JP2016064384A - Acidic gas separation module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acidic gas separation module exhibiting predetermined performance for a long term by preventing a facilitated transport membrane from breakage.SOLUTION: In a spiral type acidic gas separation module wound with a laminate including an acidic gas separation layer having a facilitated transport membrane, the facilitated transport membrane has: a carrier; a hydrophilic compound; a boron atom; a content of the carrier to a hydrophilic compound of 20-500 mass%; and a content of the boron atom to the carrier of 0.1-10 mass%.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an acidic gas separation module that selectively separates acidic gas from raw material gas. Specifically, the present invention relates to a spiral acidic gas separation module formed by winding a laminate having an acidic gas separation layer.

  In recent years, development of a technique for selectively separating an acidic gas such as carbon dioxide from a raw material gas (a gas to be treated) has been advanced. For example, an acid gas separation module that separates an acid gas from a raw material gas by using an acid gas separation layer that selectively permeates the acid gas has been developed.

For example, in Patent Document 1, a multilayer body including an acidic gas separation layer is wrapped around a central tube (a central permeate collection tube) for collecting separated acidic gas having a through-hole formed in a tube wall. An acidic gas separation module is disclosed.
The acidic gas separation module disclosed in Patent Document 1 is a dissolution diffusion type acidic gas separation module using a so-called dissolution diffusion membrane as an acidic gas separation layer. The dissolution diffusion membrane separates the acid gas from the raw material gas by utilizing the difference in solubility between the acidic gas and the substance to be separated in the membrane and the diffusivity in the membrane.

In Patent Document 2, the space is divided into a raw material chamber and a permeation chamber by an acidic gas separation layer, and a raw material gas (mixed gas composed of CO ₂ , H _2, and H ₂ O) is supplied to the raw material chamber to separate the acidic gas. An acidic gas separation module (experimental device) is disclosed in which the acidic gas selectively separated (permeated) by the layers is taken out from the permeation chamber.
The acidic gas separation module disclosed in Patent Document 2 is a facilitated transport type acidic gas separation module that uses a so-called facilitated transport membrane as the acidic gas separation layer. The facilitated transport membrane has a carrier that reacts with the acid gas 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 the carrier.

  In such an acidic gas separation module, a laminate having an acidic gas separation layer as shown in Patent Document 1 is wound around a central cylinder having a through-hole on a wall surface (wrapped around the central cylinder), so-called. The spiral type acidic gas separation module can increase the area of the acidic gas separation layer. Therefore, the spiral type acidic gas separation module can be efficiently processed.

Japanese Patent Laid-Open No. 4-215824 Japanese Patent No. 4621295

As an example, the spiral type acidic gas separation module is separated by the acidic gas separation layer and the central tube, the supply gas flow path member that becomes the flow path of the source gas from which the acidic gas is separated, and the acidic gas separation layer A permeated gas flow path member serving as a flow path for the acidic gas thus formed is configured.
A spiral acidic gas separation module made of such a member is formed by laminating one or a plurality of laminated bodies in which an acidic gas separation layer, a supply gas flow path member and a permeate gas flow path member are laminated, It has the structure wound around the center tube.

  For example, in the above-mentioned Patent Document 1, the acidic gas separation layer is folded in half and a supply gas flow path member (feed spacer) is sandwiched, and one of the folded acidic gas separation layers is used for the permeate gas flow path. There is disclosed a spiral acid gas separation module in which a laminated body in which members (permeate spacers) are laminated is manufactured, and a plurality of laminated bodies are wound around a central cylinder (permeate collecting tube). Yes.

  However, according to the study of the present inventor, when an acid gas separation module using a facilitated transport membrane is configured as a spiral-type module having such a configuration, an acid gas separation module having desired performance is often obtained. There was a case where cannot be obtained.

That is, the supply gas flow path member normally has a mesh structure so as to constitute a flow path for the raw material gas and to bring the raw material gas flowing through itself into contact with the acidic gas separation layer.
On the other hand, in general, an acidic gas separation layer having a facilitated transport membrane tends to have a higher acid gas separation rate (permeation rate) as the hygroscopic property of the facilitated transport membrane is higher. Therefore, the facilitated transport film has a configuration in which a hydrophilic compound such as a superabsorbent resin is used as a binder and carriers are dispersed in the binder, and is often soft.

Here, since the spiral type separation module has a configuration in which the laminated body is wound around the central cylinder as described above, a positional deviation between the facilitated transport film and the supply gas flow path member occurs at the time of winding. . Due to this misalignment, the facilitated transport film and the supply gas flow path member are in sliding contact with each other, and the facilitated transport film is damaged. In a severe case, almost all of the facilitated transport film is partially removed and becomes a defect.
Further, as shown in Patent Document 1, when the acidic gas separation layer is folded in half and the supply gas flow path member is sandwiched, the facilitated transport membrane is damaged when the acidic gas separation layer is folded in half. There is a case to do.
As a result, in the spiral acidic gas separation module using the facilitated transport membrane, the acidic gas separation module having the intended performance may not be obtained due to such damage of the facilitated transport membrane.

  An object of the present invention is to solve this problem, and is a spiral type acidic gas separation module using an acidic gas separation layer having a facilitated transport membrane, which is used when the acidic gas separation layer is folded in two. A module having the desired performance can be stably obtained by preventing damage to the facilitated transport film and damage of the facilitated transport film due to sliding contact between the facilitated transport film and the supply gas flow path member during winding. It is to provide an acid gas separation module that can be used.

In order to achieve this object, the acidic gas separation module of the present invention includes a central tube having a through-hole formed in a tube wall,
A supply gas flow path member serving as a flow path for the source gas;
A carrier that reacts with an acidic gas, a hydrophilic compound for supporting the carrier, and a boron atom, and the carrier content is 20 to 500% by mass with respect to the hydrophilic compound, and the boron atom content. Is 0.1 to 10% by mass with respect to the carrier, and includes an facilitated transport membrane that separates the acidic gas from the raw material gas flowing through the supply gas flow path member, and an acid having a porous support that supports the facilitated transport membrane A gas separation layer;
A permeating gas channel member that serves as a channel through which the acidic gas that has reacted with the carrier and permeated the acidic gas separation layer flows to the central cylinder;
Provided is an acidic gas separation module comprising at least one laminate having a supply gas flow path member, an acidic gas separation layer, and a permeate gas flow path member wound around a central cylinder.

In such an acidic gas separation module of the present invention, it is preferable that a boron atom and a hydrophilic compound are crosslinked in the facilitated transport membrane.
Moreover, it is preferable that a facilitated-transport film | membrane contains at least one of the structure represented by Formula (1), and the structure represented by Formula (2).
The hydrophilic compound is preferably a copolymer of polyvinyl alcohol and polyacrylic acid.
The carrier is preferably an alkali metal compound.
The facilitated transport film preferably has a thickness of 3 to 1000 μm.
The porous support preferably has a porous membrane and an auxiliary support membrane that supports the porous membrane.
The porous membrane is preferably made of polytetrafluoroethylene.
Moreover, it is preferable to have a hydrophobic intermediate layer having gas permeability between the porous support and the facilitated transport membrane.
The intermediate layer is preferably a silicone resin layer.
Further, the laminate preferably has a structure in which the acidic gas separation layer is folded in half and the supply gas flow path member is sandwiched, and the permeate gas flow path member is stacked on the sandwich body. .

According to the present invention, in a spiral acidic gas separation module using a facilitated transport membrane, damage to the facilitated transport membrane caused by sliding contact between the facilitated transport membrane and the supply gas flow path member generated during winding, or acidic gas The facilitated transport membrane can be suitably prevented from being damaged when the separation layer is folded in half. Also, the adhesion between the porous support and the facilitated transport film is good, and the facilitated transport film can be prevented from peeling off from the porous support during winding or operation.
Therefore, according to the present invention, it is possible to stably obtain an acid gas separation module that prevents deterioration in performance due to damage or peeling of the facilitated transport membrane, has excellent product stability, and exhibits desired performance. be able to.

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 the laminated body 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. (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.
As shown in FIG. 1, the acidic gas separation module 10 basically includes a center tube 12, a laminated body 14, and a telescope prevention plate 16. The laminated body 14 is formed by laminating an acidic gas separation layer 20 having a facilitated transport film 20a, a supply gas flow path member 24, and a permeate gas flow path member 26.
As an example, the acidic gas separation module 10 separates carbon dioxide as the acidic gas Gc from the raw material gas G containing carbon monoxide, carbon dioxide (CO ₂ ), water (water vapor), and hydrogen.
In the following description, the acid gas separation module is also simply referred to as a separation module.

  The separation module 10 of the present invention is a so-called spiral type separation module. That is, in the separation module 10, one or a plurality of sheet-like laminates 14 are laminated and wound around the center tube 12, and the center tube 12 is inserted into both end surfaces of the wound product of the laminate 14. Thus, the telescope prevention plate 16 is provided. The outermost peripheral surface of the wound laminated body 14 is covered with a gas impermeable coating layer 18.

  In the following description, a wound product of a laminate in which a plurality of laminates 14 are wound around the central cylinder 12 is also referred to as a laminate wound product 14a for convenience. In other words, the laminated body 14a is a substantially cylindrical object formed by the laminated body 14 that is laminated and wound.

In such a separation module 10, the raw material gas G from which the acidic gas is separated passes, for example, through the telescope prevention plate 16 (the opening portion 16 d) on the far side in FIG. 1 to the end surface of the laminated body 14 a. The acid gas Gc is separated while flowing into the laminated body 14 from the end face and flowing through the laminated body 14.
Further, the acidic gas Gc separated from the raw material gas G by the stacked body 14 is discharged from the central cylinder 12. On the other hand, the source gas G from which the acidic gas Gc has been separated (hereinafter referred to as the residual gas Gr for convenience) is discharged from the end surface opposite to the supply side of the stacked body 14a (laminated body 14), It is discharged out of the separation module 10 through the telescope prevention plate 16 (same as above).

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 central cylinder 12, the aperture ratio (area ratio of the through-hole 12a in the outer peripheral surface of the central cylinder 12) in the region sealed with the adhesive layer 30 described later is preferably 1.5 to 80%, and preferably 3 to 75. % Is more preferable, and 5 to 70% is more preferable. Among these, from the practical viewpoint, the opening ratio of the center tube 12 is particularly preferably 5 to 25%.
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.

The laminate 14 is formed by laminating an acidic gas separation layer 20, a supply gas flow path member 24, and a permeate gas flow path member 26.
In FIG. 1, reference numeral 30 denotes an acid gas Gc in the permeate gas flow path member 26 while the acid gas separation layer 20 and the permeate gas flow path member 26 are bonded together and the laminates 14 are bonded together. It is the adhesive bond layer 30 which regulates the flow path.

The separation module 10 in the illustrated example has a configuration in which a plurality of the laminated bodies 14 are laminated and wound (wound) around the central cylinder 12 to form a substantially cylindrical laminated body 14a. .
Hereinafter, for convenience, a direction corresponding to the winding of the laminate 14 is a winding direction (arrow y direction), and a direction orthogonal to the winding direction is a width direction (arrow x direction).

In the separation module 10, the laminate 14 may be a single layer. However, as shown in the illustrated example, by laminating a plurality of laminated bodies 14, the membrane area of the acidic gas separation layer 20 can be increased, and the amount of the acidic gas Gc separated by one module can be improved.
The number of stacked layers 14 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 14 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 14 to be this number, winding of the laminated body 14 around the central cylinder 12 becomes easy, and workability can be improved.

In FIG. 2, the fragmentary sectional view of the laminated body 14 is shown. As described above, the arrow x is the width direction, and the arrow y is the winding direction.
In the illustrated example, the laminated body 14 forms a sandwiching body 36 by sandwiching the supply gas flow path member 24 between the acidic gas separation layers 20 folded in half (see FIG. 4). The road 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 laminated body 14 a through the telescope prevention plate 16 (its opening 16 d). That is, the source gas G is supplied to the end portions (end surfaces) in the width direction of the stacked bodies 14.
As conceptually shown in FIG. 2, the source gas G supplied to the end surface in the width direction of the stacked body 14 flows in the width direction (arrow x direction) through the supply gas flow path member 24. In this flow, the acidic gas Gc in contact with the facilitated transport film 20a of the acidic gas separation layer 20 is separated from the raw material gas G, passes through the acidic gas separation layer 20 in the stacking direction of the stacked body 14, and permeates. It flows into the gas flow path member 26. Specifically, the acidic gas Gc in contact with the facilitated transport film 20a is separated from the source gas G, transported in the stacking direction by the carrier of the facilitated transport film 20a, and flows into the permeate gas channel 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) and reaches the central cylinder 12. The acidic gas Gc reaching the central cylinder 12 flows into the central cylinder 12 from the through hole 12a of the central cylinder 12.
The flow of the acid gas Gc is regulated by the adhesive layer 30. That is, in the separation module 10, the two acidic gas separation layers 20 (facilitated transport membrane 20a) sandwiching the permeate gas flow path member 26, the permeate gas flow path member 26, and the acidic gas separation layer 20 (porous support) 20b) and the adhesive layer 30 penetrating into the inner surface of the adhesive layer 30 in the surface direction forms an envelope-like flow path (space) that encloses the permeate gas flow path member 26 and that is open on the central tube 12 side. (See FIGS. 4 and 5A). Thereby, the separation module 10 regulates the flow path of the acidic gas Gc that has passed through the acidic gas separation layer 20 in the direction toward the central cylinder 12, and the source gas G and the residual gas Gr have passed through the acidic gas separation layer 20. Mixing into the acid gas Gc is prevented. The adhesive layer 30 will be described in detail later.

The acidic gas Gc that has flowed into the center tube 12 flows through the center tube 12 in the width direction and is discharged from the open end 12b.
The residual gas Gr from which the acid 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 laminated body 14a. 16d) and discharged to the outside of the separation module 10.

The supply gas flow path member 24 is supplied with the raw material gas G from the end in the width direction, and brings the raw material gas G flowing in the member into contact with the acidic gas separation layer 20.
Such a supply gas flow path member 24 functions as a spacer of the acid gas separation layer 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. In consideration of this point, the supply gas flow path member 24 is preferably a member having a net shape (net shape / mesh shape).

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

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.

  The separation module 10 of the present invention is a facilitated transport type. Therefore, the acidic gas separation layer 20 includes a facilitated transport film 20a and a 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, a hydrophilic compound that supports the carrier, and a boron atom. Such a facilitated transport film 20a has a function of selectively permeating the acid gas Gc from the source gas G (a function of selectively transporting the acid gas Gc).
The facilitated transport type separation module is required to be used at high temperature and high humidity. Therefore, the facilitated transport film 20a has a function of selectively permeating the acidic gas Gc even at high temperatures (for example, 50 to 200 ° C.). Moreover, even if the source gas G contains water vapor, the hydrophilic compound absorbs water vapor and the facilitated transport film 20a retains moisture, so that the carrier can more easily transport the acidic gas Gc. Compared with the case, the separation efficiency is increased.

The membrane area of the facilitated transport membrane 20a may be set as appropriate according to the size of the separation module 10, the processing capacity required for the separation module 10, and the like. Specifically, preferably 0.01～1000M ^2, more preferably 0.02～750M ^2, more preferably 0.025~500m ^2. Among these, the membrane area of the facilitated transport film 20a is particularly preferably 1 to 100 m ² from a practical viewpoint.
By setting the membrane area of the facilitated transport membrane 20a within the above range, the acidic gas Gc can be efficiently separated with respect to the membrane area, and the processability is also improved.

The length of the facilitated transport film 20a in the winding direction (the total length before folding in half) may be set as appropriate according to the size of the separation module 10, the processing capacity required for the separation module 10, and the like. Specifically, 100 to 10000 mm is preferable, 150 to 9000 mm is more preferable, and 200 to 8000 mm is even more preferable. Among them, the length of the facilitated transport film 20a is particularly preferably 800 to 4000 mm from a practical viewpoint.
By setting the length of the facilitated transport film 20a in the winding direction within the above range, the acidic gas Gc can be efficiently separated with respect to the film area. Furthermore, by setting the length of the facilitated transport film 20a in the winding direction within the above range, occurrence of winding deviation when winding the laminated body 14 is suppressed, and workability becomes easy.
The width of the facilitated transport film may be set as appropriate according to the size of the separation module 10 in the width direction.

The thickness of the facilitated transport film 20a may be appropriately set according to the size of the separation module 10, the processing capability required for the separation module 10, and the like. Specifically, 3-1000 μm is preferable, and 5-500 μm is more preferable.
By setting the thickness of the facilitated transport film 20a within the above range, it is preferable in that high gas permeability and separation selectivity can be realized.

The hydrophilic compound functions as a binder, holds moisture in the facilitated transport film 20a, and exhibits a function of separating a gas such as carbon dioxide by the carrier. A hydrophilic polymer is illustrated as a hydrophilic compound.
Here, in the separation module 10 of the present invention, the hydrophilic compound contains a boron atom, and preferably has a crosslinked structure containing a boron atom. When the hydrophilic compound contains a boron atom, and preferably has a cross-linked structure containing a boron atom, the film strength of the facilitated transport film 20a can be improved, and damage or peeling of the facilitated transport film 20a can be prevented. This will be described in detail later.

From the viewpoint that the hydrophilic compound can be dissolved in water to form a coating solution, 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, more preferably 1 g / g or more, more preferably 5 g / g of the physiological saline. More preferably, it has a hydrophilicity of g or more, particularly preferably has a hydrophilicity of 10 g / g or more, and most preferably has a hydrophilicity of 20 g / g or more.

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.
In particular, when the hydrophilic compound has a hydroxy group as a crosslinkable group, the weight average molecular weight is preferably 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. Moreover, when a hydrophilic compound has a hydroxyl group as a crosslinkable group, it is preferable that a weight average molecular weight is 6,000,000 or less from a viewpoint of manufacture aptitude.
In addition, the hydrophilic compound preferably has a weight average molecular weight of 10,000 or more when it has an amino group as a crosslinkable group. 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 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 acid copolymer is preferable because of its high water absorption ability and high hydrogel strength even at high water absorption.
In the polyvinyl alcohol-polyacrylic acid copolymer, the content ratio of polyvinyl alcohol and polyacrylic acid is, for example, preferably 0.1 to 9.5, and more preferably 0.15 to 9 in terms of a molar ratio of polyvinyl alcohol / polyacrylic acid. More preferably, 0.2-4 is especially preferable.
By setting the content ratio of polyvinyl alcohol and polyacrylic acid in the polyvinyl alcohol-polyacrylic acid copolymer to 0.1 or more in terms of a molar ratio of polyvinyl alcohol / polyacrylic acid, the facilitated transport film 20a contains boron. Preferably, it is preferable in that the effect of improving the film strength of the facilitated transport film 20a by forming a crosslinked structure containing a boron atom can be obtained more suitably.
Moreover, it is preferable at the point that high gas permeability is acquired by making the content rate of polyvinyl alcohol and polyacrylic acid into 9.5 or less by the molar ratio of polyvinyl alcohol / polyacrylic acid.
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 facilitated transport membrane 20a of the separation module 10 of the present invention, two or more hydrophilic compounds may be mixed and used.

The content of the hydrophilic compound in the facilitated transport film 20a functions as a binder for forming the facilitated transport film 20a as long as the content of the carrier described below is 20 to 500% by mass with respect to the hydrophilic compound. In addition, an amount capable of sufficiently holding water may be set as appropriate according to the type of the hydrophilic composition and the carrier.
Specifically, the content of the hydrophilic compound in the entire 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 in the facilitated transport film 20a within this range, the above-described function as a binder and moisture retention function can be stably and suitably expressed.

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

Here, in this invention, the facilitated-transport film | membrane 20a contains a boron atom in addition to a hydrophilic compound and the carrier mentioned later.
Moreover, in the facilitated-transport film | membrane 20a, content of a carrier is 20-500 mass% with respect to a hydrophilic compound, and content of a boron atom is 0.1-10 mass% with respect to a carrier. The carrier content will be described later.

Although the form of the boron atom contained in the facilitated transport film 20a is not particularly limited, it is preferably crosslinked with a hydrophilic compound (forms a crosslinked structure) in that the effect of the present invention is more excellent. .
Supply of the facilitated transport film 20a when the laminate 14 is wound by improving the film strength of the facilitated transport film 20a by forming a crosslinked structure containing boron atoms, preferably by containing boron atoms. Damage to the facilitated transport film 20a due to sliding contact with the gas flow path member 24, and damage to the facilitated transport film 20a when the acidic gas separation layer 20 is folded in two to sandwich the supply gas flow path member 24 can be prevented. . In addition, since the adhesion between the porous support 20b and the facilitated transport film 20a can be improved, the facilitated transport film can be prevented from being peeled off from the porous support during winding or operation. Thereby, according to this invention, the separation module 10 which has the target performance can be obtained stably.

As a suitable aspect of the bridge | crosslinking structure containing a boron atom, the structure represented by Formula (1) and the structure represented by Formula (2) are mentioned. The facilitated transport film 20a preferably includes either one of the structure represented by the formula (1) or the structure represented by the formula (2), and may include both. In the formula, * represents a bonding position.
In addition, IR measuring method (infrared spectroscopy) is mentioned as an identification method of the following structures in the facilitated-transport film | membrane 20a.

The crosslinked structure as described above is formed by using a hydrophilic compound having a hydroxy group and a boron atom. Examples of the hydrophilic compound having a hydroxy group include the aforementioned polyvinyl alcohol-polyacrylic acid copolymer.
The source of the boron atom is not particularly limited and may be a compound having a boron atom (boron compound). For example, boric acid or borate is preferable. That is, the boron atom is preferably derived from boric acid or borate. The boron compound functions as a so-called cross-linking agent. Examples of such a boron compound include orthoboric acid, metaboric acid, and hypoboric acid as boric acid, and borate includes sodium salt, potassium salt, Mention may be made of ammonium. Among these, orthoboric acid and sodium tetraborate which is a sodium salt are preferable.
In addition, although the formation method in particular of the said crosslinked structure is not restrict | limited, For example, it forms by mixing the boron compound mentioned above and the hydrophilic compound which has a hydroxyl group.

In the separation module 10 of the present invention, the boron atom content in the facilitated transport film 20a is 0.1 to 10% by mass with respect to the carrier.
When the content of boron atoms is less than 0.1% by mass with respect to the carrier, the effect of containing boron atoms is not sufficiently obtained, and problems such as inability to improve the film strength of the facilitated transport film 20a occur.
On the other hand, if the boron atom content exceeds 10% by mass with respect to the carrier, the degree of cross-linking is too high, the viscosity of the coating solution becomes too high, and defects are easily generated during coating. Inconveniences such as inability to form a film.
Considering the above points, the content of boron atoms is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass with respect to the carrier.

As described above, in the acidic gas separation layer 20 of the separation module 10, the facilitated transport film 20a contains a carrier in addition to such a hydrophilic compound and boron atoms.
The carrier is various water-soluble compounds having affinity with an acidic gas (for example, carbon dioxide gas) and showing basicity. Specifically, an alkali metal compound, a nitrogen-containing compound, a sulfur compound, etc. are illustrated.
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 compound.

  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.
Furthermore, examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide.
Among these, an alkali metal carbonate is preferable, and a compound containing potassium, rubidium, and cesium having high solubility in water is preferable from the viewpoint of good affinity with acidic gas.

Moreover, 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 hygroscopicity of the facilitated transport film 20a, the facilitated transport films 20a or the facilitated transport film 20a and other members are stuck together at the time of manufacture. (Blocking) can be suitably suppressed.
When two or more alkali metal compounds are used as a carrier, it is preferable to include a first compound having deliquescence and a second compound having lower deliquescence and lower specific gravity than the first compound. When the carrier contains the first compound having deliquescence and the second compound having lower deliquescence and lower specific gravity than the first compound, a blocking suppression effect can be more suitably obtained. 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.
Further, examples of the sulfur compound include amino acids such as cystine and cysteine, polythiophene, dodecylthiol and the like.

In the separation module of the present invention, the content of the carrier in the facilitated transport membrane 20a is 20 to 500 mass% with respect to the hydrophilic compound.
When the carrier content is less than 20% by mass with respect to the hydrophilic compound, problems such as inability to obtain high gas permeability occur.
On the other hand, when the carrier content exceeds 500% by mass with respect to the hydrophilic compound, there are problems such as insufficient strength of the facilitated transport film 20a.
Considering the above points, the content of the carrier is preferably 50 to 500% by mass and more preferably 100 to 450% by mass with respect to the hydrophilic compound.

Moreover, if content with respect to a hydrophilic compound is 20-500 mass%, what is necessary is just to set content of the carrier in the whole facilitated transport film | membrane 20a suitably according to the kind etc. of hydrophilic compound. Specifically, the content 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 particularly preferably 1 to 20% by mass.
By setting the carrier content in the facilitated transport film 20a within the above range, salting out before coating can be suitably prevented in the composition (paint) for forming the facilitated transport film 20a. Furthermore, by setting the carrier content in the facilitated transport film 20a within the above range, the facilitated transport film 20a can reliably exhibit the function of separating the acidic gas.

  The facilitated transport film 20a (composition for forming the facilitated transport film 20a) may contain various components as necessary in addition to such a hydrophilic compound, a crosslinking agent, and a carrier.

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 moisturizing (moisture absorbing) agent, an auxiliary solvent, a film strength adjusting agent, a defect detecting agent, and the like may be used as necessary.

The acidic gas separation layer 20 includes such a facilitated transport membrane 20a and a porous support 20b.
The porous support 20b has acid gas permeability and can be coated with a coating composition for forming the facilitated transport film 20a (supporting the coating film). It supports the transport film 20a.
As the material for forming the porous support 20b, various known materials can be used as long as they can exhibit the above functions.

In the separation module 10 of the present invention, the porous support 20b constituting the acidic gas separation layer 20 may be a single layer. However, the porous support 20b constituting the acidic gas separation layer 20 preferably has a two-layer structure including a porous membrane and an auxiliary support membrane. By having such 2 structure, the porous support body 20b expresses more reliably the function of application | coating of the coating composition used as the facilitated-transport film | membrane 20a, and support of the facilitated-transport film | membrane 20a.
When the porous support 20b is a single layer, various materials exemplified below as the porous film and the auxiliary support film can be used as the forming material.

In this two-layered porous support 20b, the porous membrane is on the facilitated transport membrane 20a side.
The porous membrane is preferably made of a material having heat resistance and low hydrolyzability. Specific examples of such a porous membrane include membrane filter membranes such as polysulfone, polyethersulfone, polypropylene, and cellulose, interfacially polymerized thin films of polyamide and polyimide, and stretching of polytetrafluoroethylene (PTFE) and high molecular weight polyethylene. Examples thereof include a porous membrane.
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 and manufacturing suitability. Among them, a stretched porous membrane of PTFE is preferably used in terms of heat resistance and low hydrolyzability.

The porous membrane is hydrophobic because the facilitated transport membrane 20a containing moisture is likely to penetrate into the porous portion under the usage environment and does not cause deterioration in film thickness distribution or performance over time. Is preferred.
The porous membrane preferably has a maximum pore diameter of 1 μm or less.
The average pore diameter of the pores of the porous membrane is preferably 0.001 to 10 μm, more preferably 0.002 to 5 μm, and particularly preferably 0.005 to 1 μm. By setting the average pore diameter of the porous membrane within this range, it is possible to suitably prevent the adhesive application region described later from sufficiently impregnating the adhesive and preventing the porous membrane from passing the acidic gas. .

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 having an average pore diameter of 0.001 to 10 μm 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.
Non-woven fabrics, woven fabrics, and knitted fabrics that have excellent durability and heat resistance include polyolefins such as polypropylene (PP), modified polyamides such as aramid (trade name), polytetrafluoroethylene, polyvinylidene fluoride, etc. A fiber made of a fluorine-containing resin is preferable. It is preferable to use the same material as the resin material constituting the mesh. Among these materials, a non-woven fabric made of PP that is inexpensive and has high mechanical strength is particularly preferably exemplified.

  When the porous support 20b has an auxiliary support film, the mechanical strength can be improved. Therefore, for example, even when handling in a coating apparatus using a roll-to-roll (hereinafter also referred to as RtoR) described later, wrinkles on the porous support 20b can be prevented, and productivity can be increased. .

If the porous 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 porous support 20b is a single layer, the thickness of the porous support 20b is preferably 30 to 500 μm.

The acidic gas separation layer 20 is prepared by a so-called coating method in which a liquid coating composition (coating / coating liquid) containing a component that becomes the facilitated transport film 20a is prepared, applied to the porous support 20b, and dried. Can be made.
That is, first, add a hydrophilic compound, a carrier, a compound serving as a source of boron, and other components to be added as necessary to water (room temperature water or warm water) in sufficient amounts, and stir well. By doing so, the coating composition used as the facilitated-transport film | membrane 20a is prepared. As described above, boric acid and / or borates are preferably used as the boron source.
In the preparation of the coating composition, if necessary, dissolution of each component may be promoted by heating with stirring. Moreover, after adding a hydrophilic compound to water and melt | dissolving, precipitation (salting out) of a hydrophilic compound can be effectively prevented by adding a carrier gradually and stirring.

By applying this composition to the porous support 20b and drying, the facilitated transport film 20a is formed on the porous support 20b, and the acidic gas separation layer 20 is produced.
As described above, in the separation module 10 of the present invention, the facilitated transport film 20a contains a boron atom, and preferably has a crosslinked structure of a hydrophilic compound containing a boron atom. It is high and is formed with good adhesion to the porous support 20b. Therefore, it is possible to prevent the facilitated transport film 20a from being peeled off from the porous support 20b when the laminate 14 described later is wound or when the separation module 10 is operated, and an appropriate separation module 10 can be stably manufactured, and Stable operation is possible for a long time.

Here, the application and drying of the composition may be performed in a so-called single-wafer type, which is performed on a cut sheet-like porous support 20b cut into a predetermined size.
Preferably, the acid gas separation layer 20 is produced by so-called RtoR. That is, the prepared coating composition is applied while the porous support 20b is sent out from the feed roll formed by winding the long porous support 20b and conveyed in the longitudinal direction, and then the applied coating composition is applied. The product (coating film) is dried to produce the acidic gas separation layer 20 formed by forming the facilitated transport film 20a on the surface of the porous support 20b, and the produced acidic gas separation layer 20 is wound up.

What is necessary is just to set the conveyance speed of the porous support body 20b in RtoR suitably according to the kind of porous support body 20b, the viscosity of a coating liquid, etc.
Here, when the conveyance speed of the porous support 20b is too fast, the film thickness uniformity of the coating film of the coating composition may be lowered, and when it is too slow, the productivity is lowered. Considering this point, the conveyance speed of the porous support 20b is preferably 0.5 m / min or more, more preferably 0.75 to 200 m / min, and particularly preferably 1 to 200 m / min.

Various known methods can be used for applying the coating composition.
Specific examples include curtain flow coaters, extrusion die coaters, air doctor coaters, blade coaters, rod coaters, knife coaters, squeeze coaters, reverse roll coaters, bar coaters, and the like.

  Further, when the acidic gas separation layer 20 is formed by a coating method, the coating composition may be impregnated into the porous support 20b such as a nonwoven fabric from the viewpoint of imparting mechanical strength. Alternatively, a method of impregnating and applying the coating composition to a nonwoven fabric or the like and placing it on the porous support 20b can also be used. In addition, the continuous impregnation of this coating composition is formed as a facilitated transport film, and if the airtightness as the acidic gas separation layer 20 can be secured, the entire surface of the porous support 20b is impregnated with the coating composition. There is no need, and some of them may be impregnated.

The coating film of the coating composition may be dried by a known method. As an example, drying with warm air is exemplified.
The speed of the warm air may be set as appropriate so that the gel film can be dried quickly and the gel film does not collapse. Specifically, 0.5 to 200 m / min is preferable, 0.75 to 200 m / min is more preferable, and 1 to 200 m / min is particularly preferable.
The temperature of the hot air may be set appropriately as long as the deformation of the porous support 20b does not occur and the gel membrane 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.
For drying the coating film, heating of the porous support 20b may be used in combination as necessary.

As described above, the porous support 20b of the acidic gas separation layer 20 has at least the facilitated transport film 20a and the facilitated transport film 20a from the viewpoint of suppressing the penetration of the coating composition to be the facilitated transport film 20a and the facilitated transport film 20a. It is preferable that the surface on the contact side has hydrophobicity.
Further, since the facilitated transport film 20a needs to retain a large amount of moisture in the film in order for the carrier to function sufficiently, a polymer having extremely high water absorption and water retention is used. In addition, the facilitated transport film 20a increases the water absorption amount as the content of the carrier such as metal carbonate increases, and the separation performance of the acid gas is improved. Therefore, the facilitated transport film 20a is often a gel film or a low-viscosity film. Further, when separating the acidic gas, a source gas having a temperature of 100 to 130 ° C. and a humidity of about 90% is applied to a pressure of about 1.5 MPa. Therefore, the separation layer gradually soaks into the porous support 20b by use, and the acid gas separation ability tends to decrease with time.

  In order to prevent such inconvenience, the acidic gas separation layer 20 is more effectively immersed between the porous support 20b and the facilitated transport membrane 20a in the porous support 20b of the facilitated transport membrane 20a. It is preferable to have an intermediate layer for suppressing the above.

  The intermediate layer may be a hydrophobic layer having gas permeability, but preferably has a gas permeability and is denser than the porous support 20b. By providing such an intermediate layer, a highly uniform facilitated transport film 20a can be formed while preventing entry into the porous support 20b.

  The intermediate layer is only required to be formed on the porous support 20b, but may have a soaking area that is soaked in the porous support 20b. The soaking area is preferably as small as possible within the range in which the adhesion between the porous support 20b and the intermediate layer is good.

As the intermediate layer, a polymer layer (silicone resin layer) having a siloxane bond in the repeating unit is preferable. Examples of such a polymer layer include silicone-containing polyacetylene such as organopolysiloxane (silicone resin) and polytrimethylsilylpropyne. 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 1,000,000, and more preferably in the range of 100 to 100,000.
R _1n , R _2n , R ₃ , and R ₄ are each a group consisting of a hydrogen atom, an alkyl group, a vinyl group, an aralkyl group, an aryl group, a hydroxyl group, an amino group, a carboxyl group, and an epoxy group. Indicates which one is selected. Note that n existing R _1n and R _2n may be the same or different. In addition, 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 are selected from an alkyl group, vinyl group, aryl group, hydroxyl group, amino group, carboxyl group, epoxy group, or fluorine atom. It is. 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 or vinyl from the viewpoint of availability. Group, an aralkyl group having 7 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms are more preferable.
In particular, R _1n , R _2n , R ₃ , and R ₄ are preferably methyl groups or epoxy-substituted alkyl groups. For example, epoxy-modified polydimethylsiloxane (PDMS) can be suitably used.

The intermediate layer is a film having gas permeability, but if it is too thick, the gas permeability may be significantly reduced. The intermediate layer may be thin as long as it covers the entire surface of the porous support 20b without leaving the surface.
Considering this point, the film thickness of the intermediate layer is preferably 0.01 to 30 μm, more preferably 0.1 to 15 μm.

Such an intermediate layer is preferably formed by a coating method.
The coating composition serving as the intermediate layer is obtained by applying a resin layer (resin film) containing a monomer, dimer, trimer, oligomer, prepolymer, or a mixture of compounds such as the aforementioned PDMS derivative. ) And the like, which is a general coating composition (coating liquid / paint). This coating composition may be obtained by dissolving (dispersing) a monomer or the like in an organic solvent, and further contains a curing agent, a curing accelerator, a crosslinking agent, a thickener, a reinforcing agent, a filler, and the like. May be included.
What is necessary is just to prepare the coating composition used as such an intermediate | middle layer by a well-known method.

Moreover, the coating method of the coating composition used as an intermediate | middle layer can utilize various well-known methods similarly to the coating composition used as the above-mentioned facilitated-transport film | membrane 20a. The coating thickness of the coating composition is appropriately set according to the type of the intermediate layer to be formed, the concentration of the coating composition, etc., so that the thickness of the intermediate layer is 0.01 to 30 μm as described above. do it.
As a method for curing the coating composition, various known methods corresponding to the monomer serving as the intermediate layer, such as UV irradiation, heat curing, and electron beam irradiation, can be used. Prior to curing of the coating composition, the coating composition such as evaporation of an organic solvent may be dried as necessary.
Further, the intermediate layer may also be formed by so-called RtoR like the facilitated transport film 20a.

  When the acidic gas separation layer 20 has such an intermediate layer between the porous support 20b and the facilitated transport membrane 20a, the intermediate layer is formed after the intermediate layer is formed on the porous support 20b. Then, the facilitated transport film 20a is formed as described above.

The laminated body 14 is further laminated with a permeating gas flow path member 26.
The permeating gas channel member 26 is a member for allowing the acidic gas Gc that has reacted with the carrier and permeated the acidic gas separation layer 20 to flow through the through hole 12a of the central cylinder 12.
As described above, in the illustrated example, the laminate 14 includes the sandwiching body 36 in which the acidic gas separation layer 20 is folded in half with the facilitated transport film 20a inside, and the supply gas flow path member 24 is sandwiched therebetween. 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 14 is configured.

The permeating gas flow path member 26 functions as a spacer between the stacked bodies 14, and the acidic gas separated from the source gas G reaches the through hole 12 a of the central cylinder 12 toward the winding center (inner side) of the stacked body 14. A flow path for the gas Gc is formed.
As described above, the adhesive layer 30 is formed inside the permeating gas channel member 26. In order to properly form the adhesive layer 30, the permeate gas flow path member 26 needs to penetrate an adhesive layer 30 (adhesive 30a) described later. Considering this point, it is preferable that the permeating gas flow path member 26 has a mesh shape (net shape / textile shape / mesh structure).

  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.

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 flow path member 26 is a flow path of the acidic gas Gc that is separated from the source gas G and permeates the acidic gas separation layer 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%.
Further, deformation when pressure is applied can be approximated by elongation when a tensile test is performed. Specifically, the elongation when a load of 10 N / 10 mm width is applied is preferably within 5%, more preferably within 4%.
Furthermore, the pressure loss can be approximated by a flow rate loss of compressed air that flows at a constant flow rate. Specifically, when 15 L / min of air is passed through the 15 cm square permeate gas channel member 26 at room temperature, the flow rate loss is preferably within 7.5 L / min, and within 7 L / min. More preferably.

  Hereinafter, the lamination method of the laminated body 14, and the winding method of the laminated body 14, ie, the production method of the laminated body 14a will be described. In FIGS. 3A and 3B to 7 used in the following description, the supply gas flow path member 24 and the permeate gas flow path member are shown in order to simplify the drawings and clearly show the configuration. 26 shows only the end face (end part) in a net shape.

First, as conceptually shown in FIGS. 3 (A) and 3 (B), the extending direction of the central cylinder 12 and the short direction coincide with each other, and a kapton tape, an adhesive, etc. The end of the permeating gas flow path member 26 is fixed using the fixing means 34.
The tube wall of the central cylinder 12 is preferably provided with a slit (not shown) along the axial direction. In this case, the distal end portion of the permeating gas flow path member 26 is inserted into the slit and fixed to the inner peripheral surface of the central cylinder 12 by the 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.

Further, as conceptually shown in FIG. 4, the acidic gas separation layer 20 is folded in half with the facilitated transport membrane 20a inside, and the supply gas flow path member 24 is sandwiched therebetween. That is, a sandwiching body 36 is produced in which the supply gas flow path member 24 is sandwiched between the acidic gas separation layers 20 folded in half. At this time, the acidic gas separation layer 20 is not equally folded in half, but is folded in half so that one is slightly longer as shown in FIG.
In order to prevent the facilitated transport film 20a from being damaged by the supply gas flow path member 24, a sheet-like protective member folded in half is disposed in a trough where the acidic gas separation layer 20 is folded in half. preferable. Examples of the protective member include Kapton tape and PTFE tape.
As described above, in the separation module 10 of the present invention, the facilitated transport film 20a contains a boron atom, and preferably has a crosslinked structure of a hydrophilic compound containing a boron atom. high. Therefore, when the acidic gas separation layer 20 is folded in half, the facilitated transport film 20a can be prevented from peeling off from the porous support 20b, and the appropriate separation module 10 can be stably manufactured.

Further, an adhesive 30a to be the adhesive layer 30 is applied to the shorter surface of the acid gas separation layer 20 folded in half (the surface of the porous support 20b). The adhesive layer 30 and the adhesive 30a will be described in detail later.
As shown in FIG. 4, the adhesive 30 a (that is, the 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) in a band shape. Furthermore, it is applied to 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 FIGS. 5 (A) and 5 (B), the surface coated with the adhesive 30a is directed to the permeating gas flow path member 26, and the folded side is directed to the central cylinder 12. The sandwiching body 36 is laminated on the permeate gas channel member 26 fixed to the central cylinder 12, and the permeate gas channel member 26 and the acidic gas separation layer 20 (porous support 20b) are bonded.

Further, as shown in FIGS. 5A and 5B, an adhesive 30a to be the adhesive layer 30 is applied to the upper surface of the laminated sandwiching body 36 (the surface of the long porous support 20b). To do. 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 is also referred to as the upper side.
As shown in FIGS. 5 (A) and 5 (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. 6, a permeate gas flow path member 26 is laminated on the sandwiched body 36 coated with the adhesive 30 a, and the acidic gas separation layer 20 (porous support 20 b) and the permeate are permeated. The gas flow path member 26 is bonded to form the laminate 14.

Next, as shown in FIG. 4, as shown in FIG. 4, a sandwiching body 36 in which the supply gas flow path member 24 is sandwiched between the acidic gas separation layers 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. 5 (A) and 5 (B), and then, as shown in FIG. Then, the permeating gas flow path member 26 is laminated and bonded, and the second laminated body 14 is laminated.

Hereinafter, the steps of FIGS. 4 to 6 are repeated to stack a predetermined number of stacked bodies 14 as conceptually shown in FIG.
As shown in FIG. 7, this stacking is preferably performed so that the stacked body 14 is gradually separated from the center tube 12 in the winding direction as it goes upward. Thereby, winding (wrapping) of the laminated body 14 around the center tube 12 is easily performed, and the end portion or the vicinity of the end portion of each permeate gas flow path member 26 on the center tube 12 side is preferably the center tube. 12 can be contacted.

  When the predetermined number of the laminated bodies 14 are laminated, as shown in FIG. The adhesive 38b is applied between the sandwiching body 36 and the adhesive 36b.

Next, as shown by an arrow yw in FIG. 7, the laminated body 14 is wound (wound) around the central cylinder 12 so as to wind the laminated body 14.
As described above, in the separation module 10 of the present invention, the facilitated transport film 20a contains a boron atom, and preferably has a crosslinked structure of a hydrophilic compound containing a boron atom. Have Therefore, it is possible to prevent the facilitated transport film 20a from being peeled off from the porous support 20b when the laminate 14 is wound, and the appropriate separation module 10 can be stably manufactured.

After winding, the permeate gas flow path member 26 on the outermost periphery (that is, the lowermost layer first fixed to the central cylinder 12) is maintained for a predetermined time in a state where tension is applied in the pulling-out direction (winding and squeezing direction). Then, the adhesive 30a and the like are dried.
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 14a formed by winding the laminated body 14 around the central cylinder is completed.

  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 (transports) in the stacking direction through the acidic gas separation layer 20 to transmit 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 porous support 20b, and the adhesive 30a is bonded to the mesh-shaped permeating gas channel member 26. Therefore, the adhesive 30a permeates (impregnates) into the porous support 20b and the permeating gas flow path member 26, and the adhesive layer 30 is formed in 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 porous support 20b by opening the central tube 12 side. Further, the permeating gas channel member 26 is sandwiched between the facilitated transport films 20a.

As a result, an envelope-like flow path is formed in the permeate gas flow path member 26 of the laminate 14 so that the central tube 12 side is open.
Therefore, the acidic gas Gc that has passed through the acidic gas separation layer 20 and has flowed into the permeate gas flow path member 26 flows toward the central cylinder 12 in the permeate gas flow path member 26 without flowing out, It flows into the center tube 12 from the through hole 12a. In addition, the raw material gas G and the residual gas Gr are blocked by the adhesive layer 30 and mixed into the acidic gas Gc that has permeated the acidic gas separation layer 20 (the acidic gas Gc in the permeating gas channel member 26). No.
That is, the adhesive layer 30 has an action as a flow path regulating member for the acidic gas Gc and an action as a sealing member that seals each gas in a predetermined region while bonding the members.

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.
Thereby, the adhesive layer 30 (adhesive 30a) can be suitably infiltrated into the porous support 20b and the permeating gas channel member 26.

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 14a produced in this way.
As described above, the telescoping prevention plate 16 is so-called that the laminated body 14a 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.
The telescope prevention plate 16 connects the annular outer ring portion 16a, the annular inner ring portion 16b that is included in the outer ring portion 16a with the center aligned, and the outer ring portion 16a and the inner ring portion 16b. And ribs (spokes) 16c to be fixed. As described above, the center tube 12 around which the stacked body 14 is wound passes through the inner ring portion 16b.
The ribs 16c are provided radially at equal angular intervals from the center of the outer ring portion 16a and the inner ring portion 16b. In the telescope prevention plate 16, the gap between the ribs 16c is an opening 16d between the outer ring portion 16a and the inner ring portion 16b and through which the raw material 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 14a. However, in general, in order to use the entire end face of the laminated body 14a for supplying the source gas and discharging the residual gas Gr, the telescope prevention plate 16 and the end face of the laminated body 14a are: It is arranged with a slight gap.

Various materials can be used for the telescope prevention plate 16 as long as it has sufficient strength, heat resistance, and moisture resistance.
Specifically, metal materials (for example, stainless steel (SUS), aluminum, aluminum alloy, tin, tin alloy, etc.), resin materials (for example, 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, epoxy resin, nitrile resin, polyetheretherketone resin (PEEK), polyacetal resin (POM), polyphenylene sulfide (PPS) Etc.), and fiber reinforced plastics of these resins (for example, as the fiber, glass fiber, carbon fiber, stainless steel fiber, aramid fiber, etc.) are particularly preferable long fibers. Fiber-reinforced polypropylene, long glass fiber-reinforced polyphenylene sulfide), as well as ceramics (such as zeolite, alumina, etc.) and the like are preferably exemplified.
In addition, when using resin, you may use resin reinforced with glass fiber etc.

  The covering layer 18 is provided so as to cover the circumferential surface of the laminated body roll 14 a or the telescope prevention plate 16. The covering layer 18 is for blocking the discharge of the raw material gas G and the residual gas Gr from the peripheral surface of the laminated body 14a to the outside. That is, the coating layer 18 is for blocking the discharge of the raw material gas G and the residual gas Gr from outside the end face of the laminated body 14a.

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, an FRP-made wire rod is impregnated with the adhesive used for the adhesive layer 30 described above, and the wire rod impregnated with the adhesive is stacked with no gaps, if necessary. Or the coating layer 18 wound around the telescope prevention board 16 further is illustrated. Moreover, you may form the coating layer 18 by well-known FRP process.
In this case, if necessary, a sheet shape such as Kapton tape for preventing the adhesive wound into the laminated body 14a between the coating layer 18 and the laminated body 14a. 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]
<Production of acid gas separation layer>
`` 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 '' The concentration of the copolymer containing a copolymer of polyvinyl alcohol (PVA) -polyacrylic acid copolymer (PAA) (molar ratio: PVA / PAA = 3/7) synthesized with reference to the described method is 4 To a 3% by mass aqueous solution, a 40% by mass cesium carbonate (manufactured by Rare Metals) aqueous solution was added so that the amount of cesium carbonate relative to the PVA-PAA copolymer was 200% by mass. That is, in this example, cesium carbonate serves as a carrier for the facilitated transport film 20a.
Further, boric acid is added to this aqueous solution so that the amount of boron atoms with respect to cesium carbonate is 0.8% by mass, and the mixture is stirred and degassed to form the facilitated transport film 20a. Was prepared.

Next, the facilitated transport film 20a is obtained by applying the prepared coating composition to a porous support 20b (a laminate (manufactured by GE Corp.) obtained by laminating porous PTFE on the surface of a PP nonwoven fabric) and drying it. And an acidic gas separation layer 20 made of a porous support 20b.
The thickness of the facilitated transport film 20a was 50 μm.

<Production of separation module>
A central cylinder 12 having a slit extending in the center line direction on the side surface was prepared. The permeating gas flow path member 26 was fixed to the slit of the central cylinder 12 so as to be sandwiched therebetween. As a result, as shown in FIGS. 3A and 3B, the end portion in the winding direction of the permeating gas flow path member 26 was fixed to the peripheral surface of the central cylinder 12. The center tube 12 has a partition inside.
As the permeating gas channel member 26, a tricot knitted polyester knitted fabric having a thickness of 350 μm was used.

On the other hand, the produced acidic gas separation layer 20 was folded in two with the facilitated transport membrane 20a inside. As shown in FIG. 4, the two folds were performed so that one acidic gas separation layer 20 was slightly longer. A fluorine-based tape was attached to the valley of the acid gas separation layer 20 folded in half, and the end of the supply gas flow path member 24 was reinforced so as not to damage the valley of the facilitated transport film 20a. Moreover, the hole of the porous support 20b in the folded portion was filled with an adhesive made of an epoxy resin.
Next, the supply gas flow path member 24 (a polypropylene net having a thickness of 0.5 mm) was sandwiched between the acid gas separation layer 20 folded in half, and a sandwich body 36 was produced.

As shown in FIG. 4, on the porous support 20b side where the acidic gas separation layer 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 having a viscosity of about 40 Pa · s (E120HP manufactured by Henkel Japan) was used.
Next, with the side to which the adhesive 30a is applied facing downward, as shown in FIGS. 5 (A) and 5 (B), the sandwiching body 36 and the permeating gas channel member 26 fixed to the central cylinder 12 are provided. Laminated and glued.
Next, on the upper surface of the acidic gas separation layer 20 of the sandwiching body 36 laminated on the permeating gas flow path member 26, as shown in FIG. The adhesive 30a was applied to the entire region in the width direction in the vicinity of the end on the side opposite to the folded portion in the winding direction. Further, as shown in FIG. 6, a permeated gas flow path member 26 is laminated on the acidic gas separation layer 20 coated with the adhesive 30a and bonded to form the first layered product 14. did.

In the same manner as described above, another sandwiched body 36 made of the acidic gas separation layer 20 shown in FIG. 4 is produced, and similarly, on the porous support 20b side of the short acidic gas separation layer 20 in the same manner. The adhesive 30a was applied to the film. Next, in the same manner as in FIG. 5 (A), the sandwiched body 36 is set to 1 side toward the first layered body 14 (the permeate gas flow path member 26) formed first on the side to which the adhesive 30a is applied. It laminated | stacked on the laminated body 14 (the member 26 for permeate gas channels) of the layer, and was adhere | attached. Further, an adhesive 30a is applied to the upper surface of the sandwiching body 36 in the same manner as in FIG. 5A, and a permeating gas flow path member 26 is laminated thereon and adhered in the same manner as in FIG. A second layered laminate 14 was formed.
Further, in the same manner as the second layer, a laminate in which the third-layer laminate 14 was formed on the second-layer laminate 14 was formed.

After laminating the three-layer laminate 14 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 onto the permeating gas flow path member 26 between the central cylinder 12 and the lowermost layered laminate 14. 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. 7, the 20 stacked layers 14 are wound around the central cylinder 12 in a multiple manner, and tension is applied in the direction of pulling the stacked body 14. Thus, a laminate wound product 14a was obtained.

Furthermore, the PPS telescope prevention plate 16 made of 40% glass fiber having the shape shown in FIG. 1 is attached to both ends of the laminated body 14a by inserting the central tube 12 through the inner ring portion 16b. It was.
Furthermore, the coating layer 18 was formed by performing FRP processing on the peripheral surface of the telescope prevention plate 16 and the peripheral surface of the laminated body 14a, and the separation module 10 was manufactured.
The membrane area of the manufactured separation module 10 is 1.2 m ² in total for the three layers (design value).

[Example 2]
In the preparation of the coating composition for forming the facilitated transport film 20a, sodium tetraborate was used instead of boric acid, and sodium tetraborate was added so that the amount of boron atoms relative to cesium carbonate was 0.8% by mass. A separation module 10 was produced in the same manner as in Example 1 except for the addition. Therefore, in this example, the amount of cesium carbonate relative to the PVA-PAA copolymer is 200% by mass.
[Examples 3 to 10 and Comparative Examples 1 and 2]
In the preparation of the coating composition for forming the facilitated transport film 20a, the amount of cesium carbonate with respect to the PVA-PAA copolymer and the amount of boron atoms with respect to cesium carbonate are the amounts shown in Table 1, A separation module 10 was produced in the same manner as in Example 2 except that the addition amount of% cesium carbonate and the addition amount of sodium tetraborate were changed.

[Examples 11 and 12]
Except for changing the thickness of the facilitated transport film 20a to 10 μm (Example 11), and
A separation module 10 was produced in the same manner as in Example 2 except that the thickness of the facilitated transport film 20a was changed to 1000 μm (Example 12).

[Example 13]
A separation module was produced in the same manner as in Example 2 except that an intermediate layer was formed between the facilitated transport film 20a and the porous support 20b. That is, the acidic gas separation layer of this separation module has an intermediate layer on the porous support 20b, and a facilitated transport membrane 20a on the intermediate layer.

The intermediate layer (acid gas separation layer) was formed as follows.
As the coating composition for forming the intermediate layer, epoxy-modified polydimethylsiloxane (KF-102 manufactured by Shin-Etsu Chemical Co., Ltd.) and 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate (Tokyo) as the curing agent The coating composition which added Kasei Kogyo Co., Ltd.) was prepared. The addition amount of the curing agent was 0.5% by mass with respect to the epoxy-modified polydimethylsiloxane.

A coating composition for forming the prepared intermediate layer is applied to the same porous support 20b as in Example 1, and the coating composition is cured by irradiating with ultraviolet rays, and silicone is applied to the porous support 20b. An intermediate layer made of resin was formed.
The thickness of the intermediate layer was 10 μm. Here, the thickness of the intermediate layer was the sum of the thickness of the silicone resin soaked in the porous support 20b and the thickness of the silicone resin formed on the porous support 20b. The thickness of the silicone resin soaked into the porous support 20b was measured by Si element distribution by EDX (energy dispersive X-ray absorption method).
On this intermediate layer, the facilitated transport film 20a was formed in the same manner as in Example 2 to obtain an acidic gas separation layer.

  In the production of the separation modules of Examples 1 to 13, a part of the produced facilitated transport film 20a is arbitrarily selected, and the facilitated transport film 20a is washed with cold water to remove the carrier and the uncrosslinked boron atomic city. Then, when confirmed by infrared absorption analysis, the structure shown in Formula (1) was confirmed.

[Comparative Example 3]
In preparation of the coating composition for forming the facilitated transport film 20a, except that glutaraldehyde was used instead of boric acid and glutaraldehyde was added so that the amount of glutaraldehyde with respect to cesium carbonate was 0.8% by mass. A separation module 10 was produced in the same manner as in Example 1.
Therefore, in this example, the amount of cesium carbonate relative to the PVA-PAA copolymer is 200% by mass.

[Performance evaluation]
Each manufactured separation module 10 was accommodated in a cylindrical airtight container with only the open end 12b of the center tube 12 protruding to the outside. This sealed container is heated to 130 ° C., and a gas of He: H ₂ O = 70: 30 (volume ratio) is introduced into the container, and a pressure of 0.3 MPa is applied, and the open end of the central cylinder 12 is opened. The flow rate of helium gas discharged from 12b was measured.
A when the flow rate of helium gas discharged from the open end 12b of the central cylinder 12 is less than 100 mL (milliliter) / min;
B when the flow rate of helium gas discharged from the open end 12b of the central cylinder 12 is 100 mL / min or more and less than 200 mL / min;
The case where the flow rate of helium gas discharged from the open end 12b of the central cylinder 12 was 200 mL / min or more was evaluated as C;
The results are shown in the table below.

As shown in the above table, the facilitated transport film contains boron atoms, the carrier content is 20 to 500% by mass with respect to the hydrophilic compound, and the boron atom content is 0.1% with respect to the carrier. 10% by mass of the separation module of the present invention has a high membrane strength of the facilitated transport membrane 20a and can prevent damage to the facilitated transport membrane 20a due to winding of the laminate, etc., and prevent gas leakage. ing.
On the other hand, in Comparative Example 1 in which the amount of boron atoms relative to the carrier is small, Comparative Example 2 in which the amount of carrier relative to the hydrophilic compound is excessive, and Comparative Example 3 that does not contain boron atoms, the film strength of the facilitated transport film 20a is poor. It is sufficient that the facilitated transport film 20a is damaged when the laminated body is wound or the like, and the gas leaks.
From the above results, the effects of the present invention are clear.

DESCRIPTION OF SYMBOLS 10 (Acid gas) separation module 12 Center tube 14 Laminated body 14a Laminated body roll 16 Telescope prevention board 16a Outer ring part 16b Inner ring part 16c Rib 16d Opening part 18 Covering layer 20 Acid gas separation layer 20a Accelerated transport film 20b Porous support body 24 Supply gas flow path member 26 Permeate gas flow path member 30 Adhesive layer 30a Adhesive 34 Fixing means 36 Holding body 40 Adhesive member

Claims (11)

A central tube having a through-hole formed in the tube wall;
A supply gas flow path member serving as a flow path for the source gas;
A carrier that reacts with an acidic gas, a hydrophilic compound for supporting the carrier, and a boron atom, and the content of the carrier is 20 to 500% by mass with respect to the hydrophilic compound, and the boron atom Content of 0.1 to 10% by mass with respect to the carrier, a facilitated transport membrane that separates the acidic gas from the source gas flowing through the supply gas flow path member, and a porous material that supports the facilitated transport membrane An acidic gas separation layer having a support;
A permeating gas channel member that serves as a channel through which the acidic gas that has reacted with the carrier and permeated the acidic gas separation layer flows to the central cylinder;
An acidic gas separation module comprising at least one laminate having the supply gas flow path member, the acidic gas separation layer, and the permeate gas flow path member wound around the central tube.   The acidic gas separation module according to claim 1, wherein the boron atom and the hydrophilic compound are cross-linked in the facilitated transport film. The acidic gas separation module according to claim 1 or 2, wherein the facilitated transport membrane includes at least one of a structure represented by formula (1) and a structure represented by formula (2).
  The acidic gas separation module according to any one of claims 1 to 3, wherein the hydrophilic compound is a copolymer of polyvinyl alcohol and polyacrylic acid.   The acidic gas separation module according to claim 1, wherein the carrier is an alkali metal compound.   The acid gas separation module according to claim 1, wherein the facilitated transport film has a thickness of 3 to 1000 μm.   The acidic gas separation module according to claim 1, wherein the porous support has a porous membrane and an auxiliary support membrane that supports the porous membrane.   The acidic gas separation module according to claim 7, wherein the porous membrane is made of polytetrafluoroethylene.   The acidic gas separation module according to any one of claims 1 to 8, further comprising a hydrophobic intermediate layer having gas permeability between the porous support and the facilitated transport membrane.   The acidic gas separation module according to claim 9, wherein the intermediate layer is a silicone resin layer.   The laminate has a structure in which the acidic gas separation layer is folded in half to sandwich the supply gas flow path member, and the permeate gas flow path member is stacked on the sandwich body. The acidic gas separation module of any one of Claims 1-10.