JP6145349B2 - Acid gas separation module - Google Patents

Description

  The present invention relates to an acid gas separation module that selectively separates an acid gas from a raw material gas. Specifically, the present invention relates to an acidic gas separation module capable of improving the raw material gas processing efficiency.

  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 acidic gas separation module that separates an acidic gas from a raw material gas using an acidic gas separation membrane that selectively permeates the acidic gas has been developed.

As an example, in Patent Document 1, a laminated body including an acidic gas separation membrane is multiplexed in a central tube (a central permeate collecting tube) for collecting separated acidic gas having a through-hole formed in a tube wall. A wound acid gas separation module is disclosed.
The acid gas separation module disclosed in Patent Document 1 is a dissolution diffusion type acid gas separation module using a so-called dissolution diffusion membrane as the acid gas separation membrane. 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 membrane, and a raw material gas (a mixed gas composed of CO ₂ , H _2, and H ₂ O) is supplied to the raw material chamber. An acidic gas separation module (experimental apparatus) is disclosed that extracts acidic gas selectively separated (permeated) by a gas separation membrane from a permeation chamber.
The acidic gas separation module disclosed in Patent Document 2 is a facilitated transport type acidic gas separation module using a so-called facilitated transport membrane as the acidic gas separation membrane. 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, as shown in Patent Document 1, a laminate having an acidic gas separation membrane is wound around a central cylinder for collecting the separated acidic gas (wound around the central cylinder). A so-called spiral acid gas separation module is known. The spiral type acidic gas separation module can increase the area of the acidic gas separation membrane. Therefore, the spiral type acidic gas separation module can be efficiently processed.

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

By the way, as shown in Patent Document 1, such an acidic gas separation module, particularly a spiral type module, generally has a supply gas flow path member (supply) in which the inside becomes a flow path of a source gas. In many cases, a spacer) and a permeate gas channel member (permeate spacer) that serves as an acid gas channel separated from the inside thereof are used. Such a flow path member is usually composed of a mesh-like sheet.
In this case, as shown in Patent Document 1, as an example, the acidic gas separation module sandwiches the supply gas flow path member with the acidic gas separation membrane and sandwiches both surfaces thereof with the permeate gas flow path member. It is comprised by the laminated body formed.

  In the acid gas separation module, the source gas contacts the acid gas separation membrane while flowing inside the supply gas flow path member, and the acid gas is separated. The acidic gas separated from the raw material gas permeates the acidic gas separation membrane and flows into the permeating gas channel member. The acidic gas that has flowed into the permeate gas flow path member flows through the permeate gas flow path member, and is discharged and collected outside. The source gas from which the acid gas has been separated flows as it is inside the supply gas flow path member, and is discharged from the supply gas flow path member to the outside for recovery.

  Therefore, in such an acidic gas separation module, the separation efficiency of acidic gas can be increased as the distance that the source gas contacts the acidic gas separation membrane is longer.

  The object of the present invention is to lengthen the distance at which the source gas contacts the acidic gas separation membrane by lengthening the source gas flow path in the supply gas flow path member in the acidic gas separation module using the acidic gas separation membrane. Thus, an object of the present invention is to provide an acidic gas separation module capable of improving the raw material gas processing efficiency, ie, the acidic gas separation efficiency.

In order to achieve this object, the acidic gas separation module of the present invention comprises a sheet-like acidic gas separation layer having an acidic gas separation membrane for separating acidic gas from a raw material gas, and a sheet-like layer laminated on the acidic gas separation layer. And having a supply gas channel member whose inside is a source gas channel,
Further, the present invention provides an acidic gas separation module characterized by having a flow path changing member for changing the flow path of the source gas inside the supply gas flow path member.

In such an acidic gas separation module of the present invention, when the feed direction of the source gas is the x direction and the direction orthogonal to the x direction is the y direction, the flow path changing member is y in the supply gas flow path member. It is preferable to extend toward the y direction from one end of the direction.
A plurality of flow path changing members are arranged in the x direction, and at least one flow path changing member is directed from one end in the y direction of the supply gas flow path member toward the y direction. It is preferable that the at least one other flow path changing member extends in the y direction from the end of the supply gas flow path member opposite to the y direction.
Moreover, it is preferable that the flow path changing member located in the uppermost stream in the x direction extends in a direction toward both the x direction and the y direction.
Moreover, it is preferable that the flow path changing member changes the flow path of the raw material gas so as to be directed in the direction of flowing backward with respect to the supply direction of the raw material gas and then to the supply direction of the raw material gas.
The flow path changing member is a wall-shaped member having a height direction in the thickness direction of the supply gas flow path member and extending in the surface direction of the supply gas flow path member. The thickness is preferably 5 to 50 mm.
In the surface direction of the supply gas flow path member, the area of the flow path changing member is preferably 0.01 to 10% of the total area of the supply gas flow path member.
Moreover, it is preferable that it is the spiral type formed by winding the laminated body containing the member for supply gas flow paths, and an acidic gas separation layer.
Furthermore, the supply gas flow path member is sandwiched by the acidic gas separation layer, and further, a sheet-like permeation gas flow path waist member that becomes the acidic gas flow path separated by the acidic gas separation membrane is laminated on both sides thereof. It is preferable to have at least one laminate.

The acidic gas separation module of the present invention changes the flow path of the raw material gas inside the supply gas flow path member by the flow path changing member provided inside the supply gas flow path member, The distance in contact with the acid gas separation membrane can be increased.
Therefore, according to the acidic gas separation module of the present invention, it is possible to improve the raw material gas processing efficiency, that is, the acidic gas separation efficiency, as compared with the conventional acidic gas separation module.

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)-(D) are figures which show notionally an example of the member for supply gas flow paths used for the acidic gas separation module of this invention. (A) And (B) is a conceptual diagram for demonstrating the preparation methods of the acidic gas separation module shown in FIG. It is a conceptual diagram for demonstrating the production method of the acidic gas separation module shown in FIG. (A) And (B) is a conceptual diagram for demonstrating the preparation methods of the acidic gas separation module shown in FIG. It is a conceptual diagram for demonstrating the production method of the acidic gas separation module shown in FIG. It is a conceptual diagram for demonstrating the production method of the acidic gas separation module shown in FIG.

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

FIG. 1 is a partially cutaway schematic perspective view of an example of the acid gas separation module of the present invention.
As shown in FIG. 1, the acid gas separation module 10 basically includes a center tube 12, a laminate 14 having an acid gas separation membrane (facilitated transport membrane 20 a), and a telescope prevention plate 16. Composed. In the following description, the acid gas separation module is also simply referred to as a separation module.
The separation module 10 separates carbon dioxide as an acidic gas Gc from a raw material gas G containing, for example, carbon monoxide, carbon dioxide (CO ₂ ), water (water vapor), and hydrogen.

  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 laminate 14 is covered with a gas impermeable coating layer 18.

  In the following description, a wound product of a product obtained by laminating a plurality of laminates 14 wound around the central cylinder 12 (that is, a substantially cylindrical product by the laminate 14 wound by being laminated) For convenience, it is also referred to as a spiral laminate 14a.

Here, the separation module of the present invention may be a flat membrane type in addition to the spiral type as illustrated.
For example, a laminate (or this laminate) in which an acid gas separation membrane (acid gas separation layer) is sandwiched between supply gas channel members described later and both surfaces thereof are sandwiched between permeate gas channel members described later. A flat membrane type separation module or a hollow fiber type separation module which is used without being wound may be used.
However, the spiral separation module 10 of the illustrated example is preferably used in that the occurrence of defects due to use under high pressure can be prevented, and the decrease in separation performance due to the occurrence of defects can be prevented.

In the separation module 10 shown in FIG. 1, the source gas G from which the acidic gas is separated is supplied to the end surface of the spiral laminate 14a through, for example, the telescope prevention plate 16 (the opening 16d) on the far side in FIG. Then, the acid gas Gc is separated while flowing into the laminate 14 from the end face and flowing through the laminate 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 has been separated (hereinafter referred to as the residual gas Gr for convenience) is discharged from the end face on the opposite side to the supply side of the spiral laminated body 14a (laminated body 14) to prevent telescoping. It is discharged out of the separation module 10 through the 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. This is an adhesive layer 30 in which the flow path is formed in an envelope shape opened on the center tube 12 side.

As described above, the separation module 10 in the illustrated example is formed by laminating a plurality of the laminates 14 and winding (wrapping) them around the central cylinder 12 to form a substantially cylindrical spiral laminate 14a. It has a configuration.
Here, in the present invention, for convenience, the supply direction of the source gas G is the x direction, and the direction orthogonal to the x direction is the y direction. In the separation module 10 of the illustrated example that is a spiral type, the winding direction of the laminated body 14 coincides with the y direction. Therefore, the direction orthogonal to the winding direction of the laminated body 14 is the supply direction of the raw material gas G. It coincides with a certain 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 supply direction of the raw material gas G, and the y direction orthogonal to the x direction coincides with the winding direction of the laminate 14 (hereinafter also referred to as the winding direction).
In the illustrated example, the laminated body 14 has a permeating gas flow path member 24 sandwiched between two folded acid gas separation layers 20 to form a sandwiching body 36 (see FIG. 5). The road member 26 is laminated. This configuration will be described in detail later.

As described above, in the separation module 10, the source gas G is supplied from one end face of the spiral laminated body 14 a through the telescope prevention plate 16. That is, the source gas G is supplied to the end portions (end surfaces) of the stacked bodies 14.
As conceptually shown in FIG. 2, the source gas G supplied to the end face in the x direction of the stacked body 14 flows in the supply gas flow path member 24 in the x direction. Here, in the separation module 10 of the present invention, the supply gas flow path member 24 has flow path changing members (flow path walls 50a and 50b) that change the flow path of the source gas G flowing inside. Therefore, the flow path of the source gas G in the supply gas flow path member 24 can be lengthened. This will be described in detail later.
The acidic gas Gc in contact with the acidic gas separation layer 20 (facilitated transport membrane 20a) in the flow in the supply gas flow path member 24 is separated from the raw material gas G, and the acidic gas separation layer 20 is separated from the laminate 14. In the laminating direction (transported in the laminating direction by the carrier of the facilitated transport film 20a) and flows into the permeating 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), reaches the central cylinder 12, and is centered from the through hole 12 a of the central passage 12. It flows into the cylinder 12. The acidic gas Gc that has flowed into the central cylinder 12 flows through the central cylinder 12 in the x direction and is discharged from the open end 12b.
Further, the residual gas Gr from which the acidic gas Gc has been removed flows in the supply gas flow path member 24 in the x direction, and is discharged from the opposite end face of the spiral laminated body 14a. 16d) and discharged to the outside of the separation module 10.

The supply gas flow path member 24 is a sheet-like member that is supplied with the source gas G from the end in the x direction and that contacts the source gas G flowing in the member with the acidic gas separation layer 20. In the illustrated example, the supply gas flow path member 24 is rectangular as an example. Further, as described above, the supply gas flow path member 24 is provided therein with a flow path changing member that changes (forcibly changes) the flow path of the source gas G.
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. Considering this point, the supply gas flow path member 24 is preferably a member having a mesh shape (net shape / mesh structure).

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

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.

  Here, in the separation module 10 of the present invention, a flow path changing member that changes the flow path of the source gas G is provided inside the supply gas flow path member 24.

FIG. 3A conceptually shows the supply gas flow path member 24 in a state in which the winding is rewound and planarized. 3A to 3D, the mesh of the supply gas flow path member 24 is omitted in order to simplify the drawing and clearly show the configuration.
As shown in FIG. 3A, the supply gas flow path member 24 has flow path walls 50a and 50b as flow path regulating members therein. Both of the flow path walls 50a and 50b have a height corresponding to the entire region in the thickness direction of the supply gas flow path member 24, and extend in the surface direction of the supply gas flow path member 24. It is a member.
The flow path wall (flow path regulating member) may be lower than the entire area in the thickness direction of the supply gas flow path member 24. However, it is preferable that the flow path wall has a height that blocks the entire region of the supply gas flow path member 24 in the thickness direction in that the flow path of more source gas G can be changed.

In the illustrated example, the channel wall 50a is inclined in the x direction (source gas supply direction) from the end on the central tube 12 side in the y direction (winding direction) in the supply gas channel member 24. Extends in the direction. On the other hand, the flow path wall 50b provided on the downstream side in the x direction (hereinafter also simply referred to as upstream / downstream) with respect to the flow path wall 50a is connected to the central cylinder 12 in the y direction in the supply gas flow path member 24. From the opposite end, it inclines in the direction opposite to the x direction and extends in the y direction. Further, both the flow path walls are formed so as not to reach the entire area in the y direction.
In the following description, for convenience, the center tube 12 side in the y direction is also referred to as a base end, and the opposite side of the center tube 12 is also referred to as a tip end.

Reference numeral 52 in the drawing is a wall-like member (wall member 52) similar to the flow path wall 50a and the like, which is formed in the entire region in the x direction at the tip of the supply gas flow path member 24.
As will be described later, since the separation module 10 has a configuration in which a plurality of stacked bodies 24 are stacked and wound, the raw material gas G flowing into one supply gas flow path member 24 is basically supplied to the separation module 10. There is no discharge from the front end side of the gas flow path member 24. However, since the raw material gas G may be discharged from the front end side of the supply gas flow path member 24 even with a small amount, the raw material gas G can be more reliably provided by having the wall member 52 as shown in the illustrated example. Can be prevented from being discharged from the front end side of the supply gas flow path member 24, and the raw material gas can be processed more efficiently.

In such a supply gas flow path member 24, as conceptually shown in FIG. 3A, most of the raw material gas G flowing into the supply gas flow path member 24 from the end in the x direction The flow path toward the x direction is changed by the upstream flow path wall 50a to the tip side (y direction) and the direction toward the x direction. Next, the raw material gas G whose flow path is changed by the flow path wall 50a is further supplied to the downstream flow path wall 50b, the distal end side end (wall member 52) or the proximal end side of the supply gas flow path member 24. The flow path is changed at the end or the like, and reaches the downstream end of the supply gas flow path member 24.
Further, the source gas G whose flow path is not changed by the flow path wall 50a is also changed in flow path by the downstream flow path wall 50b, and further, the front end side end portion and the base of the supply gas flow path member 24 are changed. The flow path is changed by the end side end or the like, and reaches the downstream end of the supply gas flow path member 24.

  That is, in the member 24 for supply gas flow path in the illustrated example, compared to a normal supply gas flow path member having no flow path wall, the flow path of the source gas G is linear in the x direction. The flow path of the source gas G in the supply gas flow path member 24 is much longer.

As described above, the source gas G flows through the supply gas flow path member 24 and contacts the acidic gas separation layer 20 (facilitated transport film 20a) to separate the acidic gas. Therefore, the longer the flow path inside the supply gas flow path member 24, the longer the distance at which the source gas G contacts the acidic gas separation layer 20, and the processing efficiency of the raw gas G, that is, the acidic gas separation efficiency is improved. .
Therefore, according to the separation module 10 of the present invention in which the supply gas flow path member 24 has flow path walls 50 a and 50 b (flow path changing members for the raw material gas G), the raw material gas G contacts the acidic gas separation layer 20. By increasing the distance, the processing efficiency of the source gas G can be greatly improved.

The supply gas flow path member 24 in the illustrated example has two flow path walls in the supply direction of the raw material gas G. However, in the separation module of the present invention, one flow path wall may be provided. .
However, in the present invention, the flow path of the source gas G in the supply gas flow path member 24 can be made longer when the supply gas flow path member 24 has a plurality of flow path walls.

  Accordingly, in the separation module 10 of the present invention, for example, as conceptually shown in FIG. 3B, the supply gas flow path member 24 has three flow path walls 50c, 50d and 50e therein. Also good. Thereby, the flow path of the source gas G in the supply gas flow path member 24 can be further increased.

Here, when the supply gas flow path member 24 has a plurality of flow path walls, as shown in FIGS. 3A and 3B, from the base end toward the front end side (y direction). It is preferable that the extending channel walls (50a, 50c and 50e) and the extending channel walls (50b, 50d) extending from the distal end toward the base end side (same as above) are mixed.
By having such a configuration, compared with the case where only the flow path wall extending in the y direction from only one end portion in the y direction (only the base end or only the front end) is provided, the supply gas flow The flow path of the source gas G in the road member 24 can be lengthened.

  In addition to the linear shape as shown in FIGS. 3A and 3B, the flow path wall may have a curved shape or a bent (reflected) bent line shape.

An example is shown in FIG. The example shown in FIG. 3C has two flow path walls, an upstream flow path wall 50f and a downstream flow path wall 50g.
In the supply gas flow path member 24, the upstream flow path wall 50f is inclined in the x direction (source gas supply direction) from the base end (end portion on the center tube 12 side) and extends toward the distal end side. A region extending from the downstream end portion in the x direction, and a region extending from the downstream end portion in the direction opposite to the x direction and extending toward the proximal end side.
On the other hand, the flow path wall 50g on the downstream side is inclined in the direction opposite to the x direction from the distal end (the end opposite to the center tube 12) and extends toward the proximal end in the supply gas flow path member 24. A region extending from the upstream end portion in the direction opposite to the x direction, and a region extending from the upstream end portion in the x direction and extending toward the distal end side.
Further, the flow path wall 50f and the flow path wall 50g do not contact each other, have an overlapping region when viewed in the y direction, and are in a direction opposite to the x direction of the downstream flow path wall 50g. The extending region is located closer to the base end side than the region extending in the x direction of the upstream flow path wall 50f.

According to the flow path wall 50f and the flow path wall 50g, the flow path is changed so that the raw material gas G flowing into the supply gas flow path member 24 flows back in the x direction by the flow path wall 50g. Then, the flow path is changed by the flow path wall 50f toward the x direction.
Therefore, according to the flow path wall 50f and the flow path wall 50g, the flow path of the source gas G is changed in the supply gas flow path member 24 so as to reciprocate 1.5 times between the supply direction and the reverse direction. Therefore, the flow path of the raw material gas G in the supply gas flow path member 24 can be made very long so that the distance at which the raw material gas G contacts the acidic gas separation layer 20 can be made very long.

In the example shown in FIGS. 3 (A) to 3 (C), the flow path walls 50a, 50c and 50f arranged at the uppermost stream change the flow path of the source gas G in the direction toward both the x direction and the y direction. doing.
However, the present invention can use various configurations other than this. For example, as in the example shown in FIG. 3D, the flow path walls 50h and 50i may both be arranged extending in the y direction. Alternatively, the most upstream flow path wall may be inclined in the direction opposite to the x direction and extend in the y direction.
However, in consideration of the pressure loss of the raw material gas G, the flow path wall arranged at the uppermost stream changes the flow path of the raw material gas G in the direction toward both the x direction and the y direction as shown in the example of the drawing. Preferably it is provided.

In each of the examples shown in FIG. 3, the most upstream flow path wall extends in the y direction from the base end (end on the central tube 12 side) of the supply gas flow path member 24. However, the present invention may have a configuration in which the most upstream channel wall extends in the y direction from the tip of the supply gas channel member 24.
Here, since the separation module in the illustrated example is a spiral type, the base end side of the supply gas flow path member 24 has a high winding curvature. For this reason, it may be advantageous in terms of efficiency and the like to change the flow path wall of the most upstream flow path from the proximal end to the distal end as in the illustrated example.

In the separation module 10 of the present invention, the thickness L of the flow path wall may be appropriately determined according to the flow rate and temperature of the supplied raw material gas G, the area of the supply gas flow path member 24, and the like.
Here, if the thickness L of the flow path wall is too thin, the strength of the flow path wall may be insufficient and may be damaged during use. Further, since the acidic gas separation layer 20 (facilitated transport membrane 20a) cannot be used effectively at the position where the flow path wall exists, if the thickness L of the flow path wall is too thick, the processing efficiency of the raw material gas G is lowered. End up.
Considering this point, the thickness L of the flow path wall is preferably 5 to 50 mm, more preferably 5 to 30 mm, and particularly preferably 5 to 20 mm.

Further, in the separation module 10 of the present invention, the formation area of the flow path wall (flow path changing member) in the surface direction of the supply gas flow path member 24 depends on the performance of the facilitated transport film 20a and the flow rate of the supplied raw material gas G. The temperature may be determined appropriately according to the temperature, the area of the supply gas flow path member 24, and the like.
Here, if the formation area of the flow path wall is too small, the effect of forming the flow path wall cannot be sufficiently obtained, and if the formation area of the flow path wall is too large, Processing efficiency is lowered.
In consideration of this point, the formation area (area B) of the flow path wall is preferably 0.01 to 10% of the area (area A) of the supply gas flow path member 24 (that is, “0.01 ≦ ((B / A) × 100 ≦ 10 ”).

If such a flow path wall (flow path changing member) does not have a shape that crosses the entire y direction (winding direction) of the supply gas flow path member 24 with one flow path wall, various shapes can be used. It is.
For example, in the example shown in FIG. 3, the flow path changing member has a wall shape extending from the end of the supply gas flow path member 24 in the y direction, but various other shapes can be used. is there. For example, it may be a wall shape that does not contact the end portion in the y direction of the supply gas flow path member 24 and exists only in the central region in the y direction. In addition to the flow path wall (wall shape), a configuration in which island-shaped flow path changing members such as circles and rectangles are regularly or irregularly scattered may be used.

However, the flow path changing member is as shown in the illustrated example in that the flow path of the source gas G can be made longer and the contact distance with the acidic gas separation layer 20 (facilitated transport film 20a) can be increased. A wall shape extending in the y direction from the end (base end or distal end) of the supply gas flow path member 24 in the arrow y direction is preferable.
Moreover, you may use together a wall-shaped flow-path change member and the flow-path change member scattered in island shape.

The forming material of the flow path wall (flow path changing member) has various heat resistance and moisture resistance, and can form a wall-shaped member inside the mesh-shaped supply gas flow path member 24. Material is available.
As an example, an adhesive, a thermoplastic resin, an adhesive tape, etc. are illustrated.
Among these, various known adhesives are suitably used in terms of the formability and convenience of the flow path wall, the degree of freedom of the flow path wall width, and the like.

Examples of adhesives include epoxy resins, vinyl chloride copolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinylidene chloride copolymers, vinyl chloride-acrylonitrile copolymers, butadiene-acrylonitrile copolymers, Polyamide resin, polyvinyl butyral, polyester, cellulose derivative (nitrocellulose, etc.), styrene-butadiene copolymer, various synthetic rubber resins, phenol resin, urea resin, melamine resin, phenoxy resin, silicone resin, urea formamide resin, etc. Preferably exemplified.
Especially, an epoxy resin is illustrated more suitably from a heat resistant and moisture resistant viewpoint.

Such a supply gas flow path member 24 is sandwiched between the acidic gas separation layers 20. In the illustrated example, the acid gas separation layer 20 is, for example, a rectangular sheet.
The separation module 10 in the illustrated example is a facilitated transport type as a preferred embodiment. Therefore, the acidic gas separation layer 20 includes a facilitated transport film 20a and a porous support 20b.
The present invention is not limited to the facilitated transport type separation module, and may be a dissolution / diffusion type separation module using a dissolution / diffusion membrane as disclosed in Patent Document 1 described above.

The facilitated transport film 20a contains at least a carrier that reacts with the acidic gas Gc contained in the source gas G flowing through the supply gas flow path member 24, and a hydrophilic compound that supports the carrier. Such a facilitated transport film 20a has a function of selectively permeating the acidic gas Gc from the source gas G (a function of selectively transporting the acidic 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, 100 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 0.025m~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, and further, the winding shift when the laminate 14 is wound. Is suppressed, and the processability 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 x 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, 1 to 200 μm is preferable, and 2 to 175 μm is more preferable.
By setting the thickness of the facilitated transport membrane 20a within the above range, sufficient 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. Moreover, it is preferable that a hydrophilic compound has a crosslinked structure from a heat resistant viewpoint.
Examples of such hydrophilic compounds include hydrophilic polymers.

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 —OH as a crosslinkable group, the hydrophilic compound preferably has a weight average molecular weight of 30,000 or more. In this case, the weight average molecular weight is more preferably 40,000 or more, and more preferably 50,000 or more. When the hydrophilic compound has —OH as a crosslinkable group, the weight average molecular weight is preferably 6,000,000 or less from the viewpoint of production suitability.
Also, when having -NH ₂ as crosslinkable groups, hydrophilic compounds are those preferably has a weight average molecular weight of 10,000 or more. In this case, the weight average molecular weight of the hydrophilic compound is more preferably 15,000 or more, and particularly preferably 20,000 or more. When the hydrophilic compound has —NH ₂ as a crosslinkable group, the weight average molecular weight is preferably 1,000,000 or less from the viewpoint of production suitability.
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 (—OH), an amino group (—NH ₂ ), a chlorine atom (—Cl), a cyano group (—CN), a carboxy group (—COOH), 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 hydrophilic compounds include those having a single crosslinkable group such as polyallylamine, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyethyleneimine, polyvinylamine, polyornithine, polylysine, Examples include polyethylene oxide, water-soluble cellulose, starch, alginic acid, chitin, polysulfonic acid, polyhydroxymethacrylate, poly-N-vinylacetamide and the like. Most preferred is polyvinyl alcohol. Moreover, as a hydrophilic compound, these copolymers are also illustrated.

Examples of the hydrophilic compound having a plurality of crosslinkable groups include polyvinyl alcohol-polyacrylic acid copolymers. A polyvinyl alcohol-polyacrylic salt copolymer is preferable because of its high water absorption ability and high hydrogel strength even at high water absorption.
The content of polyacrylic acid in the polyvinyl alcohol-polyacrylic acid copolymer is, for example, 1 to 95 mol%, preferably 2 to 70 mol%, more preferably 3 to 60 mol%, and particularly preferably 5 to 50 mol%. It is.
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, and the amount capable of sufficiently retaining moisture depends on the type of the hydrophilic composition or the carrier. It can be set as appropriate.
Specifically, 0.5-50 mass% is preferable, 0.75-30 mass% is more preferable, and 1-15 mass% is especially preferable. By setting the content of the hydrophilic compound within this range, the above-mentioned function as a binder and the 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.

For forming the facilitated transport film 20a, it is preferable to use a crosslinking agent together with the hydrophilic compound. That is, when forming the facilitated-transport film | membrane 20a by the apply | coating method, it is preferable to use the coating composition containing a crosslinking agent.
As the cross-linking agent, one containing a cross-linking agent having two or more functional groups capable of reacting with a hydrophilic compound and capable of cross-linking such as thermal cross-linking or photo-crosslinking is selected. The formed crosslinked structure is preferably a hydrolysis-resistant crosslinked structure.
From such a viewpoint, the crosslinking agent used for forming the facilitated transport film 20a includes an epoxy crosslinking agent, a polyvalent glycidyl ether, a polyhydric alcohol, a polyvalent isocyanate, a polyvalent aziridine, a haloepoxy compound, a polyvalent aldehyde, Preferred examples include valent amines and organometallic crosslinking agents. More preferred are polyvalent aldehydes, organometallic crosslinking agents and epoxy crosslinking agents, and among them, polyvalent aldehydes such as glutaraldehyde and formaldehyde having two or more aldehyde groups are preferred.

As an epoxy crosslinking agent, it is a compound which has 2 or more of epoxy groups, and the compound which has 4 or more is also preferable. Epoxy crosslinking agents are also available as commercial products, for example, trimethylolpropane triglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., Epolite 100MF, etc.), Nagase ChemteX Corporation EX-411, EX-313, EX-614B, Examples include EX-810, EX-811, EX-821, EX-830, NOF Corporation Epiol E400, and the like.
Moreover, the oxetane compound which has cyclic ether as a compound similar to an epoxy crosslinking agent is also used preferably. The oxetane compound is preferably a polyvalent glycidyl ether having two or more functional groups, and commercially available products include, for example, EX-411, EX-313, EX-614B, EX-810, EX-811, EX manufactured by Nagase ChemteX Corporation. -821, EX-830, and the like.

  Examples of the polyvalent glycidyl ether include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, propylene Examples include glycol glycidyl ether and polypropylene glycol diglycidyl ether.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, polyglycerin, propylene glycol, diethanolamine, triethanolamine, polyoxypropyl, and oxyethylene oxypropylene block copolymer. Examples include coalescence, pentaerythritol, and sobitol.

Examples of the polyvalent isocyanate include 2,4-toluylene diisocyanate and hexamethylene diisocyanate.
Examples of the polyvalent aziridines include 2,2-bishydroxymethylbutanol-tris [3- (1-acylidinyl) propionate], 1,6-hexamethylenediethyleneurea, diphenylmethane-bis-4,4′-N, N. Examples include '-diethylene urea.

Examples of the haloepoxy compound include epichlorohydrin and α-methylchlorohydrin.
Examples of the polyvalent aldehyde include glutaraldehyde and glyoxal.
Examples of the polyvalent amine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and polyethyleneimine.
Furthermore, examples of the organometallic crosslinking agent include organic titanium crosslinking agents and organic zirconia crosslinking agents.

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

What is necessary is just to set the quantity of a crosslinking agent suitably according to the kind of hydrophilic compound and crosslinking agent which are used for formation of the facilitated-transport film | membrane 20a.
Specifically, the amount is preferably 0.001 to 80 parts by weight, more preferably 0.01 to 60 parts by weight, and particularly preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the crosslinkable group possessed by the hydrophilic compound. preferable. By setting the content of the cross-linking agent in the above range, a facilitated transport film having good cross-linking structure formation and excellent shape maintainability can be obtained.
Further, when focusing on the crosslinkable group possessed by the hydrophilic compound, the crosslinked structure is formed by reacting 0.001 to 80 mol of a crosslinking agent with respect to 100 mol of the crosslinkable group possessed by the hydrophilic compound. preferable.

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

  Examples of the alkali metal compound include alkali metal carbonates, alkali metal bicarbonates, and alkali metal hydroxides. Here, as the alkali metal, an alkali metal element selected from cesium, rubidium, potassium, lithium, and sodium is preferably used. In addition, in this invention, an alkali metal compound contains the salt and its ion other than alkali metal itself.

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

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.
Moreover, when using 2 or more types of alkali metal compounds as a carrier by the point of being able to obtain the blocking inhibitory effect more suitably, the deliquescence property is more excellent than the first compound having deliquescence and the first compound. It is preferable to include a second compound having a low specific gravity. As an example, the first compound is exemplified by cesium carbonate, and the second compound is exemplified by potassium carbonate.

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

What is necessary is just to set suitably content of the carrier in the facilitated-transport film | membrane 20a according to the kind etc. of a carrier or a hydrophilic compound. Specifically, 0.3-30 mass% is preferable, 0.5-25 mass% is more preferable, and 1-20 mass% is especially preferable.
By setting the content of the carrier in the facilitated transport film 20a within the above range, in the composition (coating material) for forming the facilitated transport film 20a, salting-out before coating can be suitably prevented, and further promoted The transport membrane 20a can reliably exhibit the acid gas separation function.

  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 facilitated transport film 20a may be composed of a single layer or a plurality of layers.
Here, in the case where the facilitated transport film 20a is composed of a plurality of layers, the same film may be laminated, and films having different compositions, types and number of components to be contained, pH, concentrations of each component to be contained, etc. You may laminate.

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.

Here, 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, but has a two-layer structure including a porous membrane and an auxiliary support membrane. Is preferred. By having such two configurations, the porous support 20b more reliably expresses the functions of acid gas permeability, application of the coating composition to be the facilitated transport film 20a, and support of the facilitated transport film 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, polytetrafluoroethylene (PTFE), and high molecular weight polyethylene. An example is a stretched 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.
Furthermore, 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.
Various materials can be used as the support membrane as long as the required strength, stretch resistance and gas permeability are satisfied. 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.

Such an acidic gas separation layer 20 is prepared by preparing a liquid coating composition (coating / coating liquid) containing a component that becomes the facilitated transport film 20a, applying it to the porous support 20b, and drying it. It can be produced by a coating method.
That is, first, a hydrophilic compound, a carrier, and other components to be added as necessary are respectively added to water (room temperature water or warm water) in appropriate amounts, and sufficiently stirred to facilitate transport film 20a. A coating composition is prepared.
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.

The acidic gas separation layer 20 is produced by applying this composition to the porous support 20b and drying it.
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.

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 quickly dried and the gel film is not broken. Specifically, 0.5 to 200 m / min is preferable, 0.75 to 200 m / min is more preferable, and 1 to 200 m / min is particularly preferable.
The temperature of the hot air may be appropriately set to a temperature at which the porous support 20b is not deformed and the gel membrane can be quickly dried. Specifically, the film surface temperature is preferably 1 to 120 ° C, more preferably 2 to 115 ° C, and particularly preferably 3 to 110 ° C.
Moreover, you may use together heating of the porous support body 20b for drying of a coating film as needed.

The laminated body 14 is further laminated with a permeating gas flow path member 26. In the illustrated example, the permeating gas channel member 26 is, for example, a rectangular sheet.
The permeating gas channel member 26 is a member for causing the acidic gas Gc that has reacted with the carrier and permeated through the acidic gas separation layer 32 to flow into 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. Further, in order to properly form the flow path of the acidic gas Gc, the adhesive layer 30 described later needs to penetrate. Considering this point, the permeating gas channel member 26 is preferably a member having a mesh structure (net / mesh), like the supply gas channel member 24.

  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 preparation method of the spiral laminated body 14a, are demonstrated. 4 to 7 used in the following description, the supply gas passage member 24 and the permeate gas passage member 26 have only end faces (end portions) in order to simplify the drawings and clearly show the configuration. Shown in the form.

First, as conceptually shown in FIGS. 4 (A) and 4 (B), the extending direction of the central cylinder 12 and the short direction coincide with each other, and a fixing means such as a Kapton tape or an adhesive is attached to the central cylinder 12. 34 is used to fix the end of the permeating gas channel member 26.
Here, it is preferable that the tube wall of the center tube 12 is provided with a slit (not shown) along the axial direction. In this case, the distal end portion of the permeating gas flow path member 26 is inserted into the slit, and is fixed to the inner peripheral surface of the central cylinder 12 by a fixing means. According to this configuration, when the laminated body including the permeating gas channel member 26 is wound around the central tube 12, the inner peripheral surface of the central tube 12 and the permeating gas channel Friction with the member 26 can prevent the permeate gas flow path member 26 from coming out of the slit, that is, the permeate gas flow path member 26 is fixed.

On the other hand, as conceptually shown in FIG. 5, the acidic gas separation layer 20 is folded in half with the facilitated transport membrane 20 a 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. In this case, 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.
Further, 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 (for example, Kapton tape) folded in half at the trough portion where the acidic gas separation layer 20 is folded in half. Or a PTFE tape) is preferably disposed.

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).
Here, as shown in FIG. 5, the adhesive 30 a (that is, the adhesive layer 30) extends in the vicinity of both end portions in the x direction and extends in the whole area in the y direction. In the vicinity of the end on the opposite side, it extends over the entire region in the x direction and is applied in a strip shape.
Hereinafter, the x direction (source gas supply direction) is also referred to as a width direction. In addition, as described above, the y direction orthogonal to the x direction coincides with the winding direction of the stacked body 14.

  Next, as conceptually shown in FIGS. 6A and 6B, the surface on which the adhesive 30 a is applied is directed toward the permeating gas flow path member 26, and the folded side is sandwiched toward the central cylinder 12. The 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 FIG. 6, an adhesive 30 a to be the adhesive layer 30 is applied to the upper surface of the laminated sandwiched body 36 (the surface of the long porous support 20 b). 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 FIG. 6, the adhesive 30a on this surface is also applied in the form of a strip extending in the entire winding direction in the vicinity of both ends in the width direction, and further on the opposite side to the folded portion. It extends in the entire width direction in the vicinity of the end portion and is applied in a strip shape.

  Next, as conceptually shown in FIG. 7, a permeating gas flow path member 26 is laminated on the sandwiching body 36 coated with the adhesive 30a, and the acidic gas separation layer 20 (porous support 20b) and the permeating medium are permeated. The gas flow path member 26 is bonded to form the laminate 14.

Next, as shown in FIG. 5, as shown in FIG. 5, 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, as in the previous case, an adhesive 30a is applied to the upper surface of the laminated sandwiching body 36 as shown in FIG. 6, and then, as shown in FIG. It laminates | stacks and adheres and the laminated body 14 of the 2nd layer is laminated | stacked.

Thereafter, the steps shown in FIGS. 5 to 7 are repeated, and a predetermined number of laminated bodies 14 are laminated as conceptually shown in FIG.
In this case, as shown in FIG. 8, it is preferable that the laminated body 14 is laminated so as to be gradually separated from the central 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. 8, the center tube 12 on the upper surface of the permeating gas flow path member 26 that is first fixed to the center tube 38 with the adhesive 38 a on the outer peripheral surface of the center tube 12. The adhesive 38b is applied between the sandwiching body 36 and the adhesive 36b.

  Next, as indicated by an arrow yw in FIG. 8, the laminated body 14 is wound (wound) around the central cylinder 12 so as to wind the laminated body 14.

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 spiral laminated body 14a formed by winding the laminated body 14 around the central cylinder 12 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 permeated gas flow path member 26 having a network structure. 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) extends in the vicinity of both ends in the width direction (x direction) and extends in the entire winding direction (y direction) and is formed in a strip shape. Further, the adhesive layer 30 extends in the entire width direction in the vicinity of the end portion on the opposite side to the folded portion on the central tube 12 side so as to cross the adhesive 30 in the width direction in the vicinity of both ends in the width direction. It is formed in a strip 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 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, telescope prevention plates (telescope prevention members) 16 are disposed at both ends of the spiral laminate 14a produced in this way.
As described above, the telescope prevention plate 16 is a so-called telescope in which the spiral laminated body 14a is pressed by the source gas G, the supply-side end face is pushed in a nested manner, and the opposite end face protrudes in a nested manner. This is a member for preventing the phenomenon.

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

  Further, the telescope prevention plate 16 may be disposed in contact with the end face of the spiral laminate 14a. However, in general, since the entire end face of the spiral laminated body 14a is used for supplying the source gas and discharging the residual gas Gr, there is a slight gap between the telescope prevention plate 16 and the end face of the spiral laminated body 14a. Arranged.

Various materials having sufficient strength, heat resistance and moisture resistance can be used as the material for forming the telescope prevention plate 16.
Specifically, 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 covers the peripheral surface of the spiral laminated body 14a and blocks the discharge of the source gas G and the residual gas Gr from the peripheral surface other than the end face of the spiral laminated body 14a to the outside.

As the coating layer 18, various materials that can shield the source 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, a wire made of FRP is impregnated with the adhesive used for the adhesive layer 30 described above, and the wire impregnated with the adhesive is wound around the spiral laminated body 14a in multiple layers without a gap as necessary. The covering layer 18 is illustrated.
In this case, if necessary, a sheet-like member such as Kapton tape is provided between the coating layer 18 and the spiral laminate 14a to prevent the adhesive from penetrating into the spiral laminate 14a. Also good.

  As mentioned above, although the separation module (acid gas separation module) of this invention was demonstrated in detail, this invention is not limited to the above-mentioned example, In the range which does not deviate from the summary of this invention, various improvement and change are performed. Of course, it's also good.

  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>
An aqueous solution containing 3.3% by mass of a polyvinyl alcohol-polyacrylic acid copolymer (Clastomer AP-20 manufactured by Kuraray Co., Ltd.) and 0.016% by mass of a crosslinking agent (25% by mass glutaraldehyde aqueous solution manufactured by Wako Pure Chemical Industries, Ltd.). Prepared. To this aqueous solution, 1M hydrochloric acid was added for crosslinking.
After the crosslinking, a 40% aqueous cesium carbonate solution (manufactured by Rare Metal Co., Ltd.) was added so that the concentration of cesium carbonate was 7.0% by weight and defoamed to prepare a coating composition. That is, in this example, cesium carbonate serves as a carrier for the facilitated transport film 20a.

Then, the facilitated transport film 20a and the porous support 20b (a laminate (manufactured by GE)) obtained by laminating porous PTFE on the surface of a PP nonwoven fabric and dried are applied. An acidic gas separation layer 20 composed of the support 20b was produced.
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. A permeating gas flow path member 26 (tricot knitted epoxy-impregnated polyester) is fixed to the slit of the central cylinder 12 so as to be in a state shown in FIG. The center tube 12 has a partition inside.

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. 5, the half-folding was performed so that one acidic gas separation layer 20 was slightly longer. Kapton 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.
Next, a supply gas flow path member 24 (a polypropylene net having a thickness of 0.44 mm) was sandwiched between the folded acid gas separation layers 20 to produce a sandwiching body 36.

The supply gas flow path member 24 has flow path walls 50a and 50b as conceptually shown in FIG. 3A as flow path changing members for the source gas G. .
The channel walls 50a and 50b were formed of an epoxy adhesive. The thickness L of the channel walls 50a and 50b was 8 mm. Furthermore, the area (area ratio) of the flow path walls 50a and 50b with respect to the area of the supply gas flow path member 24 was 0.53%.

As shown in FIG. 5, on the porous support 20b side where the acidic gas separation layer 20 of the sandwiching body 36 is shorter, the entire region in the winding direction (y direction) is located in the vicinity of both ends in the width direction (x direction). And an adhesive 30a made of an epoxy resin having a high viscosity (about 40 Pa · s) extending in the entire width direction in the vicinity of the end opposite to the folded portion in the winding direction. E120HP manufactured by Henkel Japan Co., Ltd. was applied.
Next, the side to which the adhesive 30a was applied was directed downward, and the sandwiched body 36 and the permeating gas channel member 26 fixed to the central cylinder 12 were laminated and bonded as shown in FIG.
Next, on the upper surface of the acidic gas separation layer 20 of the sandwiching body 36 laminated on the permeating gas channel member 26, as shown in FIG. And the adhesive 30a was apply | coated to the whole area of the width direction in the vicinity of the edge part on the opposite side to the folding | turning part of a winding direction. Further, as shown in FIG. 7, a permeate 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 sandwich member 36 shown in FIG. 5 was produced, and similarly, the adhesive 30a was similarly applied to the porous support 20b side of the short acid gas separation layer 20 on the short side. Next, in the same manner as in FIG. 6, the sandwiched body 36 is directed to the first layered body 14 (the permeate gas flow path member 26) formed on the first layer on the side to which the adhesive 30 a has been applied. It laminated | stacked on the laminated body 14 (member 26 for permeate gas flow paths), 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. 6, and a permeating gas flow path member 26 is laminated thereon and adhered in the same manner as in FIG. An eye laminate 14 was formed.
Further, the third layered product 14 was formed on the second layered product 14 in the same manner as the second layer.

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 yx in FIG. 8, the stacked three-layer laminate 14 is wound around the central cylinder 12 in a multiple manner, and tension is applied in the direction of pulling the laminate 14. Thus, a spiral laminated body 14a was obtained.

Further, the center tube 12 was inserted into the inner ring portion 16b at both ends of the spiral laminated body 14a, and the PPS telescope prevention plate 16 made of 40% glass fiber having the shape shown in FIG. 8 was attached.
Further, 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 spiral laminated body 14a, and the separation module 10 was created.
The membrane area of the created separation module 10 is 1.2 m ² in total for the three layers (design value).

[Example 2]
Example 1 except that the thickness L of the flow path walls 50a and 50b is 26 mm and the area (area ratio) of the flow path walls 50a and 50b with respect to the area of the supply gas flow path member 24 is 1.81%. A separation module 10 was produced in the same manner.

[Example 3]
A separation module 10 was produced in the same manner as in Example 1 except that the number of laminated layers 14 was 20. The membrane area of the created separation module 10 is 30 m ² in total for 20 layers (design value).

[Example 4]
Example 1 except that the flow path wall formed in the supply gas flow path member 24 is changed to the flow path walls 50a and 50b to have the flow path walls 50c, 50d and 50e as shown in FIG. In the same manner, a separation module 10 was produced.
In this example, the area (area ratio) of the flow path walls 50c, 50d and 50e with respect to the area of the supply gas flow path member 24 is 0.82%.

[Example 5]
The flow path wall formed in the supply gas flow path member 24 is changed to the flow path walls 50a and 50b, and the flow path walls 50h and 50i as shown in FIG. Thus, the separation module 10 was produced.
In this example, the area (area ratio) of the flow path walls 50h and 50i with respect to the area of the supply gas flow path member 24 is 0.47%.

[Example 6]
The flow path walls formed in the supply gas flow path member 24 are changed to the flow path walls 50a and 50b to form flow path walls 50f and 50g as shown in FIG. 3C, and the thickness of the flow path wall. A separation module 10 was produced in the same manner as in Example 1 except that L was 13 mm.
In this example, the area (area ratio) of the flow path walls 50f and 50g with respect to the area of the supply gas flow path member 24 is 1.2%.

[Comparative Example 1]
A separation module was prepared in the same manner as in Example 1 except that the supply gas channel member 24 did not have the channel walls 50a and 50b.

<Module factor>
By measuring the separation factors of the separation modules of the produced separation modules of Examples and Comparative Examples, the separation module and the facilitated transport membrane 20a itself on the porous support 20b used in the separation module, Calculated.
In this example, the CO ₂ / H ₂ separation factor and the CO ₂ / N ₂ separation factor were measured, and the module factor was calculated for each separation factor.

(Measurement of separation factor of separation module)
CO ₂ / H ₂ separation factor; H ₂ : CO ₂ : H ₂ O = 45: 5: 50 (partial pressure ratio) of raw material gas G (flow rate 2.2 L (liter) / min) at a temperature of 130 ° C. and a total pressure of 301 The gas was supplied to each separation module at 3 kPa, and Ar gas (flow rate: 0.9 L / min) was allowed to flow on the permeation side. The permeated gas was analyzed with a gas chromatograph, and the CO ₂ / H ₂ separation factor (α) was calculated.
CO ₂ / N ₂ separation factor; N ₂ : CO ₂ : H ₂ O = 66: 21: 13 (partial pressure ratio) source gas G (flow rate 1.72 L / min) at a temperature of 130 ° C. and a total pressure of 2001.3 kPa , Supplied to each separation module. The permeated gas was analyzed with a gas chromatograph, and the CO ₂ / N ₂ separation factor (α) was calculated.

(Measurement of separation factor of facilitated transport membrane 20a itself on porous support 20b)
CO ₂ / H ₂ separation factor; H ₂ : CO ₂ : H ₂ O = 45: 5: 50 (partial pressure ratio) source gas G (flow rate 0.32 L / min) at a temperature of 130 ° C. and a total pressure of 301.3 kPa Then, it was supplied to the facilitated transport film 20a, and Ar gas (flow rate: 0.04 L / min) was allowed to flow on the permeate side. The permeated gas was analyzed with a gas chromatograph, and the CO ₂ / H ₂ separation factor (α) was calculated.
CO ₂ / N ₂ separation factor; N ₂ : CO ₂ : H ₂ O = 66: 21: 13 (partial pressure ratio) source gas G (flow rate 0.32 L / min) at a temperature of 130 ° C. and a total pressure of 2001.3 kPa , And supplied to the facilitated transport film 20a. The permeated gas was analyzed with a gas chromatograph, and the CO ₂ / N ₂ separation factor (α) was calculated.

Using the CO ₂ / H ₂ separation factor (α) and the CO ₂ / N ₂ separation factor (α) measured as described above, the module factor was calculated by the following equation.
Module factor = (α) of separation module / (α) of facilitated transport membrane 20a
The results are shown in the table below.

As shown in the above table, the separation module of the present invention having the flow path wall in the supply gas flow path member 24 shows a higher module factor than the separation module of the comparative example having no flow path wall. , Has excellent separation performance. In Example 3, since the membrane area was large, it was considered that the module factor was difficult to come out.
In particular, the separation module of Example 6 in which the source gas G is made to flow backward with respect to the supply direction and then the flow path wall is formed so as to face the supply direction shows excellent separation performance.
From the above results, the effects of the present invention are clear.

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

DESCRIPTION OF SYMBOLS 10 (Acid gas) separation module 12 Central cylinder 14 Laminated body 14a Spiral laminated body 16 Telescope prevention board 16a Outer ring part 16b Inner ring part 16c Rib 16d Opening part 18 Covering layer 20 Acid gas separation layer 20a Accelerated transport film 20b Porous Support member 24 Supply gas channel member 26 Permeate gas channel member 30 Adhesive layer 30a Adhesive 34 Fixing means 36 Holding member 40 Adhesive member 50a, 50b, 50c, 50d, 50e, 50f, 50g, 50h, 50i flow Road wall

Claims (7)

A sheet-like acidic gas separation layer having an acidic gas separation membrane that separates the acidic gas from the raw material gas, and a supply gas flow passage that is laminated on the acidic gas separation layer and has the inside serving as the raw material gas passage A member for
Furthermore, it has a flow path changing member that changes the flow path of the source gas inside the supply gas flow path member,
When the supply direction of the source gas is the x direction and the direction orthogonal to the x direction is the y direction, a plurality of the flow path changing members are arranged in the x direction, and at least one flow The path changing member extends in the y direction from one end in the y direction of the supply gas flow path member, and the other at least one flow path changing member is the y of the supply gas flow path member. Extending in the y direction from the opposite end of the direction,
Furthermore, the most upstream flow path changing member, which is the flow path changing section located at the most upstream in the x direction, extends from one end of the supply gas flow path member in the y direction in the y direction. And it inclines with respect to the y direction so as to go from one end in the y direction toward the downstream side in the x direction,
The flow path changing member located immediately downstream in the x direction of the most upstream flow path changing member is an end of the supply gas flow path member in the y direction opposite to the most upstream flow path changing member. And extending in the y direction, and is inclined with respect to the y direction so as to be directed from the opposite end of the y direction toward the upstream side in the x direction. Gas separation module.   2. The flow path of the source gas according to claim 1, wherein the flow path changing member changes a flow path of the raw material gas so as to go in a direction of flowing backward with respect to the supply direction of the raw material gas, and thereafter, in a direction of supplying the raw material gas. Acid gas separation module. The flow path changing member is a wall-shaped member having a height direction in a thickness direction of the supply gas flow path member and extending in a surface direction of the supply gas flow path member,
And the acid gas separation module of Claim 1 or 2 whose thickness of this wall is 5-50 mm.   The area of the flow path changing member in the surface direction of the supply gas flow path member is 0.01 to 10% of the total area of the supply gas flow path member. The acid gas separation module according to 1.   5. The acidic gas separation module according to claim 1, wherein the acidic gas separation module is a spiral type formed by winding a laminate including the supply gas flow path member and the acidic gas separation layer. A supply gas flow path member is sandwiched between the acidic gas separation layers, and sheet-shaped permeation gas flow path members that serve as acidic gas flow paths separated by the acidic gas separation membrane are laminated on both sides thereof. The acidic gas separation module according to claim 1, which has at least one laminate. Furthermore, the acidic gas separation module of any one of Claims 1-6 which has an island-shaped flow-path change member.