JP2015029959A - Acidic gas separation module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent deterioration of an acidic gas separation membrane caused by condensed water, in a spiral type acidic gas separation module formed by winding thereon a laminate having the acidic gas separation membrane.SOLUTION: A hydrophobic porous membrane impermeable by condensed water is provided corresponding to the end face on the raw material gas supply side of a laminate-wound object formed by winding thereon a laminate having an acidic gas separation membrane.

Description

  The present invention relates to an acid gas separation module that selectively separates an acid gas from a raw material gas. Specifically, the present invention relates to an acidic gas separation module that can prevent deterioration of an acidic gas separation membrane due to condensed water in a spiral acidic gas separation module.

  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.

For example, in Patent Document 1, a multilayer body including an acidic gas separation membrane is wound around a central cylinder (a central permeate collecting pipe) for collecting separated acidic gas, in which through holes are formed in a tube wall. An 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, as shown in Patent Document 1, a laminate having an acidic gas separation membrane is wound around a central cylinder for collecting the separated acidic gas (wound around the central cylinder). The so-called spiral acid gas separation module can greatly increase the area of the acid gas separation membrane. Therefore, the spiral type acidic gas separation module can be efficiently processed.

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

In the facilitated transport type acidic gas separation module using the facilitated transport membrane as disclosed in Patent Document 2, a high-temperature and high-humidity source gas is supplied as the source gas.
In the facilitated transport film, as the moisture is absorbed, the carrier and water react with each other to release hydroxide ions, and the viscosity of the film decreases to improve the gas diffusibility. Therefore, the facilitated transport membrane generally tends to have a higher acid gas separation rate (permeation rate) as it absorbs moisture.
That is, in the facilitated transport type acidic gas separation module, conditions of high temperature and high humidity are essential, and the raw material gas contains a large amount of water vapor.

However, acidic gas separation membranes including not only facilitated transport membranes but also dissolution and diffusion membranes disclosed in Patent Document 1 deteriorate when condensed water comes into contact therewith.
However, an acid gas separation module that positively prevents contact between the acid gas separation membrane and the condensed water in the spiral type acid gas separation module is not known.

  An object of the present invention is to solve such problems of the prior art, and in a spiral type acidic gas separation module, it is possible to prevent condensed water from coming into contact with the acidic gas separation membrane. It is an object of the present invention to provide a spiral acid gas separation module that can exhibit predetermined performance.

In order to achieve this object, the acidic gas separation module of the present invention includes a central tube having a through-hole formed in a tube wall,
A laminate including an acidic gas separation membrane that separates and transports an acidic gas from a raw material gas, and is wound around a central cylinder, and a laminate wound product that is supplied with a raw material gas from one end face;
A telescope prevention plate provided facing the end face of the laminate wound product;
Provided is an acidic gas separation module having a hydrophobic porous membrane that is disposed upstream of a raw material gas supply side end face of a laminate wound material in a raw material gas supply direction and through which condensed water does not pass. .

In such an acidic gas separation module of the present invention, it is preferable that the porous membrane is disposed between the telescope prevention plate and the end surface of the laminate wound material gas supply side.
Moreover, it is preferable that the porous film is disposed in contact with the end surface of the laminated body wound on the source gas supply side.
Moreover, it is preferable that the telescope prevention board provided facing the raw material gas supply side end surface of a laminated body has a shape which diffuses the supplied raw material gas.
Moreover, it is preferable that the telescope prevention plate diffuses the source gas by generating a swirling flow of the source gas.
Moreover, it is preferable to have a diffusing member for diffusing the supplied source gas, which is arranged upstream of the telescope prevention plate in the source gas supply direction.
The pore size of the porous membrane is preferably 0.005 to 1 μm.
Moreover, it is preferable that the porosity of a porous membrane is 20 to 90%.
Furthermore, the thickness of the porous membrane is preferably 5 to 100 μm.

According to the present invention, in the spiral acidic gas separation module, it is possible to suitably prevent the condensed water from coming into contact with the acidic gas separation membrane.
Therefore, the acidic gas separation module of the present invention can prevent deterioration of the acidic gas separation membrane due to condensed water, and can exhibit predetermined performance stably over a long period of time.

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. It is a figure which shows notionally the edge part vicinity of the laminated body roll of the acidic gas separation module shown in FIG. 1, (A) is the figure seen from the winding direction, (B) is the figure seen from the width direction. is there. It is a figure which shows notionally the edge part vicinity of the laminated body roll of another example of the acidic gas separation module of this invention, (A) is the figure seen from the winding direction, (B) was seen from the width direction. FIG. It is a figure which shows notionally the edge part vicinity of the laminated body roll of another example of the acidic gas separation module of this invention, (A) is the figure seen from the winding direction, (B) was seen from the width direction. FIG.

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

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

The separation module 10 of the present invention is a so-called spiral type separation module. That is, the separation module 10 includes a plurality of sheet-like laminates 14a laminated, and the laminate is wound around the central cylinder 12 to obtain a laminate wound product 14 (that is, a laminate that is laminated and wound). 14a, and a telescope prevention plate 16 is provided on both end surfaces of the laminate wound article 14 by inserting the central cylinder 12 therethrough. Further, the outermost peripheral surface of the wound laminated body 14 a is covered with a gas impermeable coating layer 18.
Here, in the separation module 10 of the present invention, the entire surface of the end surface of the laminated body 14 is applied between the telescope prevention plate 16 on the side to which the source gas G is supplied and the laminated body 14. The porous membrane 28 is disposed in contact with the central tube 12 (see FIG. 8).

In such a separation module 10, the raw material gas G from which the acidic gas is separated passes, for example, through the telescope prevention plate 16 (the opening portion 16 d) and the porous membrane 28 on the far side in FIG. It is supplied from the end face of the object 14 to the inside of each laminated body 14a. Here, the condensed water contained in the source gas G is prevented from entering the stacked body 14 a by the porous film 28.
The source gas G supplied to the stacked body 14a is separated from the acidic gas Gc while flowing in the stacked body 14a.
The acidic gas Gc separated from the raw material gas G by the laminated body 14a is discharged from the central cylinder 12, and the raw material gas G from which the acidic gas has been separated (hereinafter referred to as residual gas Gr for convenience) It is discharged from the end surface opposite to the supply side of the wound product 14, and discharged to the outside of the separation module 10 through the telescope prevention plate 16 (same as above).

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

In the central cylinder 12, the aperture ratio (area ratio of the through-hole 12a in the outer peripheral surface of the central cylinder 12) in the region sealed with the adhesive layer 30 described later is preferably 1.5 to 80%, and preferably 3 to 75. % Is more preferable, and 5 to 70% is more preferable. Among these, from the practical viewpoint, the opening ratio of the center tube 12 is particularly preferably 5 to 25%.
By setting the aperture ratio of the center tube 12 within the above range, the acid gas Gc can be efficiently collected, and the strength of the center tube 12 can be increased to ensure sufficient processability.

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

  The center tube 12 may be provided with a supply port (supply unit) for supplying a gas (sweep gas) for flowing the separated acidic gas Gc to the open end 12b side as necessary.

The laminate 14a is formed by laminating an acidic gas separation layer 20, a supply gas flow path member 24, and a permeate gas flow path member 26.
1 indicates that the acidic gas separation layer 20 and the permeate gas flow path member 26 are bonded, the laminates 14a are bonded together, and the acidic gas Gc in the permeate gas flow path member 26 is bonded. This is an adhesive layer 30 in which the flow path is in an envelope shape opened on the center tube 12 side.

As described above, the separation module 10 in the illustrated example has a substantially cylindrical shape in which a plurality of the laminates 14a are laminated and the laminate of the laminates 14a is wound (wrapped) around the central cylinder 12. A laminate roll 14 is provided.
Hereinafter, for convenience, a direction (arrow y direction) corresponding to the winding of the laminated body 14a is referred to as a winding direction, and a direction orthogonal to the winding direction (arrow x direction) is referred to as a width direction.

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

In FIG. 2, the fragmentary sectional view of the laminated body 14a is shown. As described above, the arrow x is the width direction, and the arrow y is the winding direction.
In the illustrated example, the laminate 14a sandwiches the permeated gas flow path member 24 between the acid gas separation layers 20 folded in half to form a sandwiched 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 raw material gas G is supplied from one end face of the laminated body 14 through the telescope prevention plate 16 (its opening 16 d) and the porous film 28. That is, the source gas G is supplied to the end portion (end surface) in the width direction (arrow x direction) of each stacked body 14a.
As conceptually shown in FIG. 2, the source gas G supplied to the end face in the width direction of the stacked body 14 a flows in the width direction through the supply gas flow path member 24. In this flow, the acidic gas Gc in contact with the acidic gas separation 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 stacked body 14a ( 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 winding direction (the direction of the arrow y), reaches the central cylinder 12, and is centered from the through hole 12 a of the central passage 12. It flows into the cylinder 12. The acidic gas Gc that has flowed into the 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 end face on the opposite side of the laminated body 14 to prevent the telescope prevention plate 16 ( Through the opening 16d), it is discharged to the outside of the separation module 10.

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.
Such a supply gas flow path member 24 functions as a spacer of the acid gas separation layer 20 folded in half as described above, and constitutes a flow path for the source gas G. Further, the supply gas flow path member 24 preferably makes the source gas G turbulent. Considering this point, the supply gas flow path member 24 is preferably a net-like (mesh / mesh structure) member.

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

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

  The separation module 10 in the illustrated example is a facilitated transport type as a preferred embodiment. Therefore, the acidic gas separation layer 20 includes a facilitated transport film 20a and a porous support 20b.

The present invention is not limited to the facilitated transport type separation module, and may be a dissolution / diffusion type separation module using a dissolution / diffusion membrane as disclosed in Patent Document 1 described above.
However, since the separation module 10 of the present invention has the porous membrane 28, the condensed water can be prevented from coming into contact with the facilitated transport membrane 20a (acid gas separation membrane). Therefore, the separation module 10 of the present invention is required to be used at a high temperature and high humidity, and is more preferably used for a facilitated transport type separation module in which condensed water easily comes into contact with the facilitated transport membrane 20a.

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 length of the facilitated transport film 20a in the winding direction (the total length before folding in half) may be set as appropriate according to the size of the separation module 10, the processing capacity required for the separation module 10, and the like. Specifically, 100 to 10000 mm is preferable, 150 to 9000 mm is more preferable, and 200 to 8000 mm is even more preferable. Among them, the length of the facilitated transport film 20a is particularly preferably 800 to 4000 mm from a practical viewpoint.
By setting the length of the facilitated transport film 20a in the winding direction within the above range, the acidic gas Gc can be efficiently separated with respect to the film area, and further, the winding deviation when the stacked body 14a is wound. Is prevented, and the processability 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. Specifically, 1 to 200 μm is preferable, and 2 to 175 μm is more preferable.
By setting the thickness of the facilitated transport membrane 20a within the above range, sufficient gas permeability and separation selectivity can be realized.

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

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

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

As the crosslinkable group forming the hydrophilic compound, those capable of forming a hydrolysis-resistant crosslinked structure are preferably selected.
Specific examples include a hydroxy group (—OH), an amino group (—NH ₂ ), a chlorine atom (—Cl), a cyano group (—CN), a carboxy group (—COOH), and an epoxy group. . Among these, an amino group and a hydroxy group are preferably exemplified. Furthermore, most preferably, a hydroxy group is illustrated from the viewpoint of affinity with a carrier and a carrier carrying effect.

  Specific examples of 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 prevented.
Moreover, when using 2 or more types of alkali metal compounds as a carrier by the point that the prevention effect of blocking is obtained more suitably, the deliquescent property is better than the first compound having deliquescent properties 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, and stretching of polytetrafluoroethylene (PTFE) and high molecular weight polyethylene. Examples thereof include a porous membrane.
Among them, a stretched porous membrane of PTFE or high molecular weight polyethylene has a high porosity, is small in inhibition of diffusion of acidic gas (especially carbon dioxide gas), and is preferable from the viewpoints of strength and manufacturing suitability. Among them, a stretched porous membrane of PTFE is preferably used in terms of heat resistance and low hydrolyzability.

The porous membrane is hydrophobic because the facilitated transport membrane 20a containing moisture is likely to penetrate into the porous portion under the usage environment and does not cause deterioration in film thickness distribution or performance over time. Is preferred.
The porous membrane preferably has a maximum pore diameter of 1 μm or less.
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 if handling is performed in a coating apparatus using a roll-to-roll described later, wrinkles on the porous support 20b can be prevented, and productivity can be improved.

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 this 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 roll-to-roll (hereinafter also referred to as RtoR). That is, the prepared coating composition is applied while the porous support 20b is sent out from the feed roll formed by winding the long porous support 20b and conveyed in the longitudinal direction, and then the applied coating composition is applied. The product (coating film) is dried to produce the acidic gas separation layer 20 formed by forming the facilitated transport film 20a on the surface of the porous support 20b, and the produced acidic gas separation layer 20 is wound up.

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

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

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

The 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 laminated body 14a has the sandwiching body 36 in which the acidic gas separation layer 20 is folded in two with the facilitated transport film 20a inside, and the supply gas flow path member 24 is sandwiched. By laminating the permeating gas flow path member 26 on the sandwiching body 36 and bonding them with the adhesive layer 30, one laminated body 14a is formed.
The permeating gas flow path member 26 functions as a spacer between the stacked bodies 14a and is separated from the source gas G that reaches the through hole 12a of the central cylinder 12 toward the winding center (inner side) of the stacked body 14a. The flow path of the acid gas Gc is configured. Further, in order to properly form the flow path of the acidic gas Gc, the adhesive layer 30 described later needs to penetrate. Considering this point, the permeating gas channel member 26 is preferably a net-like (mesh / net-like) member, 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, a lamination method of the laminated body 14a and a winding method of the laminated body 14a, that is, a manufacturing method of the laminated body 14 will be described. 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 adhesive is used for the central cylinder 12. Then, the end of the permeating gas channel member 26 is fixed.

On the other hand, 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 the supply gas flow path member 24 is sandwiched therebetween. That is, a sandwiching body 36 is produced in which the supply gas flow path member 24 is sandwiched between the acidic gas separation layers 20 folded in half. In this case, the acidic gas separation layer 20 is not equally folded in half, but is folded in half so that one is slightly longer as shown in FIG.
Further, in order to prevent the facilitated transport film 20a from being damaged by the supply gas flow path member 24, a sheet-like protective member (for example, Kapton tape) folded in half at the trough portion where the acidic gas separation layer 20 is folded in half. 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 in the entire winding direction (arrow y direction). Then, 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 winding direction in the vicinity of both ends in the width direction, and further on the opposite side of the folded portion. It extends in the entire width direction in the vicinity of the end portion and is applied in a strip shape.

  Next, as conceptually shown in FIG. 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 laminated body 14a.

Next, as shown in FIG. 4, as shown in FIG. 4, a sandwiching body 36 in which the supply gas flow path member 24 is sandwiched between the acidic gas separation layers 20 is produced, and an adhesive 30 a that becomes the adhesive layer 30 is applied. The permeated gas flow path member 26 and the sandwiching body 36 that are finally stacked are stacked and bonded with the side to which the adhesive is applied facing down.
Further, similarly to the above, 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 14a of the 2nd layer is laminated | stacked.

Hereinafter, the steps of FIGS. 4 to 6 are repeated to stack a predetermined number of stacked bodies 14a as conceptually shown in FIG.
In addition, as shown in FIG. 7, it is preferable to laminate | stack the laminated body 14a so that it may space apart from the center cylinder 12 in a winding direction gradually as it goes upwards. This facilitates winding (winding) of the laminated body 14a around the central cylinder 12, and the end of the permeate gas flow path member 26 on the central cylinder 12 side or the vicinity of the end is preferably the central cylinder. 12 can be contacted.

When the predetermined number of the laminated bodies 14a are laminated, as shown in FIG. 7, the central cylinder 12 on the upper surface of the permeate gas flow path member 26, which is first fixed to the central cylinder 38 with the adhesive 38a on the outer peripheral surface of the central cylinder 12. The adhesive 38b is applied between the sandwiching body 36 and the adhesive 36b.
Next, as indicated by an arrow yw in FIG. 7, the laminated body 14 a is wound (wrapped) around the central cylinder 12 so as to wind the laminated body 14 a.
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 laminated body 14 is obtained by winding the laminated body 14a around the central cylinder.

  As described above, the raw material gas G is supplied from the end of the supply gas flow path member 24, and the acidic gas Gc passes (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 net-like permeating gas channel member 26. Therefore, the adhesive 30a permeates (impregnates) into the porous support 20b and the permeating gas flow path member 26, and the adhesive layer 30 is formed in both.
Further, as described above, the adhesive layer 30 (adhesive 30a) is formed in a strip shape extending in the entire vicinity in the winding direction in the vicinity of both ends in the width direction. Further, the adhesive layer 30 extends 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. In addition, 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.

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

FIG. 8 conceptually shows the vicinity of the end portion on the supply side of the source gas G of the separation module 10.
In FIG. 8, (A) is a view as seen from the winding direction (a direction orthogonal to the width direction (arrow x direction)), and (B) is a view as seen from the width direction. 8 shows only the supply side of the raw material gas G, except that the porous film 28 is not provided, the discharge side of the carbon dioxide gas Gc and the residual gas Gr basically has the same configuration. Have.

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

The telescope prevention plate 16 may be disposed in contact with the end face of the laminated body 14 (the porous film 28 on the supply side of the raw material gas G).
However, in order to use the entire end face of the laminated body 14 for supplying the source gas and discharging the residual gas Gr, as shown in FIG. 8, the telescope prevention plate 16 and the end face of the laminated body 14 Is preferably arranged with a slight gap.

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.

As described above, in the separation module 10 in the illustrated example, the porous film 28 is disposed between the telescope prevention plate 16 and the laminated body 14 on the supply side of the source gas G.
In the illustrated example, the porous film 28 is provided in contact with an end surface on the raw material gas supply side (hereinafter also simply referred to as a supply-side end surface) of the laminated body 14 and covers the entire end surface. It is a quality film (film-like material / sheet-like material).

The porous film 28 is hydrophobic and has a through hole through which gas (water vapor) can pass but condensed water cannot pass.
In the present invention, in the supply direction (width direction) of the raw material gas G, such a porous membrane 28 is provided on the upstream side (hereinafter also simply referred to as upstream / downstream) of the supply side end surface of the laminated body 14. By having it, it prevents that condensed water contacts the facilitated-transport film | membrane 20a (acid gas separation membrane), and prevents deterioration of the facilitated-transport film | membrane 20a resulting from condensed water.

As described above, the accelerated separation type separation module 10 is required to operate at high temperature and high humidity, and the raw material gas G containing a large amount of water vapor is supplied. Here, the water vapor contained in the raw material gas G is partially condensed into condensed water due to contact with various members and temperature decrease.
On the other hand, the facilitated transport film 20a has high hygroscopicity as described above. However, when the condensed water comes into contact with the condensed transport film, the film is dissolved and easily deteriorated.
Therefore, in the conventional (acid gas) separation module, the deterioration of the facilitated transport membrane 20a due to condensed water progresses as the treatment is performed, and the separation performance and treatment efficiency of the acid gas decrease with time.

On the other hand, since the separation module 10 of the present invention has a porous membrane 28 that is hydrophobic and does not allow condensed water to pass through, the condensed water passes from the supply-side end surface of the laminated body 14 to the laminated body 14a. Intrusion can be prevented.
Therefore, the separation module 10 of the present invention can significantly suppress deterioration of the facilitated transport membrane 20a due to condensed water, and can exhibit predetermined performance over a long period of time. In addition, since the porous film 28 is used, the pressure loss of the source gas G is small.

In the separation module 10 of the present invention, the porous membrane 28 has sufficient heat resistance and moisture resistance, is hydrophobic, and can pass gas but cannot pass condensed water. Various porous membranes can be used.
Specifically, a porous film 28 made of PTFE, PP, polyvinylidene fluoride (PVDF), PSF, polymethylpentene (TPX), a porous inorganic film or the like, particularly a porous film 28 made of these materials with a small pore diameter. Is preferably exemplified.
In particular, the porous film 28 made of PTFE, PP, or the like can be suitably used.

The pore size of the porous membrane 28 is preferably 0.005 to 1 μm, and more preferably 0.01 to 0.5 μm.
By setting the size of the pores of the porous film 28 within this range, it is preferable in that the pressure loss of the raw material gas G can be reduced, the permeation of condensed water can be more suitably prevented, and the like.
The size of the pores is measured by the size of the fine particles capable of capturing 50% by mass or more by passing a liquid containing 0.01% by mass of the fine particles of the corresponding size through the porous film 28.

The porosity of the porous film 28 is preferably 20 to 90%, more preferably 30 to 85%.
By setting the porosity of the porous film 28 within this range, it is preferable in that the pressure loss of the raw material gas G can be reduced and the permeation of condensed water can be more suitably prevented.

The thickness of the porous film 28 is preferably 5 to 100 μm, and more preferably 8 to 80 μm.
By setting the film thickness of the porous film 28 within this range, it is preferable in that the pressure loss of the raw material gas G can be reduced and the permeation of condensed water can be more suitably prevented.

In the separation module 10 of the present invention, the position of the porous membrane 28 is not limited to the position where the porous film 28 is in contact with the supply side end face of the laminate wound product 14, but may be various positions as long as it is upstream of the supply side end face. Is available. For example, the porous film 28 may be disposed in contact with the upstream or downstream end face of the telescope prevention plate 16.
However, it is preferable to arrange the porous film 28 between the telescope prevention plate 16 and the laminated body 14 in terms of prevention of damage to the porous film 28, ease of arrangement, and the like. As described above, it is more preferable that the laminated body 14 is disposed so as to be in full contact with the supply-side end surface.

Further, the porous film 28 does not need to be provided corresponding to the entire surface of the supply-side end surface of the laminated body 14. That is, if the porous membrane 28 is provided corresponding to at least a part of the supply-side end surface of the laminated body 14, the effect of preventing the facilitated transport membrane 20 a from being deteriorated by condensed water can be obtained.
Preferably, the porous film 28 is provided on the supply side end face of the laminated body 14 so as to correspond to the entire surface of the region into which the source gas G flows. For example, the porous film 28 may be provided corresponding to only the region of the opening 16 d of the telescope prevention plate 16.
Furthermore, as shown in the illustrated example, the laminate wound product is easy in the formation and arrangement work of the porous film 28 and more reliably prevents condensed water from reaching the laminate wound product 14. It is more preferable to provide it corresponding to the entire surface of the 14 supply side end faces.

In the separation module 10 shown in FIGS. 1 and 8, the raw material gas G simply passes through the telescope prevention plate 16.
Here, in the separation module of the present invention, the telescope prevention plate disposed on the supply side end face side of the laminated body 14 does not simply pass the source gas G, but diffuses the source gas G. It preferably has a function.

  FIG. 9 conceptually shows the vicinity of the end portion on the supply side of the source gas G as an example. In FIG. 9, (A) and (B) are the same as those in FIG.

  In the telescoping prevention plate 16 shown in FIG. 8, the ribs 16c that connect the outer ring portion 16a and the inner ring portion 16b are parallel to the supply direction of the source gas G (= width direction (arrow x direction)). Accordingly, the supplied source gas G passes straight through the opening 16d of the telescope prevention plate 16, and the laminated body 14 (laminated body 14a (supply gas flow path member 24)) from the supply side end face. Flow into.

On the other hand, in the telescoping prevention plate 50 shown in FIG. 9, the plate-like rib 50c connecting the outer ring portion 50a and the inner ring portion 50b is counterclockwise toward the supply direction of the source gas G. It is inclined in the direction of arrow y1. In other words, the rib 50c has the downstream end portion of the raw material gas G positioned on the downstream side counterclockwise relative to the upstream end portion.
Therefore, when the raw material gas G passes through the telescope prevention plate 50, it is guided in the counterclockwise direction by the rib 50c and becomes a swirl flow swirling in the counterclockwise direction. 14 is incident on the supply side end face.

In the separation module, the inflow position of the source gas G is specified on the supply side end face of the laminate wound article 14 according to the source gas G supply means, the source gas flow path upstream of the telescope prevention plate, and the like. There is a case to concentrate on the part of.
When the source gas G concentrates on a specific portion of the supply-side end face of the laminate wound product 14, the contribution to the acidic gas separation by the facilitated transport membrane 20a in the other region is reduced. Area) facilitated transport membrane 20a does not contribute to the separation of acid gas at all. In such a state, the processing efficiency of the raw material gas and the separation efficiency of the acidic gas are greatly reduced.

On the other hand, the telescope prevention plate arranged on the supply-side end face of the laminate wound product 14 like the telescope prevention plate 50 shown in FIG. The gas G can be supplied to a wider region (preferably the entire surface) of the supply-side end surface of the laminate body 14.
Therefore, according to this configuration, it is possible to separate the acidic gas from the raw material gas G by using the facilitated transport film 20a constituting the laminated body 14 as a whole. Separation efficiency can be improved.

In order to obtain a sufficient diffusion effect, it is preferable that the telescope prevention plate 50 for diffusing the raw material gas G is disposed at a certain distance from the supply-side end surface of the laminated body 14.
However, if the telescope prevention plate 50 and the laminated body 14 are separated too much, problems such as the effect of having the telescope prevention plate 50 cannot be obtained.
Considering the above points, the distance a between the telescope prevention plate 50 and the supply-side end surface of the laminated body 14 is preferably 0.01 to 2 mm, and more preferably 0.05 to 1.5 mm.

As the telescope prevention plate having the function of diffusing the source gas G, various configurations can be used other than the configuration in which the ribs 50c are inclined in the counterclockwise direction as shown in the illustrated example.
For example, a structure in which the rib has a shape like a propeller, a structure in which the rib has a pyramid shape like a long prism, a structure in which a large number of through holes are regularly or irregularly formed like a punching metal, and the rib is a mesh The structure etc. which are formed in the shape of a shape or a lattice are illustrated suitably.
That is, if the telescope prevention plate having the diffusion function of the raw material gas G has a shape that can be diffused in the surface direction of the supply-side end surface of the laminated body 14 by changing the flow path of the raw material gas G that passes therethrough, Various shapes are available.

Further, the telescope prevention plate having the function of diffusing the source gas G is not limited to the configuration having the function of diffusing the source gas G in the entire surface direction of the supply side end face.
For example, when the source gas G is supplied through a supply pipe or the like, it may have a function of diffusing the source gas only in a portion corresponding to the supply pipe.

  Furthermore, the separation module according to the present invention is not limited to the configuration in which the telescope prevention plate has a function of diffusing the raw material gas G, like the telescope prevention plate 50 shown in FIG. A diffusion plate (baffle plate) for diffusing the gas G may be provided.

FIG. 10 conceptually shows the vicinity of the end portion on the supply side of the raw material gas G as an example. In FIG. 10, (A) and (B) are the same as those in FIG.
In the example shown in FIG. 10, a diffusion plate 54 is provided in contact with the telescope prevention member 16 upstream of the telescope prevention member 16. For example, the diffusing plate 54 has a shape in which through holes 54a through which the source gas G passes are formed in a disk-shaped plate material radially at equal angular intervals and at equal intervals in the radial direction.

  By providing such a diffusion plate upstream of the telescope prevention member 16, the raw material gas G is supplied to the laminate wound material 14 as in the case of using the telescope prevention plate 50 having the diffusion function described above. Supplying to a wider area (preferably the entire surface) of the side end face, and using the facilitated transport film 20a constituting the laminate wound body 14 as a whole, the raw material gas processing efficiency and the acid gas separation efficiency are improved. it can.

In addition, in the diffusing plate 54, various positions can be used as the positions of the through holes 54a other than the positions in the illustrated example.
For example, the through holes 54a may be similarly formed radially, and the formation interval, size, number, and the like of the through holes 54a may be different in each direction. Further, depending on the supply position of the source gas G (the position of the supply pipe for supplying the source gas to the separation module, etc.), a through hole 54a is provided in the vicinity of the supply position of the source gas G or the supply position of the source gas G It may not be provided.

In addition to the configuration in which the through-hole is provided in the disk-shaped plate material, the diffusion plate has a blade member such as a propeller, a configuration having a baffle plate that partially blocks the flow of the raw material gas G, and the like. Is also available. Furthermore, various configurations exemplified by the telescope prevention plate having the diffusion function of the source gas G described above, such as the configuration of the telescope prevention plate 50 using the source gas G as a swirling flow, can also be used.
That is, the diffusion plate also changes the flow path of the raw material gas G that passes therethrough in the same manner as the telescope prevention plate having the diffusion function of the raw material gas G described above, and the surface direction of the supply-side end surface of the laminate wound article 14 Various shapes can be used as long as the shape can be diffused.

Various materials can be used for the diffusion plate 54 as long as the material has sufficient heat resistance and moisture resistance.
Specifically, as the material for forming the diffusion plate 54, various materials exemplified for the telescope prevention plate 16 can be suitably used.

Similarly to the telescope prevention plate having the above-described source gas diffusion function, in order to suitably supply the source gas G over the entire supply side end face of the laminate wound product 14, the diffusion plate 54 is also provided with a laminate winding. It is preferable to dispose a certain distance from the supply-side end surface of the article 14.
On the other hand, if the distance between the diffusing plate 54 and the supply-side end surface of the laminated body 14 is too far, the effect of providing the diffusing plate 54 may not be sufficiently obtained. Furthermore, there is also a disadvantage that the separation module 10 becomes larger as the distance between the diffusion plate 54 and the laminated body 14 increases.
Considering this point, the distance b between the diffusion plate 54 and the supply-side end surface of the laminated body 14 is preferably 2 to 1000 mm, and more preferably 4 to 750 mm.

In the example shown in FIG. 10, the diffusion plate 54 is disposed in contact with the telescope prevention plate 16, but the diffusion plate 54 is in contact with the telescope prevention plate 16 according to the distance b. It does not have to be.
Also, the separation module of the present invention. When such a diffusion plate 54 is provided, the porous film 28 described above may be provided on the diffusion plate 54.
Furthermore, if necessary, the telescope prevention plate 50 having a diffusion function of the source gas G and the diffusion plate 54 may be used in combination.

  The covering layer 18 covers the peripheral surface of the laminate wound product 14 (or further, the telescope prevention plate (or further the diffusion plate 54)), and this peripheral surface, that is, from the end of the laminate wound product 14 to the outside. This is for blocking the discharge of the raw material gas G and the residual gas Gr.

As the coating layer 18, various materials that can shield the raw material gas G and the like can be used. The covering layer 18 may be a cylindrical member or may be configured by winding a wire or a sheet-like member.
As an example, the FRP wire is impregnated with the adhesive used for the adhesive member 40 and the adhesive layer 30 described above, and the wire impregnated with the adhesive is laminated with no gaps as needed. The coating layer 18 wound around the wound product 14 is illustrated.
In this case, if necessary, a sheet shape such as a Kapton tape for preventing penetration of the adhesive into the laminated body 14 between the coating layer 18 and the laminated body 14. A member may be provided.

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

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

[Example 1]
<Production of acid gas separation layer>
An aqueous solution containing 3.3% by mass of a polyvinyl alcohol-polyacrylic acid copolymer (Clastomer AP-20 manufactured by Kuraray Co., Ltd.) and 0.016% by mass of a crosslinking agent (25% by mass glutaraldehyde aqueous solution manufactured by Wako Pure Chemical Industries, Ltd.). Prepared. To this aqueous solution, 1 M hydrochloric acid was added until the pH reached 1.7 to cause crosslinking.
After crosslinking, a 40% aqueous cesium carbonate solution (manufactured by Rare Metal Co., Ltd.) was added so that the concentration of cesium carbonate was 7.0% by weight. That is, in this example, cesium carbonate serves as a carrier for the facilitated transport film 20a.
Furthermore, 0.004% by mass of a surfactant (1% by mass of Lapisol A-90 manufactured by NOF Corporation) was added to prepare a coating composition.

  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.

<Production of separation module>
First, as shown in FIG. 3, a permeating gas flow path member 26 (tricot knitted epoxy-impregnated polyester having a thickness of 0.5 mm) was fixed to a center tube 12 made of SUS. As the fixing means 34, an adhesive capable of bonding SUS and resin was used.

On the other hand, the produced acidic gas separation layer 20 was folded in two with the facilitated transport membrane 20a inside. As shown in FIG. 4, the two folds were performed so that one acidic gas separation layer 20 was slightly longer. 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 (a polypropylene net having a thickness of 0.5 mm) was sandwiched between the acid gas separation layer 20 folded in half, and a sandwich body 36 was produced.

As shown in FIG. 4, on the porous support 20b side where the acidic gas separation layer 20 of the sandwiching body 36 is short, in the vicinity of both ends in the width direction (arrow x direction), the winding direction (arrow y direction). And an adhesive made of an epoxy resin having a high viscosity (about 40 Pa · s) extending in the entire width direction in the vicinity of the end opposite to the folded portion in the winding direction. 30a (E120HP manufactured by Henkel Japan) 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 channel member 26, as shown in FIG. And the adhesive 30a was apply | coated to the whole area of the width direction in the vicinity of the edge part on the opposite side to the folding | turning part of a winding direction. Further, as shown in FIG. 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 14a. did.

In the same manner as described above, another sandwich member 36 shown in FIG. 4 was produced, and similarly, the adhesive 30a was similarly applied to the porous support 20b side of the short acid gas separation layer 20. Next, in the same manner as in FIG. 5, the sandwiched body 36 is directed to the first layer laminated body 14 a (the permeate gas flow path member 26) formed first on the side to which the adhesive 30 a has been applied. It laminated | stacked on the laminated body 14a (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. The eye laminate 14a was formed.
Further, in the same manner as the second layer, the third layered body 14a was formed on the second layered body 14a.

After laminating the three-layered laminate 14a on the permeate gas flow path member 26 fixed to the central cylinder 12, an adhesive 38a is applied to the peripheral surface of the central cylinder 12, as shown in FIG. The adhesive 38b was applied on the permeating gas flow path member 26 between the central cylinder 12 and the lowermost layered laminate 14a. The adhesives 38a and 38b were the same as the adhesive 30a.
Next, the central cylinder 12 was rotated in the direction of the arrow yw in FIG. 7, and the three-layered laminated body 14 a was wound around the central cylinder 12 in a multiple manner so as to obtain a laminated body 14.

The entire surface of one end face of the laminate wound material 14 thus produced was covered with a porous film 28 made of PP (manufactured by 3M) having a thickness of 35 μm. This porous film 28 is a film having a pore diameter of 0.16 μm and a porosity of 40%.
The porous membrane 28 has a slit in the center, is inserted through the center tube 12, and bonds the end of the slit and the center tube 12, and the covered porous membrane 28 and the upper part of the laminate wound product 14. Fixed by agent.
Therefore, in this example, the end surface on the side where the porous film 28 is provided in the laminated body 14 becomes the supply-side end surface of the source gas G.

Furthermore, the center tube 12 was inserted into the inner ring portion 16b at both ends of the laminated body 14, and a 2 cm-thick SUS telescope prevention plate 16 having a shape shown in FIG. 8 was attached. The distance between the telescope prevention plate 16 and the laminate wound product 14 was 1 mm.
Furthermore, the FRP resin tape was wound around the peripheral surface of the telescope prevention plate 16 and the peripheral wound body 14 and sealed to form the coating layer 18, thereby manufacturing the separation module 10.
The membrane area of the prepared separation module 10 was 1.2 m ² (design value) in total.

[Example 2]
A separation module 10 was produced in the same manner as in Example 1 except that the porous membrane 28 was changed to a porous membrane made of PTFE (manufactured by Gore-Tex) having a thickness of 15 μm.
The porous film 28 is a film having a pore diameter of 0.2 μm and a porosity of 80%.

[Example 3]
The PPS that prevents the telescoping prevention plate on the supply side of the raw material gas G from the telescoping prevention plate 18 shown in FIG. 8 is used to turn the raw material gas G counterclockwise by the rib 50c as shown in FIG. A separation module 10 was produced in the same manner as in Example 2 except that the telescope prevention plate 50 was changed to a manufactured one.
In addition, the distance a between the laminated body wound material 14 and the telescope prevention plate 50 was 1 mm.

[Example 4]
Upstream of the telescoping prevention plate 16 is a through-hole 54a for allowing the source gas G to pass through a disk-like plate material as shown in FIG. 10, radially at equal angular intervals and at equal intervals in the radial direction. A separation module 10 was produced in the same manner as in Example 2 except that a SUS diffusion plate 54 having a thickness of 1 cm was provided.
The distance b between the laminated body 14 and the diffusion plate 54 was 4 mm.

[Comparative example]
A separation module was produced in the same manner as in Example 1 except that the porous membrane 28 was not provided.

[Performance evaluation]
<Module factor>
By measuring the separation factors of the separation modules of the produced separation modules of Examples and Comparative Examples, the separation module and the facilitated transport membrane 20a itself on the porous support 20b used in the separation module, Calculated.
In this example, the CO ₂ / H ₂ separation factor and the CO ₂ / N ₂ separation factor were measured, and the module factor was calculated for each separation factor. In the example, the source gas G was supplied from the side where the porous film 28 was provided.

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

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

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

<Condensed water resistance>
A raw material gas G (flow rate 1.8 L / min) of N ₂ : CO ₂ : H ₂ O = 62: 20: 18 (partial pressure ratio), which is a condition exceeding the saturated water vapor pressure, is at a temperature of 130 ° C. and a total pressure of 2001.3 kPa. Then, the CO ₂ / N ₂ separation factor (α) at the start of supply of the raw material gas G and after 3 hours is calculated and the performance deterioration after 3 hours is observed. Resistance (condensation water resistance) was evaluated.
The case where there was no performance deterioration was evaluated as A; the case where there was a performance deterioration of 10% or less, B; the case where there was a performance deterioration exceeding 10%, and C;
The results are shown in the table below.

As shown in the above table, each of the separation modules 10 of the present invention has an acid gas separation performance equivalent to that of the conventional separation module and also has excellent condensate resistance (condensation water resistance).
Particularly, Example 3 in which the telescope prevention plate 50 has the diffusion performance of the raw material gas G, and Example 4 in which the diffusion plate 54 is provided upstream of the telescope prevention plate 16 are provided in the laminated body 14. By supplying the raw material gas G to more regions, good acid gas separation performance is obtained.
From the above results, the effects of the present invention are clear.

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

DESCRIPTION OF SYMBOLS 10 (Acid gas) separation module 12 Center cylinder 14 Laminated body roll 14a Laminate body 16 and 50 Telescope prevention board 16a and 50a Outer ring part 16b and 50b Inner ring part 16c and 50c Rib 16d and 50ad Opening part 18 Covering layer 20 Acid Gas Separation Layer 20a Accelerated Transport Membrane 20b Porous Support 24 Supply Gas Channel Member 26 Permeate Gas Channel Member 28 Porous Membrane 30 Adhesive Layer 30a Adhesive 34 Fixing Means 36 Holding Body 40 Adhesive Member 54 Diffusion Plate 54a Through hole

Claims (9)

A central tube having a through-hole formed in the tube wall;
A laminate including an acidic gas separation membrane that separates and transports an acidic gas from a raw material gas, wound around the central cylinder, and a laminated body supplied with the raw material gas from one end face;
A telescope prevention plate provided facing the end face of the laminate wound product;
An acidic gas separation module comprising: a hydrophobic porous membrane that does not allow condensed water to pass, and is disposed upstream of a raw material gas supply side end face of the laminate wound material in a raw material gas supply direction.   2. The acidic gas separation module according to claim 1, wherein the porous membrane is disposed between the telescope prevention plate and a raw material gas supply side end face of the laminate wound product.   The acidic gas separation module according to claim 2, wherein the porous membrane is disposed in contact with a raw material gas supply side end face of the laminate wound product.   The acidic gas according to any one of claims 1 to 3, wherein the telescope prevention plate provided facing the source gas supply side end face of the laminate wound product has a shape for diffusing the supplied source gas. Separation module.   The acidic gas separation module according to claim 4, wherein the telescope prevention plate diffuses the raw material gas by causing a swirling flow of the raw material gas.   6. The acidic gas separation module according to claim 1, further comprising a diffusion member that diffuses the supplied source gas, which is disposed upstream of the telescope prevention plate in the source gas supply direction.   The acidic gas separation module according to any one of claims 1 to 6, wherein the pore size of the porous membrane is 0.005 to 1 µm.   The acid gas separation module according to any one of claims 1 to 7, wherein a porosity of the porous membrane is 20 to 90%.   The acidic gas separation module according to claim 1, wherein the porous membrane has a thickness of 5 to 100 μm.