JP2015020147A - Spiral type module for acid gas separation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a spiral type module for acid gas separation: which is produced by winding around a laminate including an acid gas separation layer having a facilitated transport membrane; which has no defects in the facilitated transport membrane; and which has high quality.SOLUTION: A problem is solved by that a spiral type module for acid gas separation has: a supply gas flow path member which is a flow path for the raw material gas; an acid gas separating layer having, on the surface of the supply gas flow path member side, a carrier that separates the acid gas from the material gas flowing through the supply gas flow path member and reacts with the acid gas, and a facilitated transport membrane containing hydrophilic compound for supporting the carrier; a permeation gas flow path member which is a flow path where the acid gas that permeates through the facilitated transport membrane flows to a center cylinder; and at least one of a fluorine-based coating and a silicon-based coating formed on the surface of the facilitated transport membrane side of the supply gas flow path member.

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 a spiral-type module for acid gas separation, which is formed by winding a laminate having an acid gas separation membrane.

  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.

Specifically, Patent Document 1 discloses a laminate including an acidic gas separation membrane in a central tube (a central permeate collection tube) for collecting separated acidic gas, in which a through-hole is formed in a tube wall. A multi-winding acidic 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, a so-called laminated body having an acidic gas separation membrane is wound around a central cylinder having a through-hole on a wall surface (wrapped around the central cylinder). The spiral acid gas separation module can greatly increase the area of the acid gas separation membrane. Therefore, the spiral acid gas separation module can be efficiently processed and is very effective.

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

As an example, a spiral type acidic gas module is separated by an acidic gas separation membrane and a central tube, a supply gas flow path member that becomes a flow path of a source gas from which acidic gas is separated, and an acidic gas separation membrane. And a permeating gas channel member serving as the acidic gas channel.
A spiral type acidic gas module made of such a member is formed by laminating one or a plurality of laminated bodies in which an acidic gas separation membrane, a supply gas flow path member and a permeate gas flow path member are stacked. It has a configuration wound around a cylinder.

  For example, in the above-mentioned Patent Document 1, the acidic gas separation membrane is folded in half, and a supply gas flow path member (feed spacer) is sandwiched, and one of the folded acidic gas separation membranes is used for the permeate gas flow path. A spiral acid gas separation module is disclosed in which a laminate in which members (permeate spacers) are laminated and a plurality of laminates are wound around a central tube (permeate collection tube) are disclosed. Yes.

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

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

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

  An object of the present invention is to solve such problems of the prior art, and is a spiral acidic gas separation module using an acidic gas separation layer (separation membrane) having a facilitated transport membrane, Spiral type for acid gas separation that can prevent damage to the facilitated transport membrane due to sliding contact between the facilitated transport membrane and the supply gas flow path member and stably obtain a module having the desired performance To provide a module.

  In order to achieve this object, the present invention provides a center tube having a through-hole formed in a tube wall, a supply gas channel member serving as a source gas channel, and a source gas flowing through the supply gas channel member An acidic gas separation layer having a carrier that reacts with the acidic gas and a hydrophilic compound for supporting the carrier on the surface on the side of the supply gas flow path, and facilitated transportation. At least of a fluorine-based film and a silicon-based film formed on a surface of the permeated gas channel member that serves as a channel through which the acidic gas that has permeated the membrane flows to the central cylinder, and the surface of the supply gas channel member on the facilitated transport film side A spiral gas module for separating acid gas, in which one or more laminates each having a supply gas channel member, an acid gas separation layer, and a permeate gas channel member are wound around a central cylinder To do.

Here, the member for the supply gas flow path is a woven fabric or a non-woven fabric, and preferably has a fiber diameter of 100 to 900 μm and a fiber density of ² to 30 mg / cm ² .
The facilitated transport film preferably has a thickness of 5 to 150 μm.
Moreover, it is preferable that the tensile elasticity modulus of the member for supply gas flow paths in which at least one of the fluorine-type membrane | film | coat and the silicon-type membrane | film | coat was formed is 1-500 Mpa.
Further, the supply gas channel member is selected from polyethylene, polystyrene, polyethylene terephthalate, polytetrafluoroethylene, polyethersulfone, polyphenylene sulfide, polysulfone, polypropylene, polyimide, polyetherimide, polyetheretherketone, and polyvinylidene fluoride. It preferably has a network structure formed of yarns containing one or more kinds of resins.
The laminate is an acidic gas separation layer folded in half with the facilitated transport membrane inside, and a structure in which a permeate gas flow path member is laminated on a sandwich body sandwiching a supply gas flow path member. It is preferable to have.
Furthermore, the acidic gas separation layer preferably has a configuration in which the facilitated transport membrane is supported by a porous support.

According to the present invention, in a spiral acidic gas separation module using a facilitated transport membrane, it is preferable to prevent the facilitated transport membrane from being damaged due to sliding contact between the facilitated transport membrane and the supply gas flow path member that occurs during winding. it can.
Therefore, according to the present invention, it is possible to stably obtain an acid gas separation module that prevents deterioration in performance due to damage to the facilitated transport membrane, has excellent product stability, and exhibits desired performance. it can.

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

  Hereinafter, the spiral-type module for acid gas separation according to 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 a spiral-type module for acid gas separation according to the present invention.
As shown in FIG. 1, the spiral type module 10 for acid gas separation basically includes a center tube 12, a laminate 14 having an acid gas separation membrane (facilitated transport membrane 20a), and a telescope prevention plate 16. It is configured. In the following description, the spiral module for acid gas separation 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.

In such a separation module 10, the source gas G from which the acidic gas is separated is supplied to the end face of the spiral laminate 14a through, for example, the telescope prevention plate 16 (the opening portion 16d) on the far side in FIG. The acid gas Gc is separated while flowing into the laminated body 14 from the end face and flowing through the laminated body 14.
Further, the acidic gas Gc separated from the raw material gas G by the stacked body 14 is discharged from the central cylinder 12. On the other hand, the source gas G from which the acidic gas 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 acid gas separation layer 20, a supply gas flow path member 24, and a permeate gas flow path member 26. A coating 28 is formed on the surface of the supply gas flow path member 24 (see FIG. 2 and the like).
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.
Hereinafter, for convenience, a direction corresponding to the winding of the laminate 14 is a circumferential direction (arrow y direction), and a direction orthogonal to the circumferential direction is a width direction (arrow x direction). The laminated body 14 is generally a rectangular sheet, but the circumferential direction is usually the laminated body 14 (acid gas separation layer 20, supply gas flow path member 24, and permeate gas flow path member. 26) in the longitudinal 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 film area of the acidic gas separation layer 20 can be improved by increasing the length of the stacked body 14 in the width direction.
The number of stacked layers 14 may be set as appropriate according to the processing speed and processing amount required for the separation module 10, the size of the separation module 10, and the like. Here, the number of laminated bodies 14 to be laminated is preferably 50 or less, more preferably 45 or less, and particularly preferably 40 or less. By setting the number of laminated bodies 14 to be this number, winding of the laminated body 14 around the central cylinder 12 becomes easy, and workability can be improved.

In FIG. 2, the fragmentary sectional view of the laminated body 14 is shown. As described above, the arrow x is the width direction and the arrow y is the circumferential direction.
In the illustrated example, the laminated body 14 has a permeating gas flow path member 24 sandwiched between two folded acidic gas separation layers 20 to form a sandwiching body 36 (see FIG. 4). The road member 26 is laminated. This configuration will be described in detail later.

As described above, in the separation module 10, the source gas G is supplied from one end face of the spiral laminate 14 a through the telescope prevention plate 16 (its opening 16 d). That is, the source gas G is supplied to the end portion (end surface) in the width direction (arrow x direction) of each stacked body 14.
As conceptually shown in FIG. 2, the source gas G supplied to the end surface in the width direction of the stacked body 14 flows in the width direction in the supply gas flow path member 24. In this flow, the acidic gas Gc in contact with the acidic gas separation layer 20 (facilitated transport film 20a) is separated from the source gas G and passes through the acidic gas separation layer 20 in the stacking direction of the laminate 14 ( Transported in the stacking 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 circumferential direction (the direction of the arrow y), reaches the central cylinder 12, and passes through the through hole 12 a of the central cylinder 12. 12 flows in.
The flow of the acid gas Gc is regulated by the adhesive layer 30. That is, in the separation module 10, the two acidic gas separation layers 20 (facilitated transport membrane 20a) sandwiching the permeate gas flow path member 26, the permeate gas flow path member 26, and the acidic gas separation layer 20 (porous support) 20b) and the adhesive layer 30 penetrating into the inner surface of the adhesive layer 30 in the surface direction forms an envelope-like flow path (space) that encloses the permeate gas flow path member 26 and that is open on the central tube 12 side. (See FIGS. 4 and 5). Thereby, the separation module 10 prevents the acidic gas Gc that has passed through the acidic gas separation layer 20 from flowing out.
The adhesive layer 30 will be described in detail later.

The acidic gas Gc that has flowed into the center tube 12 flows through the center tube 12 in the width direction and is discharged from the open end 12b.
Further, the remaining gas Gr from which the acid gas Gc has been removed flows in the supply gas flow path member 24 in the width direction, and is discharged from the opposite end face of the spiral laminated body 14a. It is discharged to the outside of the separation module 10 through the part 16d).

The supply gas flow path member 24 is supplied with the source gas G from the end in the width direction, and brings the source gas G flowing in the member into contact with the acidic gas separation layer 20.
Here, in the separation module 10 of the present invention, the coating 28 is formed on the surface of the supply gas flow path member 24 (not shown in FIG. 1). The coating 28 is made of a fluorine-based material (fluorine-based coating) and / or a silicon-based material (silicon-based coating). The supply gas flow path member 24 is disposed so as to face the facilitated transport film 20 a of the acidic gas separation layer 20. Accordingly, the coating 28 is provided in contact with the facilitated transport film 20a. The coating 28 will be described later in detail.

  Such a supply gas flow path member 24 functions as a spacer of the acid gas separation layer 20 folded in half as described above, and constitutes a flow path for the source gas G. Further, the supply gas flow path member 24 preferably makes the source gas G turbulent. In consideration of this point, the supply gas flow path member 24 is preferably a member having a mesh structure (net shape / mesh shape). Especially, the network structure formed with the thread | yarn containing 1 or more of the resin material mentioned later is preferable.

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.
Among these, a resin material or a material containing a resin material) is preferably exemplified. Specific examples of the resin material include polyethylene, polystyrene, polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), polyethersulfone (PES), polyphenylene sulfide (PPS), polysulfone (PSF), and polypropylene (PP). , Polyimide, polyetherimide, polyetheretherketone, polyvinylidene fluoride and the like are preferably exemplified. A plurality of such resin materials may be used in combination.

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

Further, when the supply gas flow path member 24 is a woven or non-woven fabric having a network structure formed of resin threads or the like, the fiber diameter is preferably 100 to 900 μm. The fiber density is preferably ² to 30 mg / cm ² .
As will be described in detail later, in the spiral type separation module, as a cause of performance degradation, the facilitated transport film 20a and the supply when the laminated body 14 (a laminated body in which the laminated body 14 is laminated) are wound around the central cylinder 12 are supplied. The damage of the facilitated transport film 20a due to the sliding contact with the gas flow path member 24 is exemplified.
On the other hand, the separation module 10 of the present invention has the coating 28 on the surface of the supply gas flow path member 24 so that the facilitated transport film 20a and the supply when the laminate 14 is wound around the central cylinder 12 are supplied. The facilitated transport film 20a is prevented from being damaged due to sliding contact with the gas flow path member 24.

However, when the fiber diameter of the yarn (fiber) constituting the supply gas flow path member 24 is less than 100 μm, the porosity of the supply gas flow path member 24 is lowered and the pressure loss is increased. , Processing efficiency may be reduced. Therefore, the fiber diameter is preferably 100 μm or more.
In addition, when the fiber diameter exceeds 900 μm, the amount of fibers pushed into the membrane surface increases, so even if the coating 28 is formed on the surface, damage to the facilitated transport membrane 20a due to sliding contact between the two is prevented. It may not be possible. Therefore, the fiber diameter is preferably 900 μm or less.

Similarly, when the fiber density of the yarn (fiber) constituting the supply gas flow path member 24 is less than 2 mg / cm ² , the contact between the supply gas flow path member 24 (film 28) and the facilitated transport film 20a. The area is not sufficiently large, and when the module is wound, the amount of fibers pushed into the membrane surface increases, so that damage to the facilitated transport membrane 20a due to the sliding contact between them may not be prevented. Therefore, the fiber diameter is preferably ² mg / cm ² or more.
Further, when the fiber density is more than 30 mg / cm ² , the porosity of the supply gas flow path member 24 becomes low, the resistance to the flowing raw material gas G increases, and the processing efficiency may be lowered. . Accordingly, the fiber density is preferably 30 mg / cm ² or less.

Further, the tensile elastic modulus of the supply gas flow path member 24 is preferably 1 to 500 MPa.
When the tensile elastic modulus is more than 500 MPa, that is, if the supply gas flow path member 24 is hard, when the module is wound, the amount of fibers pushed into the membrane surface increases, and the facilitated transport membrane 20a may be damaged. is there. Therefore, the tensile elastic modulus is preferably 500 MPa or less.
Further, when the tensile elastic modulus is less than 1 MPa, the supply gas flow path member 24 is soft, so that it may not function as a spacer between the acidic gas separation membranes 20, that is, the flow path of the source gas may not be secured. There is. Accordingly, the tensile elastic modulus is preferably 1 MPa or more.
In this way, by controlling the fiber diameter, fiber density, and tensile modulus of the supply gas flow path member 24, it is possible to improve manufacturing stability and processing performance.

  The tensile elastic modulus of the supply gas channel member 24 is obtained from the relationship between the tensile stress and the strain amount as a structure such as a network structure. Further, the tensile elastic modulus may be a state in which the film 28 is formed on the surface of the supply gas flow path member 24.

  The separation module 10 of the present invention is a facilitated transport type. Therefore, the acidic gas separation layer 20 includes a facilitated transport film 20a and a porous support 20b.

The facilitated transport film 20a contains at least a carrier that reacts with the acidic gas Gc contained in the source gas G flowing through the supply gas flow path member 24, 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. Separation efficiency increases compared to the case.

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 circumferential length of the facilitated transport film 20a (the total length before folding in half) may be appropriately set 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 circumferential length of the facilitated transport film 20a within the above range, the acidic gas Gc can be efficiently separated with respect to the film area, and further, the winding deviation when the laminate 14 is wound can be reduced. Occurrence is suppressed and workability is facilitated.
The width of the facilitated transport film may be set as appropriate according to the size of the separation module 10 in the width direction.

  The thickness of the facilitated transport film 20a may be appropriately set according to the size of the separation module 10, the processing capability required for the separation module 10, and the like.

Here, as will be described in detail later, in the spiral type separation module, the facilitated transport film when the laminated body 14 (a laminated body in which the laminated body 14 is laminated) is wound around the central cylinder 12 as a cause of performance degradation. The damage of the facilitated transport film 20a due to the sliding contact between 20a and the supply gas flow path member 24 is exemplified.
Performance degradation due to damage to the facilitated transport film 20a can be suppressed by increasing the thickness of the facilitated transport film 20a. However, when the facilitated transport film 20a becomes thicker, the permeation performance is lowered, so that the separation performance of the acid gas Gc is lowered accordingly.
On the other hand, since the separation module 10 of the present invention has the coating 28 on the surface of the supply gas flow path member 24, the facilitated transport film 20a and the supply gas when the laminate 14 is wound around the central cylinder 12 are provided. Damage to the facilitated transport film 20a due to sliding contact with the flow path member 24 can be prevented. That is, even if the facilitated transport film 20a is thinned in order to improve the permeation performance, it is possible to prevent the performance degradation due to the damage of the facilitated transport film 20a.

Considering the above points, the thickness of the facilitated transport film 20a is preferably 5 to 150 μm, and more preferably 10 to 120 μm.
By setting the thickness of the facilitated transport membrane 20a within the above range, high gas permeability and separation selectivity can be realized.

The hydrophilic compound functions as a binder, holds moisture in the facilitated transport film 20a, and exhibits a function of separating a gas such as carbon dioxide by the carrier. 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 the hydrophilic compound include those having a single crosslinkable group such as polyallylamine, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyethyleneimine, polyvinylamine, polyornithine, polylysine, Examples include polyethylene oxide, water-soluble cellulose, starch, alginic acid, chitin, polysulfonic acid, polyhydroxymethacrylate, poly-N-vinylacetamide and the like. Most preferred is polyvinyl alcohol. Moreover, as a hydrophilic compound, these copolymers are also illustrated.

Examples of the hydrophilic compound having a plurality of crosslinkable groups include polyvinyl alcohol-polyacrylic acid copolymers. A polyvinyl alcohol-polyacrylic salt copolymer is preferable because of its high water absorption ability and high hydrogel strength even at high water absorption.
The content of polyacrylic acid in the polyvinyl alcohol-polyacrylic acid copolymer is, for example, 1 to 95 mol%, preferably 2 to 70 mol%, more preferably 3 to 60 mol%, and particularly preferably 5 to 50 mol%. It is.
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, an alkali metal carbonate is preferable, and a compound containing potassium, rubidium, and cesium having high solubility in water is preferable from the viewpoint of good affinity with acidic gas.

Moreover, when using an alkali metal compound as a carrier, two or more kinds of carriers may be used in combination.
When two or more types of carriers are present in the facilitated transport film 20a, different carriers can be separated from each other in the film. Thereby, due to the difference in deliquescence of a plurality of carriers, due to the hygroscopicity of the facilitated transport film 20a, the facilitated transport films 20a or the facilitated transport film 20a and other members are stuck together at the time of manufacture. (Blocking) can be suitably suppressed.
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 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.

As described above, in the separation module 10 of the present invention, the coating 28 is formed on the surface of the supply gas flow path member 24 in contact with the surface of the facilitated transport membrane 20a of the acidic gas separation layer 20 as described above.
The coating 28 is a fluorine-based coating, a silicon-based coating, or a coating made of both a fluorine-based coating and a silicon-based coating.
Since the separation module 10 of the present invention has the coating 28, the facilitated transport membrane 20a is prevented from being damaged, is excellent in manufacturing stability, and stably exhibits the intended performance.

As described above, the spiral type separation module is formed by stacking the acid gas separation layer 20, the supply gas flow path member 24, and the permeate gas flow path member 26, or by stacking this stack. The laminate is formed by winding (wrapping) around the central tube 12.
In the illustrated separation module 10, the acidic gas separation layer 20 is folded in two with the accelerating separation membrane 20 a inside, and a sandwiching body 36 is formed in which the supply gas flow path member 24 is sandwiched by the acidic gas separation layer 20. Then (see FIG. 4), the laminated body 14 in which the permeating gas flow path member 26 is laminated on the sandwiching body 36 is laminated, and the laminated body of the laminated body 14 is wound around the central cylinder 12.

Here, the acidic gas separation layer 20 and the permeating gas channel member 26 are fixed by the adhesive layer 30. On the other hand, the acidic gas separation layer 20 and the supply gas flow path member 24 are simply sandwiched between the acidic gas separation layer 20 and the supply gas flow path member 24.
Therefore, when winding around the central cylinder 12, the positions of the acidic gas separation layer 20 and the supply gas flow path member 24 are relatively moved in the circumferential direction.
As described above, the supply gas flow path member 24 preferably has a mesh structure formed of resin threads or the like. On the other hand, the facilitated transport film 20a has a structure in which a hydrophilic compound such as a super water-absorbent resin is used as a binder and carriers are dispersed in the binder, and is often soft.
For this reason, the acidic gas separation layer 20 and the supply gas flow path member 24 may be slidably contacted with each other during winding, and the facilitated transport film 20a may be damaged by the sliding contact. . Also, in a severe case, the facilitated transport film 20a is partially removed almost completely, resulting in a defective portion, from which the raw material gas G leaks and the separation performance is reduced, or the raw material gas G is reduced. In some cases, the pressure applied for processing is lost (decrease in confidentiality).

On the other hand, the separation module 10 of the present invention has a coating 28 made of a fluorine-based coating and / or a silicon-based coating on the surface of the supply gas flow path member 24.
By having this coating film 28, the sliding property between the facilitated transport film 20a and the supply gas flow path member 24 can be improved. As a result, when the laminate (laminate 14) of the laminate 14 is wound around the central cylinder 12 as described above, the facilitated transport film 20a and the supply gas flow path member 24 move relatively. Even if both are in sliding contact, the facilitated transport film 20a can be prevented from being damaged.
Therefore, according to the present invention, high production stability, high confidentiality, performance degradation due to damage to the facilitated transport film 20a, no leakage of the raw material gas G, no pressure loss, and the like are achieved. A separation module 10 can be obtained.

As described above, the coating 28 covering the surface of the supply gas flow path member 24 is a fluorine-based coating and / or a silicon-based coating.
The fluorine-based film is a film made of a fluorine-containing compound or a film containing a fluorine-containing compound as a main component (the largest content).
Specifically, although not particularly limited, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-perfluoropropylene copolymer, chlorotrifluoroethylene-vinylidene fluoride copolymer Coalescence etc. can be used.
The silicon-based film is a film made of an organic silicon compound or a film containing an organic silicon compound as a main component.
Specifically, although not particularly limited, low-molecular dimethyl silicone oil, organically modified dimethylsilicone oil, alkoxysilane, organically modified alkoxysilane, and a mixture thereof can be used.
The coating 28 may be a mixture of a fluorine-based coating and a silicon-based coating.

Here, in the example shown in FIG. 2, the coating 28 is formed so as to cover the entire surface of the supply gas flow path member 24, but this coating 28 covers the entire surface of the supply gas flow path member 24. There is no limitation to the configuration formed, and a portion of the surface of the supply gas flow path member 24 may be covered. For example, you may coat | cover with the coverage (area ratio) of 10% or more of the surface of the member 24 for supply gas flow paths.
If the surface coverage of the supply gas flow path member 24 by the coating 28 is less than 10%, the effect of having the coating 28 cannot be obtained sufficiently, and the facilitated transport film 20a is damaged when the laminate 14 is wound. Cannot be sufficiently prevented.

  Here, the coating of the supply gas flow path member 24 with the coating 28 may be uniform over the entire surface of the supply gas flow path member 24, but the region corresponding to the adhesive layer 30 described above (in the thickness direction). When viewed in the (lamination direction), the area where the position in the plane direction overlaps with the adhesive layer 30 is preferably higher in the coverage by the coating 28 than the other areas.

As will be described in detail later, in the separation module 10, the permeate gas flow path member 26 and the porous support 20 b (the sandwiching body 36) of the acidic gas separation layer 20 are bonded, and the stacked bodies 14 are bonded together. Therefore, the adhesive layer 30 is formed. Further, the adhesive layer 30 (adhesive 28 that becomes the adhesive layer 30) penetrates not only into the adhesive but also into the porous support 20 and the permeate gas flow path member 26, and thereby the permeate gas flow path member. The flow path of the acidic gas Gc in the interior 26 is formed.
The adhesive layer 30 is harder than the porous support 20b and the permeating gas channel member 26. For this reason, the facilitated separation membrane 20a in the region corresponding to the adhesive layer 30 is more damaged by sliding contact with the supply gas flow path member 24 than in other regions.

Therefore, in the region corresponding to the adhesive layer 30, it is preferable to increase the coverage of the supply gas flow path member 24 by the coating 28 and more reliably prevent damage due to sliding contact with the facilitated transport film 20a. .
Specifically, in the region corresponding to the adhesive layer 30, the coverage of the accelerated separation membrane 20a by the coating 28 in the region is preferably 50 to 100%, more preferably 80 to 100%. preferable.
Thereby, damage to the facilitated separation membrane 20a can be prevented more reliably.

  In the separation module 10 of the present invention, the region where the coating 28 is formed on the surface of the supply gas flow path member 24, whether in the region corresponding to the adhesive layer 30 or in other regions. It is preferable to form the film 28 so that the non-formed portions are uniformly dispersed.

In the formation portion of the coating 28, the thickness of the coating 28 depends on the material for forming the coating 28, the surface coverage of the supply gas channel member 24 by the coating 28, and the type of the supply gas channel member 24 (formation material or mesh). The thickness of the coating film 28 that can ensure sufficient slipperiness may be appropriately set according to the roughness (such as roughness) and the type of the promoting separation membrane 20a (including components and the ratio of each component).
Specifically, the thickness of the coating 28 is preferably 0.001 to 1 μm, and more preferably 0.01 to 0.5 μm.
By setting the thickness of the coating 28 within the above range, it is preferable in that damage to the accelerating separation membrane 20a by the supply gas flow path member 24 can be more suitably prevented.

As a method for forming the film 28, a known film forming method can be used according to the material for forming the film.
Specifically, a coating material containing a material to be the coating film 28 is prepared, and the object is applied to the surface of the supply gas flow path member 24 by spray coating, brushing, coating with a spatula, etc., immersion in a processing solution, or the like. An example is a method of forming the coating film 28 by applying a coating material and drying it so as to achieve the covering ratio.

The laminated body 14 is further laminated with a permeating gas flow path member 26.
The permeating gas channel member 26 is a member for 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 materials such as epoxy-impregnated polyester, polyolefin materials such as polypropylene, and fluorine materials such as polytetrafluoroethylene 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 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. 3 to 6 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. 3 (A) and 3 (B), the extending direction of the central cylinder 12 and the short direction are matched, and a fixing means 34 such as an instantaneous adhesive is provided on the central cylinder 12. Used to fix the end of the permeate gas flow path member 26.

  On the other hand, on the surface of the supply gas flow path member 24, the film 28 made of the fluorine-based film and / or the silicon-based film is formed as described above.

Next, as conceptually shown in FIG. 4, the acidic gas separation layer 20 produced as described above is folded in half with the facilitated transport membrane 20a inside, and a supply gas flow path in which a coating 28 is formed therebetween. The member 24 is sandwiched. That is, a sandwiching body 36 is produced in which the supply gas flow path member 24 is sandwiched between the acidic gas separation 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. Etc.) are preferably arranged.

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. 4, the adhesive 30 a (that is, the adhesive layer 30) extends in the vicinity of both ends in the width direction (arrow x direction) and extends in the entire circumferential direction (arrow y direction). It is applied in the form of a strip, and is further applied in the form of a strip extending in the entire width direction in the vicinity of the end opposite to the folded portion.

  Next, as conceptually shown in FIGS. 5A and 5B, the surface to which the adhesive 30a is applied is directed toward the permeating gas flow path member 26, and the folded side is sandwiched toward the central tube 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. 5, an adhesive 30 a to be the adhesive layer 30 is applied to the upper surface of the laminated sandwiching body 36 (the surface of the long porous support 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. 5, the adhesive 30a on this surface is also applied in the form of a belt extending in the entire circumferential direction in the vicinity of both ends in the width direction, and the end opposite to the folded portion as in the previous case. It is applied in the form of a strip extending in the entire width direction in the vicinity of the portion.

  Next, as conceptually shown in FIG. 6, a permeate gas flow path member 26 is laminated on the sandwiched body 36 coated with the adhesive 30 a, and the acidic gas separation layer 20 (porous support 20 b) and the permeate are permeated. The gas flow path member 26 is bonded to form the laminate 14.

Next, as shown in FIG. 4, as shown in FIG. 4, the acidic gas separation layer 20 in which the coating 28 is formed on the surface of the facilitated transport film 20 a is used to produce a sandwich 36 that sandwiches the supply gas flow path member 24. The adhesive 30a to be the adhesive layer 30 is applied, the side to which the adhesive is applied is directed downward, and the finally laminated permeated gas flow path member 26 and the sandwiching body 36 are laminated and bonded.
Further, similarly to the above, the adhesive 30a is applied to the upper surface of the laminated sandwiching body 36 as shown in FIG. 5, and then, as shown in FIG. It laminates | stacks and adhere | attaches and the laminated body 14 of the 2nd layer is laminated.

Hereinafter, the steps of FIGS. 4 to 6 are repeated to stack a predetermined number of stacked bodies 14 as conceptually shown in FIG.
In this case, as shown in FIG. 7, it is preferable that the laminated body 14 is laminated so as to be gradually separated from the central cylinder 12 in the circumferential 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 laminated bodies 14 are laminated, as shown in FIG. 7, the center tube 12 on the upper surface of the permeating gas flow path member 26 that is first fixed to the center tube 12 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 shown by an arrow yx in FIG. 7, the laminated body 14 is wound (wrapped) around the central cylinder 12 so as to wind the laminated body 14.
Here, in the separation module 10 of the present invention, the coating 28 which is a fluorine-based coating and / or a silicon-based coating is formed on the surface of the facilitated transport membrane 20a with a coverage of 10 to 90%. For this reason, even if the facilitated transport film 20a and the supply gas flow path member 24 move relative to each other when they are wound around the central cylinder 12, the facilitated transport film 20 may be damaged even if both of them slide in contact with each other. Can be suitably prevented.

After winding, the permeate gas passage member 26 on the outermost periphery (that is, the lowermost layer first fixed to the center tube 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 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.
In addition, as described above, the adhesive layer 30 (adhesive 30a) is formed in a strip shape extending in the entire circumferential direction in the vicinity of both ends in the width direction. 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 the adhesive layer 30 (adhesive 30a) as long as it 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 raw material gas G and the like can be used. The covering layer 18 may be a cylindrical member or may be configured by winding a wire or a sheet-like member.
As an example, 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 (spiral type module for acid gas separation) of the present invention has been described in detail, the present invention is not limited to the above-described examples, and various improvements and modifications can be made without departing from the gist of the present invention. Of course, changes may be made.

  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 2.4% by mass of a polyvinyl alcohol-polyacrylic acid copolymer (Clastomer AP-20 manufactured by Kuraray Co., Ltd.) and 0.01% 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 until the pH reached 1.5 to cause crosslinking.
After crosslinking, a 40% cesium carbonate aqueous solution (manufactured by Rare Metal Co., Ltd.) as a carrier was added so that the cesium carbonate concentration was 5.0% by weight to prepare a coating composition. That is, in this example, cesium carbonate serves as a carrier for the facilitated transport film 20a.

The coating composition is applied to a porous support (a laminate (manufactured by GE) obtained by laminating porous PTFE on the surface of a PP nonwoven fabric) and dried, whereby the facilitated transport membrane 20a and the porous An acidic gas separation layer 20 composed of the support 20b was produced.
The thickness of the facilitated transport film 20a was 30 μm.

<Production of separation module>
First, as shown in FIG. 3, a permeating gas flow path member 26 (tricot knitted epoxy-impregnated polyester) was fixed to the center tube 12 using an adhesive.

On the other hand, the supply gas flow path member 24 is a polypropylene net having a thickness of 0.5 mm. The fiber diameter was 150 μm, the fiber density was 3 mg / cm ² , and the tensile elastic modulus was 2.1 MPa.
The tensile elastic modulus is based on JIS K 7127, and a tensile tester (Tensilon RTC-1150A manufactured by Orientec Co., Ltd.) was prepared by using a strip of the supply gas flow path member 24 cut into a strip shape having a length of 50 mm and a width of 10 mm. ) And a tensile test at a tensile speed of 10 mm / min.
A fluorine-based coating (F-based) was formed as the coating 28 on both surfaces of the supply gas flow path member 24. In addition, the coating film 28 was formed by spray coating using Sumimold F1 manufactured by Sumiko.

Further, the acidic gas separation layer 20 was folded in two with the facilitated transport membrane 20a inside. As shown in FIG. 4, the two folds were performed so that one acidic gas separation layer 20 was slightly longer. Kapton tape was attached to the trough 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 trough of the facilitated transport film 20a.
Next, the supply gas flow path member 24 on which the film 28 was formed was sandwiched between the two folded acid gas separation layers 20 to produce a sandwiching body 36.

As shown in FIG. 4, in the vicinity of both ends in the width direction (arrow x direction), the circumferential direction (arrow y direction) is arranged on the porous support 20b side of the sandwich body 36 where the acidic gas separation layer 20 is shorter. An adhesive 30a (extending to the entire region and extending to the entire region in the width direction in the vicinity of the end on the opposite side to the circumferential folded portion, and made of an epoxy resin having a high viscosity (about 40 Pa · s). E120HP manufactured by Henkel Japan Co., Ltd. was applied.
Next, the side to which the adhesive 30a was applied was directed downward, and as shown in FIG. 5, the sandwiching body 36 and the permeating gas channel member 26 fixed to the central cylinder 12 were laminated and adhered.
Next, on the upper surface of the acidic gas separation layer 20 of the sandwiching body 36 laminated on the permeating gas flow path member 26, as shown in FIG. The adhesive 30a was applied in the vicinity of the end portion on the side opposite to the folded portion in the circumferential direction so as to extend over the entire region in the width direction. Further, as shown in FIG. 6, a permeated gas flow path member 26 is laminated on the acidic gas separation layer 20 coated with the adhesive 30a and bonded to form the first layered product 14. did.

In the same manner as described above, another holding member 36 shown in FIG. 4 in which the supply gas flow path member 24 having the film 28 formed on the surface thereof is sandwiched by the acidic gas separation layer 20 is produced. The adhesive 30a was similarly applied to the porous support 20b side of the short acidic gas separation layer 20. Next, in the same manner as in FIG. 5, the sandwiched body 36 is moved toward the first layer laminated body 14 (the permeated gas flow path member 26) formed on the side where the adhesive 30 a is applied first. 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. 5, 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. 7, 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 laminate 14a, and a 2 cm-cm thick SUS telescope prevention plate 16 having a shape shown in FIG. 1 was attached.
Further, a coating layer 18 is formed by winding an FPR resin tape around the peripheral surface of the telescope prevention plate 16 and the peripheral surface of the spiral laminated body 14a and sealing it, and the structure shown in FIG. 1 has a diameter of 4 cm and a width of 30 cm. A separation module 10 as shown was created. In addition, the thickness of the coating layer 18 was 5 mm.

[Example 2]
A separation module 10 was prepared in the same manner as in Example 1 except that the thickness of the facilitated transport film 20a was 70 μm.

[Example 3]
A separation module 10 was produced in the same manner as in Example 1 except that the thickness of the facilitated transport film 20a was 120 μm.

[Examples 4 to 6]
A separation module 10 is produced in the same manner as in Examples 1 to 3, except that the supply gas flow path member 24 is a polypropylene net having a fiber diameter of 250 μm, a fiber density of 5.5 mg / cm ² , and a tensile elastic modulus of 6.0 MPa. did.

[Examples 7 to 9]
A separation module 10 was produced in the same manner as in Examples 1 to 3, except that the supply gas flow path member 24 was a polypropylene net having a fiber diameter of 500 μm, a fiber density of 18 mg / cm ² , and a tensile elastic modulus of 320 MPa.

[Example 10]
A separation module 10 was produced in the same manner as in Example 2 except that the supply gas flow path member 24 was a polypropylene net having a fiber diameter of 120 μm, a fiber density of 2.1 mg / cm ² , and a tensile elastic modulus of 0.9 MPa.

[Example 11]
A separation module 10 was produced in the same manner as in Example 10 except that the thickness of the facilitated transport film 20a was 4 μm.

[Example 12]
A separation module 10 was produced in the same manner as in Example 10 except that the thickness of the facilitated transport film 20a was 160 μm.

[Examples 13 to 15]
A separation module 10 was produced in the same manner as in Examples 10 to 12 except that the supply gas flow path member 24 was a polypropylene net having a fiber diameter of 850 μm, a fiber density of 29 mg / cm ² , and a tensile elastic modulus of 510 MPa.

[Example 16]
The supply gas flow path member 24 is a polypropylene net having a fiber diameter of 1000 μm, a fiber density of 40 mg / cm ² , a tensile elastic modulus of 800 MPa, and the thickness of the facilitated transport film 20a is 160 μm. A separation module 10 was produced.

[Example 17]
A separation module 10 was produced in the same manner as in Example 1 except that the coating 28 was changed to a silicon-based coating (Si-based). The coating 28 was formed by spray coating using KF412SP manufactured by Shin-Etsu Chemical Co., Ltd.
[Comparative Example 1]
A separation module was prepared in the same manner as in Example 16 except that the coating 28 was omitted.

[Comparative Example 2]
A separation module was prepared in the same manner as in Example 7 except that the coating 28 was not used.

  For each of these examples and comparative examples, five separation modules 10 were produced.

[Performance evaluation]
<Airtightness (manufacturing stability)>
From the supply side, the discharge side of the manufactured separation module 10 is closed, filled with He gas until the pressure becomes 0.34 MPa, and sealed, until the pressure inside the separation module 10 decreases to 0.3 MPa. Was measured.
The separation module 10 that took 10,000 seconds or more to reach the pressure of 0.3 MPa was judged appropriate, and the number of appropriate separation modules 10 out of the five was evaluated. The evaluation is as follows.
A: 4 or more of the appropriate modules 10 out of 5 B: 3 to 1 of the appropriate modules 10 out of 5 C: 0 of the appropriate modules 10 out of 5

<Separation performance>
A mixed gas of H ₂ : CO ₂ : H ₂ O = 45: 5: 50 (partial pressure ratio) as a raw material gas G for testing was produced at a flow rate of 2.2 L / min, a temperature of 130 ° C. The supply was performed under the condition of a total pressure of 301.3 kPa. Further, a through hole for supplying a sweep gas was formed at the end of the central cylinder 12 on the raw material gas supply side, and Ar gas having a flow rate of 0.6 L / min was supplied as a sweep gas therefrom.
The gas (acid gas Gc and residual gas Gr) permeating through the separation module 10 was analyzed with a gas chromatograph, and the CO ₂ permeation rate (P (CO ₂ )) was calculated. The unit of transmission speed GPC is “1 GPU = [1 × 10 ⁻⁶ cm ³ (STP)] / [s · cm ² · cmHg]”.
For each example, the average value of the CO ₂ permeation rate of the five separation modules 10 was calculated to evaluate the separation performance. The evaluation is as follows.
A: Average value of CO ₂ transmission rate is 30 GPU or more B: Average value of CO ₂ transmission rate is 20 GPU or more and less than 30 GPU C: Average value of CO ₂ transmission rate is less than 20 GPU

<Comprehensive evaluation>
The performance of the separation module 10 was evaluated according to the following evaluation criteria.
A: Both airtightness and separation performance are evaluated as A
B: Evaluation of airtightness and separation performance, one is A and the other is B
C: Both airtightness and separation performance are evaluated as B
D: At least one C exists in the evaluation of airtightness and separation performance. The specifications of each separation module 10 and the results of the above evaluation are shown in the following table. Note that “-” in the performance evaluation result column indicates that the evaluation is not possible because a defect has occurred in the manufacturing stage of the separation module.

As shown in the above table, each of the separation modules 10 of Examples 1 to 17 of the present invention having the coating 28 on the surface of the supply gas flow path member 24 has good airtightness and separation performance. .
Among them, in the separation module 10 of Examples 1 to 15 in which the fiber diameter and fiber density of the member 24 for the supply gas flow channel are in a suitable range, at least one of hermeticity and separation performance is “A” evaluation, It demonstrates better performance.
In particular, Examples 1 to 9 in which the fiber diameter, the fiber density, and the tensile elastic modulus of the supply gas flow path member 24 are in the preferable range and the film thickness of the accelerating separation membrane 20a is in the preferable range are airtight. Both the properties and the separation performance are “A” evaluations, and particularly excellent performance is exhibited.

In contrast, Comparative Examples 1 and 2 having no coating 28 on the surface of the supply gas flow path member 24 are promoted by the supply gas flow path member 24 when the laminate 14 is wound around the central cylinder 12. It is considered that the transport membrane 20a was greatly damaged, the confidentiality was insufficient, and the separation performance could not be evaluated.
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 24 Member for supply gas flow path 26 Member for permeate gas flow path 28 Coating 30 Adhesive layer 30a Adhesive 34 Fixing means 36 Nipping body

Claims (7)

A central tube having a through-hole formed in the tube wall;
A supply gas flow path member serving as a flow path for the source gas;
A supply gas flow path member comprising a carrier that reacts with an acidic gas and that contains a hydrophilic compound for supporting the carrier, which separates the acidic gas from the source gas flowing through the supply gas flow path member. An acidic gas separation layer on the side surface;
A member for a permeating gas channel that becomes a channel through which the acidic gas that has permeated the facilitated transport membrane flows to the central cylinder;
Having at least one of a fluorine-based film and a silicon-based film formed on the surface of the supply gas flow path member on the facilitated transport film side,
A spiral-type module for acidic gas separation formed by winding one or more laminates having the supply gas flow path member, the acidic gas separation layer, and the permeate gas flow path member around the central cylinder. ^2. The acidic gas separation spiral module according to claim 1, wherein the supply gas flow path member is a woven fabric or a non-woven fabric having a fiber diameter of 100 to 900 μm and a fiber density of ² to 30 mg / cm ² .   The spiral module for acidic gas separation according to claim 1 or 2, wherein the facilitated transport membrane has a thickness of 5 to 150 µm.   4. The acidic gas separation according to claim 1, wherein a tensile elastic modulus of the member for a supply gas passage in which at least one of the fluorine-based film and the silicon-based film is formed is 1 to 500 MPa. Spiral type module.   The member for supply gas flow path is selected from polyethylene, polystyrene, polyethylene terephthalate, polytetrafluoroethylene, polyethersulfone, polyphenylene sulfide, polysulfone, polypropylene, polyimide, polyetherimide, polyetheretherketone and polyvinylidene fluoride. The spiral-type module for acidic gas separation according to any one of claims 1 to 4, wherein the spiral-type module has a network structure formed of yarns containing at least a seed resin.   The laminated body is an acidic gas separation layer folded in half with the facilitated transport membrane inside, and the permeated gas flow path member is stacked on a sandwiched body sandwiching the supply gas flow path member. The spiral-type module for acidic gas separation according to any one of claims 1 to 5, having a configuration.   The acidic gas separation layer according to any one of claims 1 to 6, wherein the acidic gas separation layer has a configuration in which the facilitated transport membrane is supported by a porous support.