacked bodies 14a and is separated from the source gas G that reaches the through hole 12a of the central cylinder 12 toward the winding center (inner side) of the stacked body 14a. The flow path of the acid gas Gc is configured. Further, in order to properly form the flow path of the acidic gas Gc, the adhesive layer 30 described later needs to penetrate. In consideration of this point, the permeating gas channel member 26 is preferably a net-like (mesh / net-like), woven fabric, non-woven fabric, porous material or the like, similar to the supply gas channel member 24. .

In the present invention, the laminated body 14a is not limited to the configuration using the sandwiching body 36 in which the supply gas flow path member 24 is sandwiched between the folded acidic gas separation membrane 20. For example, the laminated body may be configured in the same manner as the sandwiching body 36 by using the supply gas flow path member 24 attached to the surface of the acidic gas separation membrane 20.
6A, which will be described later, the supply gas flow path member 24 is folded back even when the separation membrane adhesive 20A formed by adhering two acidic gas separation membranes 20 is used. It may be sandwiched between the membrane sticking bodies 20A, or may be stuck to the separation membrane sticking bodies 20A.

  Various materials can be used as the material for forming the permeating gas channel member 26 as long as it has sufficient strength and heat resistance. Specifically, polyester-based materials such as epoxy-impregnated polyester, polyolefin-based materials such as polypropylene, fluorine-based materials such as polytetrafluoroethylene, inorganic materials such as metal, glass, and ceramics are preferably exemplified. . A plurality of materials may be used in combination as the material for forming such a permeating gas channel member 26. Further, a plurality of the same materials may be used.

The thickness of the permeating gas channel member 26 may be appropriately determined according to the supply amount of the raw material gas G, the required processing capacity, and the like.
Specifically, 100 to 1000 μm is preferable, 150 to 950 μm is more preferable, and 200 to 900 μm is particularly preferable.

As described above, the permeating gas channel member 26 is a channel for the acidic gas Gc that is separated from the source gas G and permeates the acidic gas separation membrane 20.
Therefore, it is preferable that the permeating gas channel member 26 has a low resistance to the flowing gas. Specifically, it is preferable that the porosity is high, the deformation is small when pressure is applied, and the pressure loss is small.

The porosity of the permeating gas channel member 26 is preferably 30 to 99%, more preferably 35 to 97.5%, and particularly preferably 40 to 95%.
Deformation when pressure is applied can be approximated by elongation when a tensile test is performed. The permeating gas channel member 26 preferably has an elongation of 5% or less and more preferably 4% or less when a load of 10 N / 10 mm width is applied.
The pressure loss can be approximated by a flow rate loss of compressed air that flows at a constant flow rate. The permeate gas channel member 26 has a flow rate loss of 7.5 L / min or less when air of 15 L (liter) / min is passed through the 15 cm square permeate gas channel member 26 at room temperature. Preferably, it is within 7 L / min.

The laminated body 14a is formed by laminating a supply gas flow path member 24, an acidic gas separation membrane 20, and a permeate gas flow path member 26.
As described above, the acidic gas separation membrane 20 includes the facilitated transport membrane 20a, the porous support 20b that substantially supports the facilitated transport membrane 20a, and the carrier of the facilitated transport membrane 20a is the porous support 20b. And an intermediate layer 20c that prevents the light from being transmitted therethrough.

Here, in the separation module 10 of the present invention, the intermediate layer 20c is located between the facilitated transport membrane 20a and the porous support 20b, and a support upper region located on the porous support 20b. And a permeation region inside the porous support 20b. Further, the intermediate layer 20c has a ratio “Tb / Ta” of the thickness Ta of the region on the support and the thickness Tb of the infiltrated region of 0.1 to 100 and a gas permeability of 500 Barrer or more. .
Hereinafter, the acidic gas separation membrane 20 in the separation module 10 of the present invention will be described in detail with reference to FIG.

As described above, the facilitated transport film 20a has a function of selectively allowing the acidic gas Gc to permeate from the source gas G. In other words, the facilitated transport film 20a has a function of selectively transporting the acidic gas Gc.
Such a facilitated transport film 20a contains at least a hydrophilic compound such as a hydrophilic polymer, a carrier that reacts with an acidic gas, water, and the like.

  The hydrophilic compound functions as a binder, retains moisture in the facilitated transport film 20a, and exhibits a function of separating an acidic gas such as carbon dioxide by the carrier. Moreover, it is preferable that a hydrophilic compound has a crosslinked structure from a heat resistant viewpoint.

From the viewpoint that the hydrophilic compound can be dissolved in water to form a coating composition, and the facilitated transport film 20a preferably has high hydrophilicity (moisturizing property), those having high hydrophilicity are preferable.
Specifically, the hydrophilic compound preferably has a hydrophilicity of 0.5 g / g or more in physiological saline, and has a hydrophilicity of 1 g / g or more in physiological saline. More preferably, the physiological saline has a hydrophilicity of 5 g / g or more, more preferably, the physiological saline has a hydrophilicity of 10 g / g or more, and the physiological saline has a hydrophilicity. Most preferably, the amount has a hydrophilicity of 20 g / g or more.

What is necessary is just to select the weight average molecular weight of a hydrophilic compound suitably in the range which can form a stable film | membrane. Specifically, 20,000 to 2,000,000 is preferable, 25,000 to 2,000,000 is more preferable, and 30,000 to 2,000,000 is particularly preferable.
By setting the weight average molecular weight of the hydrophilic compound to 20,000 or more, the facilitated transport film 20a having a stable and sufficient film strength can be obtained.
When the hydrophilic compound has a hydroxy group (—OH) as a crosslinkable group, the hydrophilic compound preferably has a weight average molecular weight of 30,000 or more. In this case, the weight average molecular weight is more preferably 40,000 or more, and more preferably 50,000 or more. When the hydrophilic compound has a hydroxy group as a crosslinkable group, the weight average molecular weight is preferably 6,000,000 or less from the viewpoint of production suitability.
In the case of having an amino group (—NH ₂ ) as a crosslinkable group, the hydrophilic compound preferably has a weight average molecular weight of 10,000 or more. In this case, the weight average molecular weight of the hydrophilic compound is more preferably 15,000 or more, and particularly preferably 20,000 or more. Moreover, when a hydrophilic compound has an amino group as a crosslinkable group, it is preferable that a weight average molecular weight is 1,000,000 or less from a viewpoint of manufacture aptitude.
For example, when polyvinyl alcohol (PVA) is used as the hydrophilic compound, the weight average molecular weight of the hydrophilic compound may be a value measured according to JIS K 6726. Moreover, when using a commercial item, what is necessary is just to use the molecular weight nominally mentioned in a catalog, a specification, etc.

As the crosslinkable group forming the hydrophilic compound, those capable of forming a hydrolysis-resistant crosslinked structure are preferably selected.
Specific examples include a hydroxy group, an amino group, a chlorine atom, a cyano group, a carboxy group, and an epoxy group. Among these, an amino group and a hydroxy group are preferably exemplified. Furthermore, most preferably, a hydroxy group is illustrated from the viewpoint of affinity with a carrier and a carrier carrying effect.

  Specific examples of the hydrophilic compound include those having a single crosslinkable group such as polyallylamine, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyethyleneimine, polyvinylamine, polyornithine, polylysine, Examples include polyethylene oxide, water-soluble cellulose, starch, alginic acid, chitin, polysulfonic acid, polyhydroxymethacrylate, poly-N-vinylacetamide and the like. Most preferred is polyvinyl alcohol. Moreover, as a hydrophilic compound, these copolymers are also illustrated.

Examples of the hydrophilic compound having a plurality of crosslinkable groups include polyvinyl alcohol-polyacrylic acid copolymers. A polyvinyl alcohol-polyacrylic salt copolymer is preferable because of its high water absorption ability and high hydrogel strength even at high water absorption.
The content of polyacrylic acid in the polyvinyl alcohol-polyacrylic acid copolymer is, for example, 1 to 95 mol%, preferably 2 to 70 mol%, more preferably 3 to 60 mol%, and particularly preferably 5 to 50 mol%. It is. The content of acrylic acid can be controlled by a known synthesis method.
In the polyvinyl alcohol-polyacrylic acid copolymer, the polyacrylic acid may be a salt. Examples of the polyacrylic acid salt in this case include ammonium salts and organic ammonium salts in addition to alkali metal salts such as sodium salts and potassium salts.

Polyvinyl alcohol is also available as a commercial product. Specific examples include PVA117 (manufactured by Kuraray Co., Ltd.), poval (manufactured by Kuraray), polyvinyl alcohol (manufactured by Aldrich), J-poval (manufactured by Nippon Vinegarten Poval). Although there are various molecular weight grades, those having a weight average molecular weight of 130,000 to 300,000 are preferred.
A polyvinyl alcohol-polyacrylate copolymer (sodium salt) is also available as a commercial product. For example, Crustomer AP20 (made by Kuraray Co., Ltd.) is exemplified.

  In the production method of the present invention, two or more hydrophilic compounds of the facilitated transport film 20a may be mixed and used.

In the formed facilitated transport film 20a, the content of the hydrophilic compound is appropriately determined depending on the type of the hydrophilic composition, the carrier, etc. , You can set.
Specifically, the content of the hydrophilic compound in the facilitated transport film 20a is preferably 0.5 to 50% by mass, more preferably 0.75 to 30% by mass, and particularly preferably 1 to 15% by mass. By setting the content of the hydrophilic compound within this range, the above-described function as a binder and moisture retention function can be stably and suitably expressed.

The crosslinked structure of the hydrophilic compound can be formed by a known method such as thermal crosslinking, ultraviolet crosslinking, electron beam crosslinking, radiation crosslinking, or photocrosslinking.
Photocrosslinking or thermal crosslinking is preferred, and thermal crosslinking is most preferred.

For the formation of the facilitated transport film 20a, it is preferable to use a crosslinking agent together with the hydrophilic composition. That is, the coating composition for forming the facilitated transport film 20a preferably contains a crosslinking agent.
As the crosslinking agent, one containing a crosslinking agent that reacts with a hydrophilic compound and has two or more functional groups capable of crosslinking such as thermal crosslinking or photocrosslinking is selected. The formed crosslinked structure is preferably a hydrolysis-resistant crosslinked structure.
From such a viewpoint, as a crosslinking agent added to the coating composition, an epoxy crosslinking agent, a polyvalent glycidyl ether, a polyhydric alcohol, a polyvalent isocyanate, a polyvalent aziridine, a haloepoxy compound, a polyvalent aldehyde, a polyvalent amine, An organic metal type crosslinking agent etc. are illustrated suitably. More preferred are polyvalent aldehydes, organometallic crosslinking agents and epoxy crosslinking agents, and among them, polyvalent aldehydes such as glutaraldehyde and formaldehyde having two or more aldehyde groups are preferred.

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. The epoxy crosslinking agent is also available as a commercial product, for example, trimethylolpropane triglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., Epolite 100MF, etc.), Nagase ChemteX Corporation EX-411, EX-313, EX-614B, Examples include EX-810, EX-811, EX-821, EX-830, NOF Corporation Epiol E400, and the like.
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.

  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 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 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. Examples include '-diethylene urea.

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.
Furthermore, examples of the organometallic crosslinking agent include organic titanium crosslinking agents and organic zirconia crosslinking agents.

For example, when polyvinyl alcohol having a weight average molecular weight of 130,000 or more is used as the hydrophilic compound, it is possible to form a crosslinked structure having good reactivity with this hydrophilic compound and excellent hydrolysis resistance. Therefore, an epoxy crosslinking agent or glutaraldehyde is preferably used as the crosslinking agent.
When a polyvinyl alcohol-polyacrylic acid copolymer is used as the hydrophilic compound, an epoxy crosslinking agent or glutaraldehyde is preferably used as the crosslinking agent.
When a polyallylamine having a weight average molecular weight of 10,000 or more is used as the hydrophilic compound, it is possible to form a crosslinked structure having good reactivity with this hydrophilic compound and excellent hydrolysis resistance. As the crosslinking agent, an epoxy crosslinking agent, glutaraldehyde, and an organometallic crosslinking agent are preferably used.
When polyethyleneimine or polyallylamine is used as the hydrophilic compound, an epoxy crosslinking agent is preferably used as the crosslinking agent.

What is necessary is just to set the quantity of a crosslinking agent suitably according to the kind of hydrophilic compound and crosslinking agent.
Specifically, the amount is preferably 0.001 to 80 parts by weight, more preferably 0.01 to 60 parts by weight, and particularly preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the crosslinkable group possessed by the hydrophilic compound. preferable. By setting the content of the cross-linking agent in the above range, a facilitated transport film having good cross-linking structure formation and excellent shape maintainability can be obtained.
Focusing on the crosslinkable group possessed by the hydrophilic compound, the crosslinked structure is preferably formed by reacting 0.001 to 80 mol of a crosslinking agent with respect to 100 mol of the crosslinkable group possessed by the hydrophilic compound.

  The facilitated transport film 20a preferably contains a metal element. One preferred embodiment of the facilitated transport film 20a includes an embodiment in which the facilitated transport film contains at least one metal element selected from the group consisting of Ti, Zr, Al, Si, and Zn. By including such a metal element, the strength of the facilitated transport film 20a is improved. In particular, as described later, the strength of the facilitated transport film 20a is further improved by forming a cross-linked structure containing the metal element, and as a result, the facilitated transport film 20a is deteriorated when wound in a spiral shape, for example. Is more suppressed.

The form of the facilitated transport film 20a containing such a metal element is not particularly limited, but a facilitated transport film containing a structural unit represented by the following formula (1) is preferable. In the following formula (1), * represents a bonding position.
Formula (1) M- (O- *) _m
In the above formula, M represents a metal element selected from the group consisting of Ti (titanium), Zr (zirconium), Al (aluminum), Si (silicon), and Zn (zinc).
m represents the valence of the metal element represented by M. For example, as shown below, m represents 2 when M is Zn, m represents 3 when M is Al, and m represents 4 when M is Ti, Zr, and Si. .
More specifically, structural formulas (formula (2) to formula (4)) when m is 2 to 4 are shown below.

The structural unit represented by the above formula (1) can be obtained by using a hydrolyzable compound and a hydrophilic compound having a crosslinkable group (for example, a hydroxy group) as described above, for example, as described later. It can be introduced into the facilitated transport film 20a. In that case, the structural unit functions as a so-called cross-linked site (cross-linked structure).
In addition, as a detection method of the structural unit represented by the said Formula (1) in the facilitated-transport film | membrane 20a, it can confirm by detecting a specific peak by IR measurement, for example. If necessary, after removing the carriers in the facilitated transport film 20a, IR measurement may be performed on the remaining film.

Although the total mass of the metal element in the facilitated transport film 20a is not particularly limited, the content of the metal element is 0.1 to 0.1% of the total mass of the hydrophilic compound in that the strength of the facilitated transport film 20a is more excellent. It is preferably 50% by mass, more preferably 0.3 to 20% by mass, and still more preferably 0.5 to 10% by mass.
Although the measuring method of content of the said metal element is not restrict | limited in particular, For example, it can measure by a fluorescent X ray analysis method.

As described above, when the structural unit represented by the above formula (1) is introduced into the facilitated transport film 20a, it is preferable to use a hydrolyzable compound containing the metal element described above. Specifically, the hydrolyzable metal compound represented by Formula (5) is mentioned. These compounds function as so-called organometallic crosslinking agents.
Formula (5) M (X) _m
In formula (5), M represents a metal element selected from the group consisting of Ti (titanium), Zr (zirconium), Al (aluminum), Si (silicon), and Zn (zinc).
X represents a hydrolyzable group. Examples of the hydrolyzable group include an alkoxyl group, an isocyanate group, a halogen atom such as a chlorine atom, an oxyhalogen group, an acetylacetonate group, and a hydroxy group. A plurality of X may be the same or different.
m represents the valence of the metal element represented by M.

In the facilitated transport film 20a, the carrier (acid gas carrier) reacts with an acid gas (for example, carbon dioxide gas (CO ₂ )) to transport the acid gas.

The carrier is a water-soluble compound having affinity with acidic gas and showing basicity. Specific examples include alkali metal compounds, nitrogen-containing compounds, and sulfur oxides.
The carrier may react indirectly with the acid gas, or the carrier itself may react directly with the acid gas.
The former reacts with other gas contained in the supply gas, shows basicity, and the basic compound reacts with acidic gas. More specifically, OH react with steam (water) ^- was released, the OH ^- that reacts with CO _2, a compound can be incorporated selectively CO ₂ in facilitated transport membrane 20a For example, an alkali metal compound.
The latter is such that the carrier itself is basic, for example, a nitrogen-containing compound or a sulfur oxide.

  Examples of the alkali metal compound include 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 invention, an alkali metal compound contains the salt and its ion other than alkali metal itself.

Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate.
Examples of the alkali metal bicarbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate.
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide.
Among these, alkali metal carbonates are preferable, and compounds having high solubility in water, potassium, rubidium, and cesium are preferable from the viewpoint of good affinity with acidic gas.

When using an alkali metal compound as a carrier, two or more kinds of carriers may be used in combination.
When two or more types of carriers are present in the facilitated transport film 20a, different carriers can be separated from each other in the film. Thereby, due to the difference in deliquescence of a plurality of carriers, due to the water absorption of the facilitated transport film 20a, the facilitated transport films 20a or the facilitated transport film 20a and other members are adhered to each other during production. (Blocking) can be suitably suppressed.
In the case where two or more alkali metal compounds are used as a carrier in terms of more suitably obtaining a blocking inhibitory effect, the first compound having deliquescence and the specific gravity having lower deliquescence than the first compound It is preferable to contain the 2nd compound with small. As an example, the first compound is exemplified by cesium carbonate, and the second compound is exemplified by potassium carbonate.

Nitrogen-containing compounds include amino acids such as glycine, alanine, serine, proline, histidine, taurine, diaminopropionic acid, hetero compounds such as pyridine, histidine, piperazine, imidazole, triazine, monoethanolamine, diethanolamine, triethanolamine , Alkanolamines such as monopropanolamine, dipropanolamine and tripropanolamine, cyclic polyetheramines such as cryptand [2.1] and cryptand [2.2], cryptand [2.2.1] and cryptand [ And bicyclic polyetheramines such as 2.2.2], porphyrin, phthalocyanine, ethylenediaminetetraacetic acid and the like.
Examples of sulfur compounds include amino acids such as cystine and cysteine, polythiophene, dodecyl thiol and the like.

What is necessary is just to set suitably content of the carrier in the facilitated-transport film | membrane 20a according to the kind etc. of a carrier or a hydrophilic compound. Specifically, the amount of the carrier in the facilitated transport film 20a is preferably 0.3 to 30% by mass, more preferably 0.5 to 25% by mass, and 1 to 20% by mass. Is particularly preferred.
By setting the content of the carrier in the coating composition in the above range, salting out before coating can be suitably prevented, and the facilitated transport film 20a formed can reliably exhibit the function of separating acidic gas. .
The amount ratio of the hydrophilic compound to the carrier in the coating composition is preferably 1: 9 to 2: 3 or less, more preferably 1: 4 to 2: 3 or less, and more preferably 3: 7 in terms of the hydrophilic compound: carrier mass ratio. ~ 2: 3 is particularly preferred.

The facilitated transport film 20a may contain a thickener as necessary. That is, the coating composition for forming the facilitated-transport film | membrane 20a may contain a thickener as needed.
As the thickener, for example, thickening polysaccharides such as agar, carboxymethylcellulose, carrageenan, chitansan gum, guar gum and pectin are preferable. Among these, carboxymethylcellulose is preferable from the viewpoints of film forming property, availability, and cost.
By using carboxymethyl cellulose, a coating composition having a desired viscosity can be easily obtained with a small amount of content, and at least a part of components other than the solvent contained in the coating composition cannot be dissolved in the coating composition. There is little risk of precipitation.

The content of the thickener is preferably as small as possible as long as it can be adjusted to the target viscosity.
As a general index, 10% by mass or less is preferable, 0.1 to 5% by mass is more preferable, and 0.1 to 2% by mass or less is more preferable.

  The facilitated transport film 20a (coating composition for forming the facilitated transport film 20a) contains various components as necessary in addition to such a hydrophilic compound, a crosslinking agent and a carrier, or a thickener. May be.

Examples of such components include an antioxidant such as dibutylhydroxytoluene (BHT), a compound having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms and a hydrophilic group, and a siloxane structure. Specific compounds such as compounds having a surfactant, surfactants such as sodium octoate and sodium 1-hexasulfonate, polymer particles such as polyolefin particles and polymethyl methacrylate particles, and the like.
In addition, a catalyst, a humectant, a hygroscopic agent, an auxiliary solvent, a film strength modifier, a defect detector, and the like may be used as necessary.

Further, in the separation module of the present invention, the thickness (thickness Tc) of the facilitated transport membrane 20a may be set appropriately according to the composition of the facilitated transport membrane 20a and the like to obtain the desired performance. Good. Specifically, 3-1000 μm is preferable, 5-500 μm is more preferable, and 5-100 μm is particularly preferable.
By making the film thickness of the facilitated-transport film | membrane 20a into the said range, it is preferable at points, such as being able to improve gas-permeation performance and suppressing generation | occurrence | production of a defect. The film thickness of the facilitated transport film 20a can be measured by cross-sectional observation using a scanning electron microscope or the like.

The porous support 20b (hereinafter also referred to as the support 20b) is permeable to an acidic gas such as carbon dioxide, and has an intermediate layer 20c formed on the support 20b and an acceleration formed on the intermediate layer 20c. It supports the transport film 20a.
As the support 20b, various known materials can be used as long as they have this function.

In the production method of the present invention, the support 20b may be a single layer. However, the support 20b preferably has a two-layer structure in which a porous film and an auxiliary support film are stacked. By having such a two-layer configuration, the above-described acidic gas permeability and the function of supporting the facilitated transport film 20a are more reliably expressed.
In the two-layer structure support 20b, the porous film serves as the formation surface of the intermediate layer 20c. That is, the porous membrane is on the facilitated transport membrane 20a side.
When the porous support is a single layer, various materials exemplified below as the porous film and the auxiliary support film can be used as the forming material.

The porous membrane is preferably made of a material having heat resistance and low hydrolyzability. Specific examples of such a porous membrane include membrane filter membranes such as polysulfone (PSF), polyethersulfone, polypropylene (PP) and cellulose, interfacially polymerized thin films of polyamide and polyimide, polytetrafluoroethylene (PTFE). And a stretched porous membrane of high molecular weight polyethylene.
Among them, a porous film containing one or more materials selected from fluorine-containing polymers such as PTFE, PP and PSF is preferably exemplified. Among them, a stretched porous membrane of PTFE or high molecular weight polyethylene has a high porosity, is small in inhibition of diffusion of acidic gas (especially carbon dioxide gas), and is preferable from the viewpoints of strength, suitability for manufacturing, and the like. In particular, a stretched porous membrane of PTFE is preferably used in terms of heat resistance and low hydrolyzability.

As the porous film, in addition to such an organic material, an inorganic material or an organic-inorganic hybrid material may be used.
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. There are no particular limitations on the type of ceramic, and various commonly used ceramics can be used. Examples of the ceramic include alumina, silica, silica-alumina, mullite, cordierite, and zirconia.
Further, a combination of two or more kinds of ceramics, a composite of ceramic and metal, or a composite of ceramic and organic compound may be used.

In the support 20b, the auxiliary support membrane is provided for reinforcing the porous membrane.
As the auxiliary support membrane, various materials can be used as long as they satisfy the required strength, stretch resistance and gas permeability. For example, a nonwoven fabric, a woven fabric, a net, and a mesh can be appropriately selected and used.

The auxiliary support membrane is also preferably made of a material having heat resistance and low hydrolyzability, like the porous membrane described above.
Considering this point, the fibers constituting the nonwoven fabric, woven fabric, and knitted fabric are excellent in durability and heat resistance, polyolefin such as polypropylene (PP), modified polyamide such as aramid (trade name), polytetrafluoro Fibers made of fluorine-containing resins such as ethylene and polyvinylidene fluoride are preferred. It is preferable to use the same material as the resin material constituting the mesh. Among these materials, a non-woven fabric made of PP that is inexpensive and has high mechanical strength is particularly preferably exemplified.

  When the support 20b has an auxiliary support film, the mechanical strength can be improved. Therefore, as will be described later, even when the acidic gas separation membrane 20 is formed by using so-called RtoR (roll to roll), it is possible to prevent wrinkles on the support 20b, and productivity. Can also be increased.

If the support 20b is too thin, the strength is difficult. Considering this point, the thickness of the porous membrane is preferably 5 to 100 μm, and the thickness of the auxiliary support membrane is preferably 50 to 300 μm.
When the support 20b is a single layer, the thickness of the support 20b is preferably 30 to 500 μm.

The maximum pore diameter of the porous film on which the intermediate layer 20c is formed is preferably 5 μm or less, more preferably 1 μm or less, and particularly preferably 0.3 μm or less. In addition, what is necessary is just to measure the largest hole diameter of a porous membrane with a palm porometer, for example.
The average pore diameter of the pores of the porous membrane is preferably 0.001 to 1 μm, and more preferably 0.001 to 0.3 μm.
By setting the maximum pore size and the average pore size of the porous membrane within this range, it is possible to improve the controllability of the penetration of the intermediate layer 20c described later, and it is preferable that the porous membrane hinders the passage of acid gas. It is possible to prevent the film surface from becoming non-uniform due to capillarity or the like when a silicone coating composition described later is applied.

As conceptually shown in FIG. 3, in the separation module 10 of the present invention, the acidic gas separation membrane 20 has an intermediate layer 20c between the support 20b and the facilitated transport membrane 20a.
The intermediate layer 20c has a support upper region on the support 20b and a permeation region in the support 20b. In other words, the intermediate layer 20c has a support upper region on the support 20b and a soaked region soaked in the support 20b.
In the intermediate layer 20c, the ratio “Tb / Ta” between the thickness Ta of the region on the support and the thickness Tb of the penetration region is 0.1 to 100. Furthermore, the intermediate layer 20c has a gas permeability of 500 Barrer or more.
In the separation module 10 of the present invention, the acidic gas separation membrane 20 has such an intermediate layer 20c, whereby the carrier flowing out from the facilitated transport membrane 20a is prevented from permeating the support 20b, and has durability. A good separation module can be obtained.

As described above, the facilitated transport membrane is in the form of a gel, and when the acidic gas is separated, the source gas G having a temperature of 100 to 130 ° C. and a humidity of about 90% is supplied at a pressure of about 1.5 MPa. As a result, the acidic gas separation membrane using the facilitated transport membrane gradually loses its ability to separate the acidic gas as the carrier gradually escapes from the facilitated transport membrane through the support 20b. Therefore, the acid gas module using the facilitated transport membrane cannot be said to have sufficient durability.
In addition, as described in Patent Document 2, it is also known to provide a carrier diffusion suppression layer for preventing the permeation of carriers between the porous support and the facilitated transport film. Depending on the nature, the carrier permeation has not been sufficiently suppressed.

On the other hand, the separation module 10 of the present invention includes an intermediate layer 20c in which the acid gas separation membrane 20 has soaked into the support 20b by a predetermined thickness and has a gas permeability of 500 Barrer or more. A facilitated transport film 20a is formed thereon.
Therefore, according to the present invention, the carrier that has escaped from the facilitated transport film 20a is prevented from permeating the support 20b, and the deterioration of the acid gas separation performance due to the escape of the carrier is suppressed. A separation module 10 can be obtained.

In the present invention, when the gas permeability of the intermediate layer 20c is less than 500 Barrer (1 Barrer = 1 × 10 ⁻¹⁰ cm ³ (STP) · cm / (sec · cm ² · cmHg)), the permeability of the acidic gas is reduced. Inconveniences such as failure to obtain desired separation performance occur.
The gas permeability of the intermediate layer 20c is preferably 700 Barrer or more, more preferably 1000 Barrer or more, in that the above disadvantage can be avoided more reliably.
In the present invention, the gas permeability of the intermediate layer 20c may be measured with the intermediate layer 20c formed on the support 20b.

In the present invention, the ratio “Tb / Ta” of the thickness of the intermediate layer 20c between the region on the support and the infiltrated region is 0.1 to 100. If the thickness ratio “Tb / Ta” is less than 0.1, the adhesiveness between the intermediate layer 20c and the support 20b is lowered, resulting in inconveniences such as a reduction in durability in a high-pressure process.
On the other hand, when the thickness ratio “Tb / Ta” exceeds 100, the film thickness of the intermediate layer 20c is actually increased, resulting in inconveniences such as a decrease in acid gas permeability.
The thickness ratio “Tb / Ta” is preferably 0.1 to 50, more preferably 0.1 to 10 in that the above inconvenience can be avoided more reliably.

The thickness Ta of the intermediate layer 20c on the support is preferably 0.1 to 10 μm.
By setting the thickness Ta to the above range, it is preferable in that the carrier diffusion can be suitably suppressed while maintaining the desired acidic gas separation performance.
Considering this point, the thickness Ta of the region on the support is more preferably 0.1 to 7 μm, and particularly preferably 0.1 to 4 μm.

On the other hand, the thickness Tb of the soaking area of the intermediate layer 20c is preferably 0.2 to 10 μm.
By making thickness Tb into the said range, it is preferable at points, such as ensuring desired durability, suppressing the fall of acidic gas permeability.
Considering this point, the thickness Tb of the soaking area is more preferably 0.2 to 5 μm, and particularly preferably 0.2 to 3 μm.

The thickness of the intermediate layer 20c (that is, Ta + Tb) is preferably 0.5 to 15 μm.
By setting the thickness of the intermediate layer 20c within the above range, it is possible to suppress the occurrence of defects in the process of manufacturing the separation module 10 described later, and to obtain desired separation performance while suppressing a decrease in acid gas permeability. Is preferable.
Considering this point, the thickness of the intermediate layer 20c is more preferably 0.5 to 10 μm, and particularly preferably 0.5 to 5 μm.

In the separation module 10 of the present invention, the acid gas separation membrane 20 has a ratio “Tc / (Ta + Tb)” of the thickness Tc of the facilitated transport membrane 20a and the thickness Ta + Tb of the intermediate layer 20c is 0.3. It is preferably ~ 500.
As described above, the thickness Tc of the facilitated transport film 20a is preferably 3 to 1000 μm.

As will be described later, the separation module 10 produces a sandwiching body 36 in which the supply gas flow path member 24 is sandwiched by the acidic gas separation membrane 20 that is folded in half with the facilitated transport membrane 20a on the inside. The laminated body 14a in which the gas flow path member 26 is laminated is produced by winding. During this winding, the facilitated transport film 20a and the supply gas flow path member 24 may come into sliding contact with each other, and the facilitated transport film 20a may be damaged. Here, the damage due to the sliding contact is likely to be affected by the hardness of the intermediate layer 20c which is the base of the facilitated transport film 20a. On the other hand, by setting the facilitated transport film 20a to a certain thickness or more with respect to the intermediate layer 20c, the facilitated transport film 20a caused by the sliding contact between the facilitated transport film 20a and the supply gas flow path member 24 is achieved. Damage can be suppressed. Specifically, by setting the thickness ratio “Tc / (Ta + Tb)” to 0.3 or more, the facilitated transport film 20a resulting from the sliding contact between the facilitated transport film 20a and the supply gas flow path member 24 is achieved. Damage can be suppressed.
On the other hand, when the facilitated transport film 20a is thicker than the intermediate layer 20c, the effective membrane area for one module tends to decrease due to a decrease in permeation performance and an increase in film thickness. On the other hand, by setting the ratio of thickness “Tc / (Ta + Tb)” to 500 or less, the reduction of the effective membrane area is suppressed, and the facilitated transport membrane 20a is effectively used, so that the separation efficiency of acid gas A good separation module can be obtained.

  Considering the above points, the ratio “Tc / (Ta + Tb)” between the thickness Tc of the facilitated transport film 20a and the thickness Ta + Tb of the intermediate layer 20c is more preferably 1 to 500, and particularly preferably 2 to 200.

The intermediate layer 20c can be formed of various materials.
Specifically, the intermediate layer 20c preferably has a functional group that reacts with a hydroxyl group and / or a carboxyl group. More specifically, the intermediate layer 20c preferably contains a compound having at least one of an epoxy group, an amino group, a methoxy group, an ethoxy group, a hydroxyl group, and a carboxyl group as a main component.

As an example of the intermediate layer 20c, a layer made of a compound having a silicone bond or a silicone-containing compound is exemplified. Specifically, silicone-containing polyacetylene such as organopolysiloxane (silicone resin) and polytrimethylsilylpropyne can be used. Specific examples of the organopolysiloxane include those represented by the following general formula.
In the above general formula, n represents an integer of 1 or more. Here, from the viewpoints of availability, volatility, viscosity, and the like, the average value of n is preferably in the range of 10 to 1000000, and more preferably in the range of 100 to 100,000.
R _1n , R _2n , R ₃ and R ₄ are each selected from the group consisting of a hydrogen atom, alkyl group, vinyl group, aralkyl group, aryl group, hydroxyl group, amino group, carboxyl group and epoxy group. Indicates either. Note that n R _1n and R _2n may be the same or different. Further, the alkyl group, aralkyl group and aryl group may have a ring structure. Further, the alkyl group, vinyl group, aralkyl group and aryl group may have a substituent, and the substituent in this case is, for example, an alkyl group, a vinyl group, an aryl group, a hydroxyl group, an amino group, a carboxyl group. Selected from a group, an epoxy group and a fluorine atom. These substituents may further have a substituent, if possible.
The alkyl group, vinyl group, aralkyl group and aryl group selected from R _1n , R _2n , R ₃ and R ₄ are each an alkyl group having 1 to 20 carbon atoms, a vinyl group, or a carbon number from the viewpoint of availability. A 7-20 aralkyl group and a C6-C20 aryl group are more preferable.

R _1n , R _2n , R ₃ and R ₄ are preferably methyl groups or epoxy-substituted alkyl groups. For example, PDMS derivatives such as epoxy-modified polydimethylsiloxane (PDMS) can be suitably used.

  Further, as the intermediate layer 20c, in addition to the above organopolysiloxane, silicone materials such as poly [1- (trimethylsilyl) -1-propyne] (PTMSP), butadiene-based / isoprene-based rubber materials, low-density polymethyl A layer made of pentene or the like can also be used.

In the separation module 10 of the present invention, the acidic gas separation membrane 20 preferably has a protective layer on the surface, that is, the facilitated transport membrane 20a.
As described above, when the separation module 10 winds the laminate 14a in which the sandwiched body 36 formed by the acidic gas separation membrane 20 and the supply gas flow path member 24 and the permeate gas flow path member 26 are wound, The facilitated transport film 20a may be damaged by the sliding contact between the facilitated transport film 20a and the supply gas flow path member 24.
On the other hand, by having a protective layer on the surface of the acidic gas separation membrane 20, the facilitated transport membrane 20a is prevented by the sliding contact between the facilitated transport membrane 20a and the supply gas flow path member 24, and more acidic. A separation module 10 having excellent gas separation performance can be obtained.

  Various materials can be used as the material for forming the protective layer, and various compounds exemplified in the intermediate layer 20c are preferably used. In particular, like the intermediate layer 20c, the PDMS derivative is preferably exemplified.

What is necessary is just to set the thickness of a protective layer suitably according to the characteristic of the facilitated-transport film | membrane 20a, the characteristic of the member 24 for supply gas flow paths, etc. Specifically, 0.1 to 500 μm is preferable, and 0.5 to 100 μm is more preferable.
Setting the thickness of the protective layer in the above range is preferable in that the facilitated transport film 20a can be suitably protected while suppressing a decrease in gas permeability due to the presence of the protective layer.

Such an acidic gas separation membrane 20 may be produced by various known methods. Preferably, it is produced by a coating method using RtoR.
As is well known, RtoR means that a substrate is delivered from a roll formed by winding a long substrate (object to be processed) and conveyed in the longitudinal direction, and the coating composition is applied and dried. It is a manufacturing method which winds up the board | substrate in roll shape.

When the acidic gas separation membrane 20 is produced, a roll formed by winding a long support 20b is loaded into an apparatus for forming the intermediate layer 20c, and the support is sent out from the roll. The coating composition to be the intermediate layer 20c is applied while being conveyed in the longitudinal direction.
Here, the conveyance speed of the support 20b is preferably faster from the viewpoint of productivity. However, in order to apply | coat a coating composition uniformly, 3-200 m / min is preferable, 5-150 m / min is more preferable, and 10-120 m / min is especially preferable.

  The coating composition to be the intermediate layer 20c includes monomers, dimers, trimers, oligomers, prepolymers, and mixtures of the compounds to be the intermediate layer 20c such as the above-described PDMS derivatives, curing agents, curing accelerators, and crosslinking agents. , A general coating used when a resin layer (resin film) is formed by a coating method in which a thickener, a reinforcing agent, a filler, and the like are dissolved and / or dispersed in an organic solvent. It is a composition (coating liquid / paint). Such a coating composition may be prepared by a known method.

As described above, the support 20b is a porous body. Therefore, when the coating composition to be the intermediate layer 20c is coated on the support 20b, the coating composition gradually soaks into the support 20b (porous film). Thereby, the intermediate | middle layer 20c which has the penetration area | region in the support body 20b, and the area | region on a support body on the support body 20b can be formed.
Further, the viscosity of the coating composition to be the intermediate layer 20c, the maximum pore size and average pore size of the support 20b (porous film), the time from application of the coating composition to curing, the coating amount of the coating composition, etc. By appropriately controlling the intermediate layer 20c, the thickness ratio “Tb / Ta” between the region on the support and the penetration region can satisfy 0.1 to 100.

  The coating amount of the coating composition to be the intermediate layer 20c depends on the characteristics of the support 20b (such as the maximum pore diameter), the conveyance speed of the support 20b, the thickness of the intermediate layer 20c, the viscosity concentration of the coating composition, etc. By performing simulations and experiments, etc., the amount by which the thickness Ta of the region on the support, the thickness Tb of the soaked region, and the like become target values may be set as appropriate.

Here, the coating composition to be the intermediate layer 20c preferably has a viscosity at 25 ° C. of 100 cp or more.
By setting the viscosity at 25 ° C. of the coating composition to be the intermediate layer 20c to 100 cp or more, the amount of coating composition soaked into the support 20b can be controlled appropriately, and the thickness Ta of the region on the support can be soaked. The intermediate layer 20c having a ratio “Tb / Ta” to the region thickness Tb of 0.1 to 100 can be stably formed.
Considering this point, the viscosity at 25 ° C. of the coating composition to be the intermediate layer 20c is more preferably 400 cp or more, and particularly preferably 500 cp or more.
Therefore, it is preferable to apply the coating composition to be the intermediate layer 20c at room temperature, or it is preferable to apply the coating composition at a temperature at which the viscosity is 100 cp or more.

  On the other hand, what is necessary is just to set the upper limit of the viscosity in 25 degreeC of the coating composition used as the intermediate | middle layer 20c according to the limit viscosity in the coating device to be used. Specifically, the upper limit of the viscosity at 25 ° C. of the coating composition to be the intermediate layer 20c is 1 in that the thickness of the intermediate layer 20c and the amount of penetration into the support 20b can be suitably controlled. 1,000,000 cp or less is preferable.

  In addition, what is necessary is just to measure the viscosity of the coating composition used as the intermediate | middle layer 20c at 25 degreeC in the rotation speed of 60 rpm by a B-type viscosity meter according to JISZ8803.

  Various known coating devices for the silicone coating composition can be used as the coating composition coating device to be the intermediate layer 20c. In particular, a roll coater, a direct gravure coater, an offset gravure coater, a 1 roll kiss coater, a 3 reverse roll coater, a forward rotation roll coater, a squeeze coater, a reverse roll coater and the like are preferably exemplified.

  If the coating composition used as the intermediate layer 20c is applied, the coating composition is then dried. The drying may be performed by a known method such as hot air drying or drying with a heater.

After the coating composition to be the intermediate layer 20c is dried, the coating composition is then cured to form the intermediate layer 20c.
For curing, a method capable of curing, such as heat curing, ultraviolet irradiation, electron beam irradiation, or the like, may be appropriately selected according to the forming material of the intermediate layer 20c. Here, for the reason that curling and deformation of the support 20b can be suppressed and deterioration of the resin constituting the support 20b can be prevented, curing of the coating composition by ultraviolet irradiation or short heating is preferably used. Is done. In particular, curing by ultraviolet irradiation is most preferably used. That is, in the present invention, it is preferable to form the intermediate layer 20c with a coating composition using a monomer or the like that can be cured by irradiation with ultraviolet rays.

Curing of the coating composition to be the intermediate layer 20c is preferably performed within 7 seconds after the coating composition is applied.
When the coating composition to be the intermediate layer 20c is applied to the support 20b, the coating composition gradually soaks into the support 20b. That is, the thickness Tb of the soaking area is increased.
On the other hand, by curing the coating composition to be the intermediate layer 20c within 7 seconds after coating the coating composition, the amount of the coating composition soaked into the support 20b is appropriately controlled. The intermediate layer 20c in which the ratio “Tb / Ta” of the thickness Ta of the region on the support and the thickness Tb of the penetration region is 0.1 to 100 can be stably formed.

Depending on the composition of the coating composition to be the intermediate layer 20c, the coating composition may be dried and cured at the same time.
Moreover, you may perform drying and / or hardening of a coating composition in inert atmosphere, such as nitrogen atmosphere, as needed.

  When the intermediate layer 20c is formed on the support 20b in this manner, the support 20b on which the intermediate layer 20c is formed is wound into a roll.

  In addition, the protective layer formed on the facilitated-transport film | membrane 20a can be fundamentally formed similarly to the intermediate | middle layer 20c.

  Next, the roll of the support 20b (hereinafter also referred to as a composite) on which the intermediate layer 20c is formed is loaded into the forming device for the facilitated transport film 20a, and the composite is sent out from the roll and conveyed in the longitudinal direction. A coating composition to be the facilitated transport film 20a is applied.

What is necessary is just to set suitably the conveyance speed of the composite_body | complex at the time of forming the facilitated-transport film | membrane 20a according to a composition, a viscosity, etc. of a coating composition.
Here, when the conveyance speed of the composite is too fast, there is a fear that the coating film thickness uniformity of the coating composition is lowered and drying of the coating composition is insufficient, and when it is too slow, the productivity is lowered. In consideration of this point, the conveyance speed of the composite is preferably 0.5 m / min or more, more preferably 0.75 to 200 m / min, and particularly preferably 1 to 200 m / min.

As described above, the facilitated transport film 20a contains a hydrophilic compound such as a hydrophilic polymer, a carrier that reacts with an acidic gas, water, and the like.
Accordingly, the coating composition (coating liquid / paint) for forming such a facilitated transport film 20a includes the above-described hydrophilic compound, carrier and water, or further a necessary composition such as a crosslinking agent. It is a thing. The water may be room temperature water or warm water.
The hydrophilic compound may be crosslinked, partially crosslinked, or uncrosslinked, or a mixture of these. This coating composition may also be prepared by a known method.

The coating composition to be the facilitated transport film 20a preferably has a viscosity at 25 ° C. of 100 cp or more.
By setting the viscosity at 25 ° C. of the coating composition to 100 cp or more, it is preferable from the standpoint that repelling at the time of applying the coating composition can be suppressed, and uniformity of coating of the coating composition can be improved.
In addition, what is necessary is just to measure a viscosity similarly to the coating composition used as the intermediate | middle layer 20c.

  For the application of the coating composition to be the facilitated transport film 20a, various known materials can be used, and the same materials as those for the intermediate layer 20c described above are exemplified. In consideration of the preferable viscosity of the coating composition to be the facilitated transport film 20a, the coating amount of the coating composition, and the like, a roll coater, a bar coater, a positive rotation roll coater, a knife coater, and the like are preferably used.

If the coating composition used as the facilitated-transport film | membrane 20a is apply | coated, then this applied composition is dried and the facilitated-transport film | membrane 20a is formed.
Various known methods for drying by removing water, such as warm air drying or drying by heating the support 20b, can be used as the drying method.
When performing warm air drying, the speed of the warm air may be set as appropriate so that the coating composition can be dried quickly and the coating film (gel film) of the coating composition does not collapse. Specifically, 0.5 to 200 m / min is preferable, 0.75 to 200 m / min is more preferable, and 1 to 200 m / min is particularly preferable.
Further, the temperature of the hot air may be appropriately set at a temperature at which the support 20b is not deformed and the coating composition can be dried quickly. Specifically, the film surface temperature is preferably 1 to 120 ° C, more preferably 2 to 115 ° C, and particularly preferably 3 to 110 ° C.

When drying the facilitated transport film 20a by heating the support 20b, the temperature at which the support 20b is not deformed and the coating composition can be quickly dried may be appropriately set. Moreover, you may use blowing of dry air together with the heating of the support body 20b.
Specifically, drying of the facilitated transport film 20a by heating the support 20b is preferably performed at a temperature of the support 20b of 60 to 120 ° C, more preferably 60 to 90 ° C, and more preferably 70 to 80 ° C. It is particularly preferable to carry out as In this case, the film surface temperature is preferably 15 to 80 ° C, and more preferably 30 to 70 ° C.

  When the coating composition is dried to produce the facilitated transport membrane 20a, that is, the acidic gas separation membrane 20, the acidic gas separation membrane 20 is wound into a roll.

In the above example, the support 20b on which the intermediate layer 20c is formed is wound up once, and the support 20b on which the intermediate layer 20c is formed is sent out from this roll to form the facilitated transport film 20a.
However, in addition to this, the support 20b on which the intermediate layer 20c is formed is not wound up, but is transported in the longitudinal direction as it is, and the facilitated transport film 20a is formed to produce the acid gas separation membrane 20 and wind it up Good.

In the present invention, the acidic gas separation membrane 20 thus produced may be used as it is, and the separation module 10 (laminated body 14a and laminated body 14) may be produced as will be described later.
Alternatively, two acidic gas separation membranes 20 are prepared, and the two acidic gas separation membranes 20 are laminated and adhered with the facilitated transport membrane 20a facing each other as shown in FIG. Then, the separation membrane sticking body 20A is manufactured, and using this separation membrane sticking body 20A, the separation module 10 (laminate 14a and laminate roll 14) is produced in the same manner as the acidic gas separation membrane 20. May be.
As described above, the facilitated transport film 20a is a gel-like film and has adhesiveness, so that the two acidic gas separation membranes 20 are adhered with a sufficient adhesion force. Thereby, also when winding the laminated body 14a mentioned later, the facilitated-transport film | membrane 20a is not rubbed. Furthermore, in the separation membrane sticking body 20A in which the two acidic gas separation membranes 20 are stuck in this way, the facilitated transport membrane 20a contacts only the other facilitated transport membrane 20a and the support 20b.
Therefore, according to this configuration, when the laminated body 14a including the separation membrane sticking body 20A, the supply gas flow path member 24, and the permeate gas flow path member 26 is spirally wound, the facilitated transport film 20a is It is possible to suitably prevent damage.

In such a separation membrane sticking body 20A, both the acidic gas separation membranes 20 may have the intermediate layer 20c.
However, when the pressure is applied from the support 20b side, the intermediate layer 20c that prevents the carrier from escaping to the support 20b due to the pressurization is not necessary. Accordingly, in consideration of pressure loss and the like, in the separation membrane sticking body 20A obtained by sticking the two acid gas separation membranes 20, when the intermediate layer 20c is the laminated body 14a, the supply gas flow path is used. It is preferably provided only on the acidic gas separation membrane 20 on the side away from the member 24.

What is necessary is just to produce the separation membrane sticking body 20A formed by sticking the two acid gas separation membranes 20 using the lamination | stacking and sticking method of a well-known sheet-like material.
For example, when the acidic gas separation membrane 20 is produced by RtoR as described above, similarly, the separation membrane sticking body 20A may be produced by a known method using RtoR. Specifically, two separation membrane rolls 20R are produced as described above. As shown conceptually in FIG. 4B, the two separation membrane rolls 20R are mounted at predetermined positions of a known laminating apparatus. The separation membrane roll 20R is mounted so that the facilitated transport membranes 20a of the acidic gas separation membranes 20 sent out from the separation membrane rolls 20R face each other.
Next, the acid gas separation membrane 20 is sent out from each separation membrane roll 20R, inserted through a predetermined path passing through the guide roller 50, the lamination roller pair 52, and the conveyance roller pair 54, and the tip ends of the two acid gas separation membranes 20 are inserted. Then, it is wound around the winding shaft 56.

When the above preparation is completed, the acidic gas separation membrane 20 is sent out from each separation membrane roll 20R, guided to a predetermined conveyance path by the guide roller 50 or the like, and conveyed in the longitudinal direction, while the facilitated transport membrane is formed by the laminated roller pair 52. Two acidic gas separation membranes 20 are laminated and pasted with 20a facing each other to form a separation membrane stuck body 20A.
Furthermore, the produced separation membrane sticking body 20A is guided to a predetermined transport path by the transport roller pair 54, wound by the take-up shaft 56, and the separation membrane sticking body 20A is wound in a roll shape. The body roll is 20AR.

In this case, the conveying speed of the acidic gas separation membrane 20 and the like is preferably higher in terms of productivity and the like, but may be appropriately set according to the strength and the like of the acidic gas separation membrane 20.
Further, as described above, since the facilitated transport film 20a has adhesiveness, it is basically not necessary to use an adhesive member such as an adhesive or a pressure-sensitive adhesive when the acidic gas separation film 20 is attached.

Here, in the manufacturing method of this invention, when producing 20 A of separation membrane sticking bodies, it is preferable to pressurize the two acid gas separation membranes 20 bonded together. Thereby, the sticking force of the two acidic gas separation membranes 20 (facilitated transport membrane 20a) can be further improved.
What is necessary is just to set a pressurizing force suitably according to the kind, thickness, etc. of the facilitated-transport film | membrane 20a. Specifically, the applied pressure is preferably 10 to 500 kPa, and more preferably 100 to 300 kPa.
By setting the applied pressure within this range, the adhesive force of the two acidic gas separation membranes 20 can be improved, and the displacement between the facilitated transport membranes 20a during winding described later can be more suitably prevented. Is preferable.

Pressurization of the bonded acidic gas separation membrane 20 (separation membrane sticking body 20A) may be performed by a known method using a pressure roller, a press device, or the like.
For example, when the separation membrane sticking body 20 </ b> A is manufactured by RtoR as described above, the pressure may be applied when the two acidic gas separation membranes 20 are stuck by the laminated roller pair 52. Or you may provide one or more pressure rollers in the conveyance path | route of 20 A of separation membrane sticking bodies, such as making the conveyance roller pair 54 into a pressure roller pair. Or you may use together the pressurization by the lamination | stacking roller pair 52, and the pressurization by a pressurization roller.
Moreover, when performing this pressurization, you may perform heating, humidification, etc. of the acidic gas separation membrane 20 and / or the separation membrane sticking body 20A as needed. These processes may be performed by a known method such as a method of heating the laminated roller pair 52.

In the separation membrane sticking body 20A, the total film thickness of the two facilitated transport membranes 20a by the two acidic gas separation membranes 20 is such that the desired performance can be obtained according to the composition of the facilitated transport membrane 20a. It can be set as appropriate.
Specifically, 5-1000 micrometers is preferable and 10-500 micrometers is more preferable.

Further, the two acidic gas separation membranes 20 constituting the separation membrane sticking body 20A may have the same or different thicknesses of the facilitated transport membrane 20a. The two acid gas separation membranes 20 may have the same or different thickness and / or configuration of the support 20b.
Further, the two acidic gas separation membranes 20 constituting the separation membrane sticking body 20A may have the same or different facilitated transport membranes 20a.

Hereinafter, in the separation module 10, a method for producing the laminated body 14 a including the acidic gas separation membrane 20, the supply gas flow path member 24 and the permeate gas flow path member 26, and a winding method of the laminated body 14 a, that is, lamination A method for producing the wound body 14 will be described.
In addition, also when using the above-mentioned separation membrane sticking body 20A instead of the acidic gas separation membrane 20, the laminated body 14a may be similarly produced and the laminated body wound material 14 may be produced.
In FIGS. 5A to 9 used in the following description, the supply gas flow path member 24 and the permeate gas flow path member 26 have end faces (end portions) in order to simplify the drawings and clearly show the configuration. Only the net is shown.

First, as conceptually shown in FIGS. 5 (A) and 5 (B), the extending direction of the central cylinder 12 and the short direction coincide with each other, and a fixing means 34 such as an adhesive is attached to the central cylinder 12. Is used to fix the end of the permeating gas flow path member 26.
Here, as described above, it is preferable that the tube wall of the center tube 12 is provided with a slit (not shown) along the axial direction. In this case, a distal end portion of a permeating gas channel member 26 to be described later is inserted into the slit, and is fixed to the inner peripheral surface of the center tube 12 by fixing means. According to this configuration, when the laminated body including the permeating gas channel member 26 is wound around the central tube 12, the inner peripheral surface of the central tube 12 and the permeating gas channel Friction with the member 26 can prevent the permeate gas flow path member 26 from coming out of the slit, that is, the permeate gas flow path member 26 is fixed.

On the other hand, as conceptually shown in FIG. 6, the acidic gas separation membrane 20 (separation membrane adhering body 20A) produced as described above is folded in half with the facilitated transport membrane 20a inside, and the supply gas flow The road member 24 is sandwiched. That is, a sandwiching body 36 is produced in which the supply gas flow path member 24 is sandwiched between the acidic gas separation membranes 20 folded in half (or the separation membrane sticking body in which the supply gas flow path member 24 is folded in half). A sandwiching body 36A is sandwiched between 20A). In this case, the acidic gas separation membrane 20 is not equally folded in half, but is folded in half so that one is slightly longer as shown in FIG.
Further, in order to prevent the facilitated transport membrane 20a from being damaged by the supply gas flow path member 24, a sheet-like protective member (for example, Kapton tape) folded in half at the trough portion where the acidic gas separation membrane 20 is folded in half. Etc.) are preferably arranged.

In addition, when utilizing the separation membrane sticking body 20A which stuck two sheets of facilitated-transport films | membranes 20, as above-mentioned, it is preferable to form the intermediate | middle layer 20c only in one acidic gas separation membrane 20. As shown in FIG. .
In this case, the separation membrane sticking body is provided so that the acidic gas separation membrane 20 having the intermediate layer 20c is separated from the supply gas flow path member 24 rather than the acidic gas separation membrane 20 having no intermediate layer 20c. It is preferable to fold 20A in half and sandwich the supply gas channel member 24 therebetween.

Further, an adhesive 30a to be the adhesive layer 30 is applied to the shorter surface of the acid gas separation membrane 20 folded in half (the surface of the support 20b).
Here, as shown in FIG. 6, the adhesive 30a (adhesive layer 30) extends in the vicinity of both ends in the width direction (arrow x direction) and extends in the entire winding direction (arrow y direction). Furthermore, it is applied to the entire region in the width direction in the vicinity of the end portion opposite to the folded portion, and is applied in a band shape.

  Next, as conceptually shown in FIGS. 7A and 7B, the surface coated with the adhesive 30a is directed to the permeating gas flow path member 26, and the folded side is directed to the central cylinder 12. The sandwiching body 36 (sandwiching body 36A) is laminated on the permeate gas flow path member 26 fixed to the central cylinder 12, and the permeate gas flow path member 26 and the acidic gas separation membrane 20 (support 20b) are bonded. .

Further, as shown in FIGS. 7A and 7B, an adhesive 30a to be the adhesive layer 30 is applied to the upper surface (the surface of the longer support 20b) of the sandwiched sandwich 36. In the following description, the direction opposite to the permeating gas flow path member 26 first fixed to the central cylinder 12 by the fixing means 34 (upper side in the drawing) is also referred to as the upper side.
As shown in FIGS. 7 (A) and 7 (B), the adhesive 30a on this surface is also applied in the form of a belt extending in the entire area in the winding direction in the vicinity of both ends in the width direction, as before. Furthermore, it extends in the entire region in the width direction in the vicinity of the end opposite to the folded portion and is applied in a band shape.

Next, as conceptually shown in FIG. 8, the permeate gas flow path member 26 is laminated on the sandwiched body 36 coated with the adhesive 30a, and the acidic gas separation membrane 20 (support 20b) and the permeate gas flow are laminated. The road member 26 is bonded to form the laminated body 14a.
Note that a plurality of permeate gas channel members 26 may be used as necessary.

Next, as shown in FIG. 6, as shown in FIG. 6, a sandwiching body 36 in which the supply gas flow path member 24 is sandwiched between the acidic gas separation membranes 20 is produced, and an adhesive 30 a that becomes the adhesive layer 30 is applied. The permeated gas flow path member 26 and the sandwiching body 36 that are finally stacked are stacked and bonded with the side to which the adhesive is applied facing down.
Further, similarly to the above, an adhesive 30a is applied to the upper surface of the laminated sandwiching body 36 as shown in FIGS. 7A and 7B, and then, as shown in FIG. Then, the permeating gas flow path member 26 is laminated and bonded, and the second layered body 14a is laminated.

The following steps of FIGS. 6 to 8 are repeated to stack a predetermined number of stacked bodies 14a as conceptually shown in FIG.
As shown in FIG. 9, it is preferable that the laminated body 14a is laminated so that the laminated body 14a is gradually separated from the central tube 12 in the winding direction as it goes upward. Thereby, the laminated body 14a is easily wound around the central cylinder 12, and the end of the permeate gas flow path member 26 on the central cylinder 12 side or the vicinity of the end is preferably in contact with the central cylinder 12. it can.

When the predetermined number of the laminated bodies 14a are laminated, as shown in FIG. 9, the central cylinder 12 on the upper surface of the permeating gas flow path member 26, which is first fixed to the central cylinder 12 with the adhesive 38a on the outer peripheral surface of the central cylinder 12. The adhesive 38b is applied between the sandwiching body 36 and the adhesive 36b.
Next, as shown by an arrow yw in FIG. 9, the stacked body 14 a is wound around the central cylinder 12 so as to wind the stacked stacked body 14 a.
When the winding is completed, the permeate gas passage member 26 on the outermost periphery is maintained for a predetermined time in a state where tension is applied in the pulling-out direction, that is, the direction of squeezing and the adhesive 30a and the like are dried. The outermost permeating gas channel member 26 is the lowermost permeating gas channel member 26 fixed to the central cylinder 12 first.
When a predetermined time has elapsed, the outermost permeate gas channel member 26 is fixed by ultrasonic welding or the like at a position where it has made one round, and the excess permeate gas channel member 26 outside the fixed position is cut. Thus, the laminated body 14 is obtained by winding the laminated body 14a around the central cylinder.

  As described above, the raw material gas G is supplied from the end of the supply gas flow path member 24, and the acidic gas Gc passes through the acidic gas separation membrane 20 by being transported in the stacking direction, and passes through the permeated gas flow. It flows into the road member 26, flows through the permeate gas flow path member 26, and reaches the central cylinder 12.

Here, the adhesive 30a is applied to the support 20b, and the adhesive 30a is bonded to the net-shaped permeating gas channel member 26. Therefore, the adhesive 30a penetrates (impregnates) the support 20b and the permeating gas flow path member 26, and the adhesive layer 30 is formed inside of both.
Further, as described above, the adhesive layer 30 (adhesive 30a) is formed in a strip shape extending in the entire vicinity in the winding direction in the vicinity of both ends in the width direction. Further, the adhesive layer 30 extends across the entire width direction in the vicinity of the end portion on the side opposite to the folded portion on the central tube 12 side so as to cross the adhesive layer 30 in the vicinity of both ends in the width direction in the width direction. Then, it is formed in a band shape. That is, the adhesive layer 30 is formed so as to surround the outer peripheries of the permeating gas flow path member 26 and the support 20b by opening the central tube 12 side. In addition, the permeating gas channel member 26 is sandwiched between the facilitated transport films 20a.
As a result, an envelope-like flow path that opens on the side of the central tube 12 is formed in the permeating gas flow path member 26 of the laminate 14a. Therefore, the acidic gas Gc that has passed through the acidic gas separation membrane 20 and has flowed into the permeate gas flow path member 26 flows through the permeate gas flow path member 26 toward the central cylinder 12 without flowing out, It flows into the center tube 12 from the through hole 12a.
That is, the adhesive layer 30 acts not only for bonding but also as a sealing portion for sealing the acidic gas Gc to a predetermined channel in the permeating gas channel member 26 and the like.

In the separation module 10 of the present invention, various known adhesives can be used as long as the adhesive layer 30 (adhesive 30a) has sufficient adhesive strength, heat resistance, and moisture resistance.
Examples include epoxy resins, vinyl chloride copolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinylidene chloride copolymers, vinyl chloride-acrylonitrile copolymers, butadiene-acrylonitrile copolymers, polyamide resins, polyvinyl butyral. Suitable examples include polyesters, cellulose derivatives (nitrocellulose, etc.), styrene-butadiene copolymers, various synthetic rubber resins, phenol resins, urea resins, melamine resins, phenoxy resins, silicone resins, urea formamide resins, and the like. .

  The adhesive 30a to be the adhesive layer 30 may be applied once, but preferably, an adhesive diluted with an organic solvent such as acetone is applied first, and only the adhesive is applied thereon. preferable. In this case, the adhesive diluted with an organic solvent is preferably applied in a wide width, and the adhesive is preferably applied in a narrower width.

Further, in the separation module 10, when the support 20b is a laminate of the porous membrane and the auxiliary support membrane described above, the peripheral portion, that is, the adhesive layer 30 forming portion, in the stacking direction of the support 20b. In addition, the adhesive is soaked into the porous film at a penetration rate of 10% or more, and the auxiliary protective membrane is provided with a membrane protection portion in which the penetration rate of the adhesive is smaller than the penetration rate into the porous membrane. preferable.
By having such a membrane protection part, when the acidic gas separation membrane 20 is incorporated into the separation module 10 and used for use, stress concentration occurs and the facilitated transport membrane 20a is easily damaged. In addition, the occurrence of defects can be suppressed, and when a defect occurs, the permeation of the supply gas can be suppressed, so that a decrease in the separation performance of the separation module 10 can be suppressed.
The film protection part can be formed with various known adhesives as long as it has heat resistance and moisture resistance. Specifically, various examples are exemplified for the adhesive layer 30 described above.
As an example, the film protection part may be formed by applying an adhesive having a low viscosity by addition of a solvent or the like to the porous support film of the support 20b prior to the formation of the adhesive layer 30.
The width of the membrane protection part may be appropriately set according to the size of the separation module 10 and the like, but is preferably 20 mm or more, and more preferably 40 mm or more.

In the separation module 10 of the present invention, a telescope prevention plate (telescope prevention member) 16 is disposed at both ends of the laminated body 14 produced in this way.
As described above, the telescope prevention plate 16 is so-called that the laminated body 14 is pressed by the raw material gas G, the supply-side end surface is pushed in a nested manner, and the opposite-side end surface protrudes in a nested manner. It is a member for preventing the telescope phenomenon.

In the present invention, as the telescoping prevention plate 16, various known types used for spiral type separation modules can be used.
In the illustrated example, the telescope prevention plate includes an annular outer ring portion 16a, an annular inner ring portion 16b arranged in the outer ring portion 16a so as to coincide with the center, an outer ring portion 16a and an inner ring. And a rib (spoke) 16c for connecting and fixing the portion 16b. The central cylinder 12 around which the laminate in which the laminate 14a is laminated is wound passes through the inner ring portion 16b.
In the illustrated example, the ribs 16c are provided radially at equal angular intervals from the center of the outer ring part 16a and the inner ring part 16b, and between the outer ring part 16a and the inner ring part 16b and each rib 16c. Is an opening 16d through which the source gas G or the residual gas Gr passes.

The telescoping prevention plate 16 may be disposed in contact with the end face of the laminated body 14.
However, in order to use the entire end face of the laminate wound product 14 for supplying the source gas and discharging the residual gas Gr, there is a slight gap between the telescope prevention plate 16 and the end face of the laminate wound article 14. Are preferably arranged.

Various materials having sufficient strength, heat resistance and moisture resistance can be used as the material for forming the telescope prevention plate 16.
Specifically, a metal material, a resin material, ceramics, etc. are illustrated suitably.
Examples of the metal material include stainless steel (SUS), aluminum, aluminum alloy, tin, and tin alloy.
Examples of the resin material include polyethylene resin, polypropylene resin, aromatic polyamide resin, nylon 12, nylon 66, polysulfin resin, polytetrafluoroethylene resin, polycarbonate resin, acrylic / butadiene / styrene resin, acrylic / ethylene / styrene resin, Examples include epoxy resins, nitrile resins, polyether ether ketone resins (PEEK), polyacetal resins (POM), polyphenylene sulfide (PPS), and the like. Examples of the resin material include fiber reinforced plastics of these resins. Examples of the fibers include glass fibers, carbon fibers, stainless steel fibers, and aramid fibers, and long fibers are particularly preferable. More specifically, examples of the fiber reinforced plastic include long glass fiber reinforced polypropylene and long glass fiber reinforced polyphenylene sulfide.
Examples of ceramics include zeolite and alumina.

The covering layer 18 covers the peripheral surface of the laminated body 14 and blocks the discharge of the raw material gas G and the residual gas Gr from outside the peripheral surface, that is, the end surface of the laminated body 14. It is.
The covering layer 18 may be provided to cover not only the peripheral surface of the laminated body 14 but also the telescope prevention plate as necessary.

As the coating layer 18, various materials that can shield the raw material gas G and the like can be used. The covering layer 18 may be a cylindrical member or may be configured by winding a wire or a sheet-like member.
As an example, the FRP wire is impregnated with the adhesive used for the adhesive layer 30 described above, and the wire impregnated with the adhesive is laminated in multiple layers as necessary without gaps. The coating layer 18 wound around is illustrated. There are no limitations on the fiber or matrix resin used in FRP. As an example, 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, and an epoxy resin is preferable from the viewpoint of heat resistance and hydrolysis resistance.
In this case, if necessary, a sheet shape such as a Kapton tape for preventing penetration of the adhesive into the laminated body 14 between the coating layer 18 and the laminated body 14. A member may be provided.

  The acid gas separation module of the present invention has been described in detail above. However, the present invention is not limited to the above-described example, and various improvements and modifications may be made without departing from the gist of the present invention. Of course.

  Hereinafter, the specific example of this invention is given and the acidic gas separation module of this invention is demonstrated in detail.

[Example 1]
<Preparation of coating composition (1) to be facilitated transport film 20a>
An aqueous solution containing 3.3% by mass of a polyvinyl alcohol-polyacrylic acid copolymer (Clastomer AP-20 manufactured by Kuraray Co., Ltd.) and 0.016% by mass of a crosslinking agent (25% by mass glutaraldehyde aqueous solution manufactured by Wako Pure Chemical Industries, Ltd.). Prepared. To this aqueous solution, 1 M hydrochloric acid was added until the pH reached 1.7 to cause crosslinking.
After crosslinking, a 40% aqueous cesium carbonate solution (manufactured by Rare Metals) was added so that the concentration of cesium carbonate was 6.0% by mass. That is, in this example, cesium carbonate serves as a carrier for the facilitated transport film 20a.
Further, 0.004% by mass of a surfactant (1% by mass of Lapisol A-90 manufactured by NOF Corporation) was added to prepare a coating composition (1) to be the facilitated transport film 20a.

<Preparation of coating composition to be intermediate layer 20c>
Polymerizable polydimethylsiloxane (UV9300, manufactured by Momentive Performance) 20% by mass and 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate (I0591, manufactured by Tokyo Chemical Industry Co., Ltd.) 0.1% by mass The coating composition used as the intermediate | middle layer 20c was prepared.
The viscosity of the coating composition at 25 ° C. was 300 cP.

<Production of acid gas separation membrane>
<< Formation of Intermediate Layer >>
As the support 20b, a support roll formed by winding a long laminate (manufactured by GE), which is formed by laminating a porous film on the surface of a PP nonwoven fabric, was prepared. This porous membrane is porous PTFE.
A general film forming apparatus that has a coating apparatus (roll coater), a drying apparatus, and an ultraviolet irradiation apparatus and that forms a film by a coating method using RtoR is loaded with this support roll, and the support 20b is placed in a predetermined transport path. The tip was wound around a take-up shaft. In addition, the previously prepared coating composition to be the intermediate layer 20c was filled in the material tank of the coating means.
With this film forming apparatus, the coating composition that becomes the intermediate layer 20c is applied by the coating apparatus while the support 20b is conveyed in the longitudinal direction, the coating composition is dried by the drying apparatus, and the coating set is cured by the ultraviolet irradiation apparatus. And the intermediate | middle layer 20c was formed in the support body 20b, and it wound in roll shape.
Application | coating of the coating composition was performed at normal temperature. The ultraviolet irradiation was performed so that the coating composition was cured in 2 seconds after the coating composition was applied. The relationship between the curing time of the coating composition and the ultraviolet irradiation conditions (irradiation time and ultraviolet intensity) was previously examined by experiments.

The intermediate layer 20c thus formed had a thickness Ta of the support upper region of 0.5 μm, a penetration region thickness Tb of 2 μm, and a thickness ratio “Tb / Ta” of 4.
The relationship between the viscosity of the coating composition to be the intermediate layer 20c, the time from application to curing of the coating composition, the thickness Ta of the region on the support and the thickness Tb of the soaking region, and the coating composition The relationship between the coating amount and the thickness of the intermediate layer 20c was previously examined by experiments.

The gas permeability of this intermediate layer 20c was measured and found to be 750 Barrer.
The gas permeability (Barrer) of the intermediate layer 20c is measured by supplying a measurement gas to the support 20b on which the intermediate layer 20c is formed, analyzing the permeated gas with a gas chromatograph, evaluating the permeation performance (GPU), and then SEM. -It calculated from the product with the film thickness of the intermediate | middle layer 20c measured from the EDX analysis. As the measurement gas, a mixed gas of N ₂ : CO ₂ : H ₂ O = 66: 21: 13 (partial pressure ratio) was used. The measurement gas was supplied to the support 20b under the conditions of a flow rate of 0.32 L / min, a temperature of 130 ° C., and a total pressure of 2001.3 kPa.

<< Formation of facilitated transport film 20a >>
A support roll and a roll formed by winding the support 20b on which the intermediate layer 20c was formed were removed from the film forming apparatus in which the intermediate layer 20c was formed on the support 20b.
A general film forming apparatus that has a coating apparatus (roll coater) and a drying apparatus and forms a film by a coating method using RtoR is loaded with a roll formed by winding the support 20b on which the intermediate layer 20c is formed. The support 20b on which the intermediate layer 20c was formed was inserted through a predetermined transport path, and the tip was wound around the winding shaft. Moreover, the coating composition (1) which becomes the facilitated-transport film | membrane 20a prepared previously was filled into the material tank of the coating device.
Next, the coating composition (1) is applied by the coating apparatus while the support 20b is transported in the longitudinal direction by the film forming apparatus, and the coating composition (1) is dried by the drying apparatus, whereby the intermediate layer 20c. By forming the facilitated transport membrane 20a on the substrate, the acidic gas separation membrane 20 having the support 20b, the intermediate layer 20c and the facilitated transport membrane 20a as shown in FIG. 3 was prepared and wound into a roll shape. .
The coating composition (1) was applied so that the facilitated transport film 20a formed by drying had a thickness of 20 μm (Tc = 20 μm). Therefore, the thickness ratio “Tc / (Ta + Tb)” is 8. In addition, the relationship between the coating amount (coating film thickness) of the coating composition (1) and the thickness of the facilitated transport film 20a to be formed was examined in advance by experiments.

<Production of separation module>
First, as shown in FIGS. 5A and 5B, a permeating gas flow path member 26 was fixed to the center tube 12 made of SUS. As the permeating gas channel member 26, a 100-mesh stainless steel wire mesh (wire diameter: 0.1 mm, aperture: 0.154 mm) was used. As the fixing means 34, an adhesive capable of adhering SUS was used.

On the other hand, the produced acidic gas separation membrane 20 was cut into a predetermined length and folded in half with the facilitated transport membrane 20a inside. As shown in FIG. 6, the two folds were performed so that one acidic gas separation membrane 20 was slightly longer. Kapton tape was applied to the trough of the acid gas separation membrane 20 folded in half, and the end of the supply gas flow path member 24 was reinforced so as not to damage the trough of the facilitated transport membrane 20a.
Subsequently, the supply gas flow path member 24 was sandwiched between the folded acidic gas separation membranes 20 to produce a sandwiching body 36. As the supply gas flow path member 24, a PP net having a thickness of 0.5 mm was used.

As shown in FIG. 6, on the porous support 20b side where the acidic gas separation membrane 20 of the sandwiching body 36 is short, in the vicinity of both ends in the width direction (arrow x direction), the winding direction (arrow y direction). The adhesive 30a was applied to the entire region in the width direction in the vicinity of the end portion on the side opposite to the folded portion in the winding direction. As the adhesive 30a, an adhesive made of an epoxy resin (E120HP manufactured by Henkel Japan) was used.
Next, with the side to which the adhesive 30a is applied facing downward, as shown in FIGS. 7A and 7B, the sandwiching body 36 and the permeating gas channel member 26 fixed to the central cylinder 12 are provided. Laminated and glued.
Then, on the upper surface of the acidic gas separation membrane 20 of the sandwiching body 36 laminated on the permeating gas flow path member 26, as shown in FIGS. The adhesive 30a was applied so as to extend over the entire region in the width direction and in the vicinity of the end portion on the opposite side of the folded portion in the winding direction. Further, as shown in FIG. 8, a permeate gas flow path member 26 is laminated on the acidic gas separation membrane 20 coated with the adhesive 30a and bonded to form the first layered product 14a. did.

In the same manner as described above, another sandwiching body 36 shown in FIG. 6 was produced, and similarly, the adhesive 30a was similarly applied to the porous support 20b side of the short acid gas separation membrane 20. Next, in the same manner as in FIGS. 7A and 7B, the side to which the adhesive 30 a is applied is directed toward the first layered body 14 a (the permeate gas flow path member 26) formed first, The sandwiching body 36 was laminated on the first layered body 14a (permeating gas flow path member 26) and adhered. Further, an adhesive 30a is applied to the upper surface of the sandwiching body 36 in the same manner as in FIGS. 7A and 7B, and a permeating gas flow path member 26 is laminated thereon, as in FIG. Then, the second layered product 14a was formed by bonding.
Further, in the same manner as the second layer, the third layered body 14a was formed on the second layered body 14a.

After laminating the three-layered laminate 14a on the permeate gas flow path member 26 fixed to the central cylinder 12, an adhesive 38a is applied to the peripheral surface of the central cylinder 12, as shown in FIG. The adhesive 38b was applied on the permeating gas flow path member 26 between the central cylinder 12 and the lowermost layered laminate 14a. The adhesives 38a and 38b were the same as the adhesive 30a.
Next, by rotating the central cylinder 12 in the direction of the arrow yw in FIG. 9, the laminated body 14 a having three layers was wound around the central cylinder 12 in a multiple manner so as to be a laminated body 14.

The center tube 12 is inserted into the inner ring portion 16b and the telescoping prevention plate 16 having a thickness of 2 cm as shown in FIG. . The telescope prevention plate 16 was made of PPS containing 40% by mass of glass fiber. The distance between the telescope prevention plate 16 and the laminate wound product 14 was 1 mm.
Furthermore, the coating layer 18 was formed by winding the FRP resin tape around the peripheral surface of the telescope prevention plate 16 and the peripheral surface of the laminated body 14 to produce the separation module 10. The membrane area of the prepared separation module 10 was 1.2 m ² (design value) in total.
In addition, the separation module 10 produced five similar things.

[Example 2]
An acidic gas separation membrane 20 was formed in the same manner as in Example 1 except that the coating amount of the coating composition to be the intermediate layer 20c and the time until curing were changed.
In addition, the thickness Ta of the region on the support of the intermediate layer 20c was 2 μm, and the thickness Tb of the soaking region was 0.2 μm. Therefore, the thickness ratio “Tb / Ta” is 0.1, and the thickness ratio “Tc / (Ta + Tb)” is 9.09.
When measured in the same manner as in Example 1, the gas permeability of the intermediate layer 20c was 570 Barrer.
Using this acidic gas separation membrane 20, a separation module 10 was produced in the same manner as in Example 1.

[Example 3]
The acidic gas separation membrane 20 is the same as in Example 1, except that the coating amount of the coating composition to be the intermediate layer 20c and the time until curing are changed and the thickness of the facilitated transport membrane 20a is 350 μm. Formed.
The thickness Ta of the region on the support of the intermediate layer 20c was 2 μm, and the thickness Tb of the soaking region was 0.2 μm. Therefore, the thickness ratio “Tb / Ta” is 0.1, and the thickness ratio “Tc / (Ta + Tb)” is 159.
When measured in the same manner as in Example 1, the gas permeability of the intermediate layer 20c was 570 Barrer.
Using this acidic gas separation membrane 20, a separation module 10 was produced in the same manner as in Example 1.

[Example 4]
The acidic gas separation membrane 20 was changed in the same manner as in Example 1 except that the coating amount of the coating composition to be the intermediate layer 20c and the time until curing were changed and the thickness of the facilitated transport membrane 20a was changed to 950 μm. Formed.
The thickness Ta of the region on the support of the intermediate layer 20c was 2 μm, and the thickness Tb of the soaking region was 0.2 μm. Therefore, the thickness ratio “Tb / Ta” is 0.1, and the thickness ratio “Tc / (Ta + Tb)” is 432.
When measured in the same manner as in Example 1, the gas permeability of the intermediate layer 20c was 570 Barrer.
Using this acidic gas separation membrane 20, a separation module 10 was produced in the same manner as in Example 1.

[Example 5]
An acidic gas separation membrane 20 was formed in the same manner as in Example 1 except that the coating amount of the coating composition to be the intermediate layer 20c and the time until curing were changed.
The thickness Ta of the intermediate layer 20c on the support was 0.1 μm, and the thickness Tb of the soaking area was 9 μm. Therefore, the thickness ratio “Tb / Ta” is 90, and the thickness ratio “Tc / (Ta + Tb)” is 2.2.
When measured in the same manner as in Example 1, the gas permeability of the intermediate layer 20c was 1000 Barrer.
Using this acidic gas separation membrane 20, a separation module 10 was produced in the same manner as in Example 1.

[Example 6]
Acid gas separation was carried out in the same manner as in Example 1 except that the coating amount of the coating composition to be the intermediate layer 20c and the time until curing were changed and the thickness of the facilitated transport film 20a was 2.5 μm. A film 20 was formed.
The thickness Ta of the intermediate layer 20c on the support was 0.1 μm, and the thickness Tb of the soaking area was 9 μm. Accordingly, the thickness ratio “Tb / Ta” is 90, and the thickness ratio “Tc / (Ta + Tb)” is 0.27.
When measured in the same manner as in Example 1, the gas permeability of the intermediate layer 20c was 1000 Barrer.
Using this acidic gas separation membrane 20, a separation module 10 was produced in the same manner as in Example 1.

[Example 7]
An acidic gas separation membrane 20 was formed in the same manner as in Example 1 except that the thickness of the facilitated transport membrane 20a was 70 μm.
Accordingly, the thickness Ta of the intermediate layer 20c on the support is 0.5 μm, the penetration area thickness Tb is 2 μm, the thickness ratio “Tb / Ta” is 4, and the thickness ratio “Tc / (Ta + Tb). ) ”Is 8, and the gas permeability of the intermediate layer 20c is 750 Barrer.
Using this acidic gas separation membrane 20, a separation module 10 was produced in the same manner as in Example 1.

[Example 8]
A coating composition to be the intermediate layer 20c was prepared in the same manner as in Example 1 except that KF-102 manufactured by Shin-Etsu Chemical Co., Ltd. was used as the polymerizable polydimethylsiloxane. The viscosity of this coating composition at 25 ° C. was 4000 cP.
An acidic gas separation membrane 20 was formed in the same manner as in Example 1 except that the intermediate layer 20c was formed using this coating composition.
The thickness Ta of the intermediate layer 20c on the support was 2.3 μm, and the thickness Tb of the soaking area was 0.6 μm. Therefore, the thickness ratio “Tb / Ta” is 0.26, and the thickness ratio “Tc / (Ta + Tb)” is 6.9.
When measured in the same manner as in Example 1, the gas permeability of the intermediate layer 20c was 620 Barrer.
Using this acidic gas separation membrane 20, a separation module 10 was produced in the same manner as in Example 1.

[Example 9]
The acidic gas separation membrane 20 was used in the same manner as in Example 2 except that a coating layer having a thickness of 3 μm was formed on the facilitated transport membrane 20a in the same manner as the intermediate layer 20c using the coating composition to be the intermediate layer 20c. Formed.
Therefore, the thickness Ta of the intermediate layer 20c on the support is 2 μm, the penetration area thickness Tb is 0.2 μm, the thickness ratio “Tb / Ta” is 0.1, and the thickness ratio “Tc / ( Ta + Tb) ”is 9.09, and the gas permeability of the intermediate layer 20c is 570 Barrer.

[Example 10]
To an aqueous solution (copolymer concentration: 4.3% by mass) containing polyvinyl alcohol (PVA) -polyacrylic acid copolymer (PAA) (molar ratio: PVA / PAA = 3/7), 40% by mass cesium carbonate ( A rare aqueous metal) aqueous solution was added so that the concentration of cesium carbonate was 6.0% by mass. Further, ORGATICS TC-100 (manufactured by Matsumoto Fine Chemical Co., Ltd.), which is a Ti-based cross-linking agent, is added so as to have a ratio of 10% by mass with respect to the PVA-PAA copolymer, and the mixture is stirred and degassed. A product (2) was prepared.
The PVA-PAA copolymer is described in “T. Sato, et al. (1993). Synthesis of poly (vinyl alcohol) having a thiol group at one end and new block copolymers containing poly (vinyl alcohol) as one cinsistent. Macromolecular Chemistry and Physics, 194, 175-185 ”.
An acidic gas separation membrane 20 was formed in the same manner as in Example 8, except that the facilitated transport membrane 20a was formed using the coating composition (2) instead of the coating composition (1).
Therefore, the thickness Ta of the region on the support of the intermediate layer 20c is 2.3 μm, the thickness Tb of the soaking region is 0.6 μm, the thickness ratio “Tb / Ta” is 0.26, and the thickness ratio “ Tc / (Ta + Tb) ”is 6.9, and the gas permeability of the intermediate layer 20c is 620 Barrer.
Using this acidic gas separation membrane 20, a separation module 10 was produced in the same manner as in Example 1.
The facilitated transport film 20a of the separation module 10 includes a structural unit in which M in Formula (1) is Ti. When the Ti content in the facilitated transport film was measured by fluorescent X-ray analysis, the Ti content was 1.1% by mass relative to the PVA-PAA copolymer that is a hydrophilic compound. In addition, Ti content in the facilitated-transport film | membrane by a fluorescent X ray analysis method was measured by analyzing and quantifying in the measurement area 10mmphi using Primusell (Rh ray source) made from Rigaku.

[Example 11]
In the coating composition (2), acidity was determined in the same manner as in Example 10 except that Olgatics TC-100 (manufactured by Matsumoto Fine Chemical Co., Ltd.) was added to 1% by mass with respect to the PVA-PAA copolymer. A gas separation membrane 20 was formed.
Therefore, the thickness Ta of the region on the support of the intermediate layer 20c is 2.3 μm, the thickness Tb of the soaking region is 0.6 μm, the thickness ratio “Tb / Ta” is 0.26, and the thickness ratio “ Tc / (Ta + Tb) ”is 6.9, and the gas permeability of the intermediate layer 20c is 620 Barrer.
Using this acidic gas separation membrane 20, a separation module 10 was produced in the same manner as in Example 1.
In the same manner as in Example 10, the Ti content of the facilitated transport film 20a was measured. As a result, Ti content was 0.11 mass% with respect to the PVA-PAA copolymer which is a hydrophilic compound.

[Example 12]
In the coating composition (2), acidity was determined in the same manner as in Example 10 except that Olgatics TC-100 (manufactured by Matsumoto Fine Chemical Co., Ltd.) was added so as to be 50% by mass with respect to the PVA-PAA copolymer. A gas separation membrane 20 was formed.
Therefore, the thickness Ta of the region on the support of the intermediate layer 20c is 2.3 μm, the thickness Tb of the soaking region is 0.6 μm, the thickness ratio “Tb / Ta” is 0.26, and the thickness ratio “ Tc / (Ta + Tb) ”is 6.9, and the gas permeability of the intermediate layer 20c is 620 Barrer.
Using this acidic gas separation membrane 20, a separation module 10 was produced in the same manner as in Example 1.
In the same manner as in Example 10, the Ti content of the facilitated transport film 20a was measured. As a result, Ti content was 5.3 mass% with respect to the PVA-PAA copolymer which is a hydrophilic compound.

[Example 13]
In the coating composition (2), ORGATICS TC-401 (manufactured by Matsumoto Fine Chemical Co.) was used instead of ORGATICS TC-100 (manufactured by Matsumoto Fine Chemical Co., Ltd.), and the amount was 15% by mass with respect to the PVA-PAA copolymer. An acidic gas separation membrane 20 was formed in the same manner as in Example 10 except that the addition was performed.
Therefore, the thickness Ta of the region on the support of the intermediate layer 20c is 2.3 μm, the thickness Tb of the soaking region is 0.6 μm, the thickness ratio “Tb / Ta” is 0.26, and the thickness ratio “ Tc / (Ta + Tb) ”is 6.9, and the gas permeability of the intermediate layer 20c is 620 Barrer.
Using this acidic gas separation membrane 20, a separation module 10 was produced in the same manner as in Example 1.
In the same manner as in Example 10, the Ti content in the facilitated transport film 20a was measured. As a result, Ti content was 1 mass% with respect to the PVA-PAA copolymer which is a hydrophilic compound.

[Example 14]
An acidic gas separation membrane 20 was formed in the same manner as in Example 5 except that the coating composition (2) was used instead of the coating composition (1).
Therefore, the thickness Ta of the intermediate layer 20c on the support is 0.1 μm, the penetration area thickness Tb is 9 μm, the thickness ratio “Tb / Ta” is 90, and the thickness ratio “Tc / (Ta + Tb). ) ”Is 2.2, and the gas permeability of the intermediate layer 20c is 1000 Barrer.
Using this acidic gas separation membrane 20, a separation module 10 was produced in the same manner as in Example 1.

[Example 15]
An acidic gas separation membrane 20 was formed in the same manner as in Example 9 except that the coating composition (2) was used instead of the coating composition (1).
Accordingly, the thickness Ta of the intermediate layer 20c on the support is 2 μm, the thickness Tb of the soaking area is 0.2 μm, the thickness ratio “Tb / Ta” is 0.1, and the thickness ratio “Tc / (Ta + Tb) ”is 9.09, and the gas permeability of the intermediate layer 20c is 570 Barrer.
Using this acidic gas separation membrane 20, a separation module 10 was produced in the same manner as in Example 1.

[Example 16]
<Production of acid gas separation membrane>
A laminated body in which a 10 μm thick porous film (porous PTFE, average pore diameter 0.15 μm) is laminated on the surface of a 200 μm thick PP nonwoven fabric is used as the support 20b, and the intermediate layer 20c is formed in the same manner as in Example 8. In addition, an acidic gas separation membrane 20 was produced in the same manner as in Example 1 except that the same coating composition (2) as in Example 10 was used to form the facilitated transport membrane 20a.
The thickness Ta of the intermediate layer 20c on the support was 2.3 μm, and the thickness Tb of the soaking area was 0.6 μm. Therefore, the thickness ratio “Tb / Ta” is 0.26, and the thickness ratio “Tc / (Ta + Tb)” is 6.9. Further, when measured in the same manner as in Example 1, the gas permeability of the intermediate layer 20c was 620 Barrer.
Separately, a laminated body in which a 10 μm thick porous film (porous PTFE, average pore diameter of 0.15 μm) is laminated on the surface of a 200 μm thick PP nonwoven fabric is used as the support 20b. In addition, an acid gas separation membrane 20 was produced in the same manner as in Example 1 except that the facilitated transport membrane 20a was formed using the same coating composition (2) as in Example 10. That is, the acidic gas separation membrane 20 does not have the intermediate layer 20c.
As shown in Example 1 described above, the acidic gas separation membrane 20 is manufactured using RtoR. Therefore, in this example, the separation membrane roll 20R formed by winding the acidic gas separation membrane 20 having the intermediate layer 20c, and the separation membrane roll 20R formed by winding the acidic gas separation membrane 20 not having the intermediate layer 20c, The two separation membrane rolls 20R were prepared.

<Preparation of Separation Membrane Paste 20A>
The two separation membrane rolls 20R thus produced were mounted at predetermined positions of a general apparatus for laminating and sticking sheet-like materials using RtoR as shown in FIG. 4 (B). The two separation membrane rolls 20R were mounted in the laminated roller pair 52 so that the facilitated transport membranes 20a of the sent acid gas separation membrane 20 face each other. Next, the acidic gas separation membrane 20 is sent out from the two separation membrane rolls 20R mounted, and is inserted into a predetermined conveyance path passing through the guide roller 50, the lamination roller pair 52, and the conveyance roller pair 54, and the leading end is taken up by the winding shaft 56. I wound it.
After finishing the above preparation, the acidic gas separation membrane 20 fed from both separation membrane rolls 20R is conveyed in the longitudinal direction, and the facilitated transport membrane 20a is laminated and pasted by the laminating roller pair 52. Separation membrane sticking body 20A as shown to 4 (A) was produced. The clamping pressure by the laminated roller pair 52 was 300 kPa.
The manufactured separation membrane sticking body 20A was wound around the take-up shaft 56 while being transported in a predetermined direction by the pair of transporting rollers 54 to obtain a sticking body roll 20AR.

<Production of separation module>
As shown in FIGS. 5 (A) and 5 (B), a SUS center tube 12 (through hole diameter 1.5 mm, opening ratio 1.8%) is connected to a permeating gas channel member 26 (100 mesh stainless steel). A metal mesh (wire diameter: 0.1 mm, aperture: 0.154 mm) was fixed.
A slit having a width of 1 mm and a length of 150 mm was formed at the center of the central cylinder 12, and the end of the permeating gas channel member 26 was inserted and fixed.

On the other hand, the produced separation membrane sticking body 20A was pulled out from the sticking body roll 20AR, cut into a predetermined length, and folded in half. As shown in FIG. 6, the two folds were performed so that one separation membrane sticking body 20 </ b> A was slightly longer. A fluororesin tape was affixed to the trough of the separation membrane sticking body 20A folded in half, and the end of the supply gas flow path member 24 was reinforced so as not to damage the trough of the support 20b.
Next, the supply gas flow path member 24 (PP net having a thickness of 0.5 mm) was sandwiched between the two folded separation membrane stickers 20A to produce a sandwich 36A. At this time, the separation film sticking body 20A is folded in half so that the facilitated transport film 20 provided with the intermediate layer 20c is separated from the supply gas flow path member 24, and is sandwiched between the supply gas flow path members 24. 36A was produced.

A relatively low-viscosity adhesive was applied to four sides of the peripheral edge of one surface with a brush on the support 20b having the shorter separation membrane sticker 20A of the sandwich 36A to form a membrane protection part. As the adhesive having a relatively low viscosity, 50 parts by mass of acetone was mixed with 50 parts by mass of an epoxy resin (E120HP: manufactured by Henkel Japan).
Next, as shown in FIG. 6, an adhesive 30 a was applied in the vicinity of both ends in the width direction (arrow x direction) extending in the entire winding direction (arrow y direction). Further, an adhesive 30a was applied in the vicinity of the end portion on the side opposite to the folded portion in the winding direction so as to extend over the entire width direction. As the adhesive 30a, an adhesive made of an epoxy resin (E120HP manufactured by Henkel Japan) was used.
Further, with the side to which the adhesive 30a is applied facing downward, as shown in FIGS. 7 (A) and 7 (B), the sandwiching body 36A, the permeating gas flow path member 26 fixed to the central cylinder 12, and Were laminated and adhered.
Next, a relatively low-viscosity adhesive is applied to the upper surface of the separation membrane sticking body 20A (support 20b) of the sandwiching body 36A in which the permeating gas flow path member 26 is laminated with brushes on three sides of the peripheral edge of one surface. The film protective part was formed by coating.
Further, as shown in FIGS. 7 (A) and 7 (B), adhesive 30a is applied in the vicinity of both ends in the width direction so as to extend over the entire area in the winding direction, and the folded portion in the winding direction. The adhesive 30a was applied in the vicinity of the end on the opposite side, extending in the entire width direction.
Further, as shown in FIG. 8, a permeating gas flow path member 26 is laminated on the separation membrane sticking body 20A to which the adhesive 30a is applied, and bonded to form the first layered body 14a. did. In this example, two gas flow path members 26 were stacked and bonded together.

In the same manner as described above, another sandwiching body 36A shown in FIG. 6 was produced, and similarly, the adhesive 30a was similarly applied to the porous support 20b side of the separation membrane sticking body 20A on the short side. . Next, in the same manner as in FIGS. 7A and 7B, the side to which the adhesive 30 a is applied is directed toward the first layered body 14 a (the permeate gas flow path member 26) formed first, The sandwiching body 36A was laminated on the first layered body 14a (permeating gas flow path member 26) and adhered. Further, an adhesive 30a is applied to the upper surface of the sandwiching body 36A in the same manner as in FIG. 6, and a permeating gas flow path member 26 is laminated thereon and adhered in the same manner as in FIG. The eye laminate 14a was formed. Similarly to the above, two gas flow path members 26 were stacked and bonded.
Further, in the same manner as in the second layer, a third-layer laminate 14a is formed on the second-layer laminate 14a, and a laminate in which a 20-layer laminate 14a is laminated in the same manner. Formed.

After laminating 20 layers of the laminated body 14a on the permeate gas flow path member 26 fixed to the central cylinder 12, an adhesive 38a is applied to the peripheral surface of the central cylinder 12, as shown in FIG. The adhesive 38b was applied on the permeating gas flow path member 26 between the central cylinder 12 and the lowermost layered laminate 14a. The adhesives 38a and 38b were the same as the adhesive 30a.
Next, the central cylinder 12 is rotated in the direction of the arrow yw in FIG. 9 to wrap the 20-layer laminated body 14a in multiple layers so as to be wound, and tension is applied in the direction of pulling the laminated body 14a. Thus, a laminate wound product 14 was obtained. This winding was performed so that the diameter of the laminated body wound product 14 was 200 mm.

Furthermore, after cutting the end surface of the laminated body 14 and aligning both ends, the central tube 12 is inserted into the inner ring portion 16b at both ends of the laminated body 14, and the shape shown in FIG. A telescoping prevention plate 16 made of SUS having a thickness of 2 cm was attached.
Furthermore, the FRP resin tape which consists of glass fiber and an epoxy resin is wound around the surrounding surface of the telescope prevention board 16 and the laminated body wound material 14, and the coating layer 18 with a thickness of 5 mm is sealed. The separation module 10 as shown in FIG. 1 having a width of 30 cm was formed.

[Comparative Example 1]
An acidic gas separation membrane 20 was formed in the same manner as in Example 1 except that the coating amount of the coating composition to be the intermediate layer 20c and the time until curing were changed.
The thickness Ta of the intermediate layer 20c on the support was 2 μm, and the thickness Tb of the soaking area was 0.1 μm. Therefore, the thickness ratio “Tb / Ta” is 0.05, and the thickness ratio “Tc / (Ta + Tb)” is 9.52.
When measured in the same manner as in Example 1, the gas permeability of the intermediate layer 20c was 560 Barrer.
Using this acidic gas separation membrane 20, a separation module 10 was produced in the same manner as in Example 1.

[Comparative Example 2]
An acidic gas separation membrane 20 was formed in the same manner as in Example 1 except that the coating amount of the coating composition to be the intermediate layer 20c and the time until curing were changed.
The thickness Ta of the region on the support of the intermediate layer 20c was 0.15 μm, and the thickness Tb of the soaking region was 20 μm. Therefore, the thickness ratio “Tb / Ta” is 133.3, and the thickness ratio “Tc / (Ta + Tb)” is 0.99.
When measured in the same manner as in Example 1, the gas permeability of the intermediate layer 20c was 1020 Barrer.
Using this acidic gas separation membrane 20, a separation module 10 was produced in the same manner as in Example 1.

[Comparative Example 3]
A coating composition to be the intermediate layer 20c was prepared in the same manner as in Example 1 except that a PVA aqueous solution (Mw = 88,000 manufactured by Kanto Chemical Co., Inc.) was used instead of the polymerizable polydimethylsiloxane. The coating composition had a viscosity at 25 ° C. of 800 cP.
An acidic gas separation membrane 20 was formed in the same manner as in Example 1 except that the intermediate layer 20c was formed using this coating composition.
The thickness Ta of the region on the support of the intermediate layer 20c was 2 μm, and the thickness Tb of the soaking region was 0.2 μm. Therefore, the thickness ratio “Tb / Ta” is 0.1, and the thickness ratio “Tc / (Ta + Tb)” is 9.09.
When measured in the same manner as in Example 1, the gas permeability of the intermediate layer 20c was 15 Barrer.
Using this acidic gas separation membrane 20, a separation module 10 was produced in the same manner as in Example 1.

[Performance evaluation]
<Airtightness>
The supply side of the manufactured separation module 10 was filled with He gas so that a pressure of 0.34 MPa was applied, sealed, and hermeticity (manufacturing stability) was measured during the time when the pressure decreased to 0.3 MPa. The separation module 10 in which the time for the pressure to decrease from 0.34 MPa to 0.3 MPa was 10,000 seconds or more was determined to be free of defects.
In each example, the same test was performed on the five separation modules produced, and the following evaluation was performed.
A: 4 out of 5 with no defects B: 1-3 with 5 without defects C: 0 with 5 defects without 5

<Separation performance durability evaluation>
The source gas G was supplied to each separation module 10 under the conditions of a flow rate of 0.32 L / min, a temperature of 130 ° C., and a total pressure of 2001.3 kPa. As the source gas G, a mixed gas (partial pressure ratio) of N ₂ : CO ₂ : H ₂ O = 66: 21: 13 was used. A through hole for supplying a sweep gas was formed at the end of the central cylinder 12 on the raw material gas permeation side, and Ar gas having a flow rate of 0.6 L / min was supplied as a sweep gas from here.
The gas (acid gas Gc and residual gas Gr) that has permeated through the separation module 10 was analyzed by a gas chromatograph at the time when 1 hour passed after starting the supply of the raw material gas G and the time when 200 hours passed, and CO ₂ / N ₂ separation factor (α) was measured.

The rate of change of the CO ₂ / N ₂ separation factor (α) was calculated at the time of 1 hour and at the time of 200 hours, and the separation performance durability was evaluated.
Rate of change =
[(Value at the time of 1 hour elapse-Value at the time of 200 hours elapse) / Value at the time elapse of 1 hour] × 100
The evaluation is as follows. In addition, evaluation was performed by the average of five modules.
A: Change rate between 1 hour and 200 hours is less than 5% B: Change rate after 1 hour and after 200 hours is 5% or more and less than 10% C: After 1 hour and 200 hours 10% or more change rate from after

[Comprehensive evaluation]
The performance of each separation module was comprehensively evaluated as follows.
A: When both airtightness and separation performance durability are A B: When one of airtightness and separation performance durability is A and the other is B C: When both airtightness and separation performance durability are B D: Airtightness When either the property or the separation performance durability is C, the results are shown in the following table.

As shown in the above table, the thickness ratio “Tb / Ta” between the thickness Ta of the support upper region and the thickness Tb of the soaking region falls within a predetermined range, and the gas permeability is 500 Barrer or more. The module of the present invention having an intermediate layer is excellent in both airtightness (product stability) and durability in separation performance. In particular, Example 9 having a protective layer on the facilitated transport membrane 20a is very excellent in both airtightness and durability in separation performance. In addition, Examples 10 to 15 using a Ti-based crosslinking agent for the facilitated transport film 20a are also excellent in both airtightness and durability of separation performance.
In Example 6, “Tc / (Ta + Tb)” is as low as 0.27. Therefore, the hardness of the intermediate layer 20c has an effect, and the facilitated transport film 20a is damaged by sliding contact with the supply gas flow path member 24 when the laminate 14a is wound, resulting in other It is considered that the airtightness is slightly reduced as compared with the example.
In contrast, in the separation module of Comparative Example 1, since the thickness Tb of the soaked region is too thin with respect to the thickness Ta of the region on the support, the durability of the separation performance is low although the airtightness is excellent. In contrast, in the separation module of Comparative Example 2, since the thickness Tb of the infiltration region is too thick with respect to the thickness Ta of the upper region of the support, the airtightness is low and the pressure that can be measured can be applied. Since the separation module was not obtained, the durability of the separation performance could not be measured. Furthermore, although the separation module of Comparative Example 3 has low gas permeability, it has excellent airtightness but low separation performance durability.

In addition, regarding Example 16, after evaluating airtightness and separation performance durability, the module was disassembled, and the width of the adhesive layer 30 (sealing portion) and the width of the membrane protection portion were measured.
Specifically, in each laminated body 14a, three different cross-sections were taken out for one specific side other than the bent portion of the sandwiching body 36A among three sides or four sides. Next, by using image processing for each cross section, the area of the hole in each part of the porous film and the auxiliary support film of the support 20b and the permeating gas channel member 26 every 0.01 mm width from the end of the laminate 14a. The penetration rate of the adhesive was determined from the adhesive filling area.
Based on the obtained penetration rate of the adhesive, the penetration rate of the adhesive in the porous membrane is 60% or more, and the penetration rate of the adhesive in the auxiliary support membrane and the permeating gas channel member 26 is the penetration rate in the porous membrane. The above portion is used as the adhesive layer 30, and further, the penetration rate of the adhesive in the porous membrane is 10% or more, and the penetration rate of the adhesive in the auxiliary support membrane and the permeating gas channel member 26 is that of the porous membrane. The width of the adhesive layer 30 and the width of the film protective part were determined using the part that is smaller than the adhesive soaking rate as the film protective part.
As a result, the sealing width of the adhesive layer 30 is 40 mm, the membrane protection part is 80 mm from the end, and the penetration rate of the adhesive in the membrane protection part is 86% porous membrane; 10% auxiliary support membrane; Permeate gas channel member; 0%.
From the above results, the effects of the present invention are clear.

  It can be suitably used for hydrogen gas production, natural gas purification, and the like.

DESCRIPTION OF SYMBOLS 10 (Acid gas) separation module 12 Center tube 14 Laminated body roll 14a Laminate body 16 Telescope prevention board 16a Outer ring part 16b Inner ring part 16c Rib 16d Opening part 18 Covering layer 20 Acid gas separation membrane 20R Separation membrane roll 20A Separator Membrane Adhesive 20AR Adherent Roll 20a Accelerated Transport Membrane 20b Porous Support 20c Intermediate Layer 24 Supply Gas Channel Member 26 Permeate Gas Channel Member 30 Adhesive Layer 30a Adhesive 34 Fixing Means 36.36A Nipping Body 50 Guide roller 52 Laminated roller pair 54 Conveying roller pair 56 Winding shaft

Claims (11)

A porous support, an intermediate layer formed on the porous support, a carrier that reacts with an acid gas, and a hydrophilic compound for supporting the carrier, formed on the intermediate layer An acidic gas separation membrane having a facilitated transport membrane, and a supply gas flow path member serving as a flow path for the source gas,
And the intermediate layer has a support upper region located on the porous support, and a permeation region inside the porous support, the thickness Ta of the support upper region, The acidic gas separation module characterized in that the ratio “Tb / Ta” with respect to the thickness Tb of the soaking area is 0.1 to 100, and the gas permeability is 500 Barrer or more.   2. The acidic gas separation module according to claim 1, wherein a ratio “Tc / (Ta + Tb)” between a thickness Tc of the facilitated transport film and a thickness “Ta + Tb” of the intermediate layer is 0.3 to 500. 3.   The acidic gas separation module according to claim 1 or 2, wherein the acidic gas separation module is a spiral type formed by winding a laminate including the acidic gas separation membrane and the supply gas flow path member.   3. The acidic gas separation module according to claim 1, wherein the acidic gas separation module is a flat plate type in which a laminate including the acidic gas separation membrane and the supply gas flow path member is maintained in a flat plate shape.   5. The acid according to claim 1, wherein the intermediate layer contains a compound having at least one of an epoxy group, an amino group, a methoxy group, an ethoxy group, a hydroxyl group, and a carboxyl group as a main component. Gas separation module.   The acidic gas separation module according to claim 1, wherein the intermediate layer is a polydimethylsiloxane derivative.   The acidic gas separation module according to claim 1, further comprising a protective layer on the facilitated transport membrane.   The acidic gas separation module according to claim 7, wherein the protective layer is a polydimethylsiloxane derivative.   The acid gas separation module according to any one of claims 1 to 8, wherein the facilitated transport film contains at least one metal element selected from the group consisting of Ti, Zr, Al, Si, and Zn. .   The acidic gas separation module according to claim 9, wherein the content of the metal element in the facilitated transport film is 0.1 to 50% by mass with respect to the total mass of the hydrophilic compound. The acidic gas separation module according to claim 9 or 10, wherein the facilitated transport membrane contains a structural unit represented by the formula (1).
Formula (1) M- (O- *) _m
M represents a metal element selected from the group consisting of Ti, Zr, Al, Si, and Zn. m represents the valence of the metal element represented by M. * Represents a binding position.