JP5999844B2 - Acid gas separation module - Google Patents

Description

  The present invention relates to an acid gas separation module that separates and extracts an acid gas from a raw material gas containing water vapor using a facilitated transport membrane.

  Conventionally, in order to selectively separate a specific component such as an acid gas from a raw material gas containing a plurality of gas components, a spiral type, a flat membrane type, and a hollow fiber type having a separation membrane that selectively permeates the specific component Various types of membrane modules are used.

  The spiral type separation membrane module is formed by winding a separation membrane, a raw material gas supply side channel member and a permeation side channel member around a central tube, and is relatively thin as a separation membrane. Since an easy sheet-like separation membrane is used, it is relatively easy to improve the membrane area, and it has an advantage that it has excellent pressure resistance and can be manufactured at a relatively low cost.

  In a spiral type separation membrane module, in order to efficiently collect a specific component separated by passing through a separation membrane into a central tube, a permeate-side flow path member having a plurality of substantially parallel grooves is divided into a plurality of grooves. It arrange | positions so that the center axis | shaft of a center pipe | tube may become substantially perpendicular | vertical, and it is made to wind around a center pipe | tube with the separation membrane and the raw material gas supply side flow path member (patent documents 1-3 etc.).

  In such a spiral separation membrane module, separation of the most permeable component (first permeable component) in the raw material gas is generally performed by separating the flow of the raw material gas on the supply side and the permeable gas on the transmission side. By making the flow counter-current, the most efficient implementation is possible. The reason is that by forming a countercurrent flow state, the partial pressure difference between the raw material gas side and the permeate gas side of the separation membrane, which becomes the permeation driving force of the first easily permeable component, It is because it can hold | maintain well over.

  On the other hand, when a raw material gas containing water vapor contains a component having higher permeability than the separation target (here, water vapor), the partial pressure difference between the raw material gas side and the permeate gas side of the separation membrane is different from that of the raw material gas side. It is greatly influenced by the amount of water vapor present on both the permeate gas sides. Most of the water vapor permeates near the inlet side of the raw material gas, so that there is no water vapor over most of the length direction of the module. Therefore, on the permeate gas side, there is almost no water vapor in most parts except near the entrance, and the partial pressure of the separation target is high. When the partial pressure on the permeate gas side is high, there is a problem that the partial pressure difference that becomes the driving force for permeation becomes small and the permeability of the separation target is deteriorated.

  In Patent Document 4, in a separation membrane module that separates carbon dioxide from a raw material gas containing water vapor, a permeate gas outlet is provided in an intermediate portion between the inlet and outlet of the raw material gas, and the raw material gas inlet side is co-flowed. Discloses a method for efficiently separating and recovering carbon dioxide by making the outlet side counter-current. In Patent Document 4, the separation membrane used in the separation membrane module is exemplified by a polymer separation membrane such as a polyimide membrane.

  On the other hand, as a separation membrane for an acidic gas such as carbon dioxide, the membrane contains a substance (carrier) that selectively and reversibly reacts with one or more specific components in the raw material gas, and transports them. A spiral separation membrane module using a facilitated transport membrane that uses this carrier to transport and separate a specific component to the opposite side of the membrane has been proposed.

The acidic gas separation membrane module proposed by the present applicant described in Patent Document 5 and the like shows basicity (releases OH ⁻ ) in the presence of water, and the OH ⁻ reacts with CO _2. Thus, an alkali metal compound capable of selectively incorporating CO ₂ into the film is used as a carrier.

JP-A-11-197469 JP 2000-288541 A JP 2004-283701 A JP-A-10-57746 JP 2013-111507 A

  As in Patent Document 5, in membrane separation using a facilitated transport membrane in the presence of water, the carrier does not function unless water (water vapor) is present, so water is essential in the separation membrane. However, as already mentioned, water vapor has a very high membrane permeability, and most of the water is permeated near the inlet side of the raw material gas, so that water vapor does not exist over most of the length direction of the module.

  Patent Document 4 discloses a separation and recovery method corresponding to the easy permeability of water vapor. However, in Patent Document 4, although only the flow of the permeate gas is controlled in order to maintain the partial pressure difference between the raw material gas side and the permeate gas side of the separation membrane, there is an effect of retaining water vapor in the separation membrane. Not enough.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide an acidic gas separation module having a high separation performance, including an facilitated transport membrane containing an acidic gas carrier that reacts with acidic gas in the presence of water. To do.

The acid gas separation module of the present invention comprises:
A supply gas flow path member to which a source gas containing at least an acid gas and water vapor is supplied;
A facilitated transport membrane comprising at least a hydrophilic compound and an acidic gas carrier that reacts in the presence of water with an acidic gas in the raw material gas supplied to the supply gas flow path member;
It has a laminate formed by laminating a permeate gas channel member through which acid gas that has reacted with the acid gas carrier and permeated the facilitated transport membrane flows.
This laminated body is an acid gas separation module wound around a permeating gas collecting pipe having a through-hole formed in the pipe wall,
The permeate gas flow path member has at least a plurality of grooves on the surface on the facilitated transport membrane side;
An angle θ formed by the plurality of grooves and the central axis of the permeating gas collecting pipe is 0 ° or more and 75 ° or less. The formed angle θ is preferably 45 ° or less.

  In this specification, “the angle θ formed by the plurality of grooves and the central axis of the permeate gas collecting pipe” means that the downstream direction of the raw material gas in the acidic gas separation module on the central axis of the permeate gas collecting pipe is 0 degrees upstream It means the angle between the groove and the central axis when the direction is 180 degrees.

The permeate gas flow path member is preferably made of a synthetic knitted fabric knitted with synthetic fibers so as to have irregularities (grooves), is made of a tricot knitted fabric, and the groove is formed by two wales adjacent to the tricot knitted fabric. It is more preferable that it is formed.
As the acidic gas carrier that reacts with the acidic gas in the presence of water, an alkali metal compound is preferable.

  A mode in which the raw material gas is supplied from one end side of the permeate gas collecting pipe to the supply gas flow path member in the length direction of the permeate gas collecting pipe and the acid gas is taken out from the other end of the permeate gas collecting pipe, that is, used in parallel flow It is preferable that

  The acidic gas separation module of the present invention is a spiral-type module using a facilitated transport membrane including an acidic gas carrier that reacts a raw material gas containing at least an acidic gas and water vapor in the presence of the acidic gas in the raw material gas, The permeate gas flow path member is provided with a plurality of grooves whose angle θ formed with the central axis of the permeate gas collecting pipe is 0 ° or more and 75 ° or less on at least the surface on the facilitated transport membrane side. According to such a configuration, since the plurality of grooves for guiding the permeated gas in the permeate gas flow path member have the components in the downstream direction of the supply gas, the easily permeable water vapor has a length within the permeate gas flow path member. The water component can be supplied to the facilitated transport membrane adjacent to the permeate gas channel member while staying in a wide range of directions. Therefore, according to the present invention, high separation performance can be realized in the spiral acidic gas separation module including the facilitated transport membrane including the acidic gas carrier that reacts with the acidic gas in the presence of water.

It is a partially notched schematic block diagram which shows one Embodiment of the module for acidic gas separation of this invention. It is a schematic diagram of the thickness direction cross-sectional shape of a permeation gas channel member. It is a schematic diagram showing an angle θ formed by the groove of the permeate gas flow path member and the central axis of the permeate gas collecting pipe. It is an upper surface schematic diagram which shows arrangement | positioning of a permeate gas collection pipe and the conventional permeate gas flow member. It is an upper surface schematic diagram which shows arrangement | positioning of the permeate gas collection pipe and permeate gas flow member of this embodiment. It is sectional drawing which shows a part of cylindrical winding body by which the laminated body was wound by the permeation gas collection pipe. It is a schematic diagram which shows the state before winding a laminated body around the permeation gas collection pipe of the module for acidic gas separation. It is a manufacturing-process figure of the module for acidic gas separation. It is a manufacturing-process figure of the module for acidic gas separation following FIG. 7A. It is a manufacturing-process figure of the module for acidic gas separation following FIG. 7B. It is a figure which shows a spiral type module manufacturing process. It is a figure which shows the modification of a spiral type module manufacturing process.

  An acidic gas separation module according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a partially cutaway schematic configuration diagram showing an embodiment of an acid gas separation module of the present invention. In the drawings of this specification, the scale of each part is appropriately changed and shown for easy visual recognition.

  As described in the “Background Art” section, in the case of performing gas separation of a raw material gas containing water vapor, in the spiral gas separation module, the flow direction of the raw material gas and the flow direction of the permeate gas are the same as the raw material gas. From the viewpoint of maintaining the partial pressure difference between the side and the permeate gas side, the counterflow is not always good. According to Patent Document 4, it is preferable that the inlet side of the raw material gas is a parallel flow and the outlet side is a countercurrent.

  In the case of a facilitated transport membrane having an acid gas carrier that reacts with an acid gas in the presence of water, the permeation rate of the facilitated transport membrane on the upstream side of the source gas is very fast because the water is almost saturated. Since the raw material gas is at a high temperature of 100 ° C. or higher including water vapor, the downstream raw material gas from which the water vapor has already been separated is a dry gas that maintains the high temperature. Therefore, the water originally contained in the facilitated transport membrane on the downstream side is also heated to become water vapor, and is easily recovered to the permeate gas collecting pipe 12. Furthermore, according to the knowledge obtained by the present inventors, in the facilitated transport membrane having an acidic gas carrier that reacts with acidic gas in the presence of water, the contribution to the separation performance is more or less due to the presence or absence of water in the separation membrane. It is much larger than the partial pressure difference between the source gas and the permeate gas.

  Based on this point of view, the present inventors have studied a configuration that can retain moisture inside the facilitated transport membrane and realize high separation performance by retaining moisture as far as possible in the permeate gas flow path member. As a result, the present invention has been achieved.

As shown in FIG. 1, the acid gas separation module 10 includes:
A supply gas flow path member 30 to which a source gas 20 containing at least an acid gas and water vapor is supplied;
A gas separation membrane 1 comprising a facilitated transport membrane comprising at least a hydrophilic compound and an acidic gas carrier that reacts in the presence of water with an acidic gas in the raw material gas 20 supplied to the supply gas flow path member 30;
Having one or a plurality of laminates 14 formed by laminating a permeate gas passage member 36 through which a permeate gas 22 containing water vapor and an acid gas that has reacted with an acid gas carrier and permeated the facilitated transport film;
One or a plurality of laminated bodies 14 are provided with a cylindrical spiral unit that is wound around a permeating gas collecting pipe 12 having a through-hole 12A formed in the pipe wall and whose outermost periphery is covered with a coating layer 16. ,
Telescope prevention plates 18 are attached to both ends of the spiral unit, respectively.
In the acidic gas separation module 10, the permeate gas flow path member 36 has a plurality of grooves 36 </ b> R on at least the surface of the gas separation membrane 1 provided with the facilitated transport film. It is formed with an angle θ of 0 ° to 75 ° with the central axis of the gas collecting pipe 12.

  When the source gas 20 containing acid gas and water vapor is supplied to the laminated body 14 from the one end portion 10A side of the acidic gas separating module 10 having such a configuration, from the raw material gas 20 according to the configuration of the laminated body 14 to be described later, The permeate gas 22 containing acid gas and water vapor is accumulated in the permeate gas collecting pipe 12 via the permeate gas flow path member 36 and the through hole 12A, and is recovered from the discharge port 26 connected to the permeate gas collective pipe 12. The The residual gas 24 separated from the acidic gas 22 that has passed through the gap or the like of the supply gas flow path member 30 is supplied to the supply gas flow path on the side where the discharge port 26 is provided in the acidic gas separation module 10. It is discharged from the end of the member 30 and the acid gas separation membrane 1.

  First, the permeating gas channel member 36 will be described. The permeate gas flow path member 36 is a member in which the permeate gas 22 containing the acid gas and water vapor that has reacted with the carrier and permeated the acid gas separation layer flows toward the through hole 12A. The permeating gas channel member has a function as a spacer, and also has a function of allowing the permeated acidic gas to flow inside the permeating gas channel member.

FIG. 2 is a schematic cross-sectional view in the thickness direction of the permeating gas channel member 36. As shown in the figure, the groove 36R of the permeating gas flow path member 36 is formed by two elongated protrusions 36W. In FIG. 2, the plurality of grooves 36 </ b> R have substantially the same cross-sectional area, and an example in which they are formed approximately regularly is shown, but the cross-sectional areas of the individual grooves 36 </ b> R may be different. However, it may not be formed substantially regularly. 2 and the cross-sectional view of the laminated body 14 to be described later, the plurality of grooves 36R are described as being formed only on the surface on the gas separation membrane 1 side, but may be formed on both surfaces.
In the permeate gas flow path member 36, the permeate gas 22 tends to flow through the groove 36R. However, when the elongated convex portion 36W is made of a material having a gap, there is also a permeate gas 22 flowing inside the convex portion 36W. To do. In particular, when the supplied raw material gas has a pressure higher than the atmospheric pressure, the permeate gas in the radial direction of the spiral unit toward the permeate gas collecting pipe 12 due to the differential pressure between the supply gas side and the permeate gas side. 22 is easy to flow.

  As already described, in the permeate gas flow path member 36, the plurality of grooves 36R are formed at an angle θ of 0 ° to 75 ° with the central axis of the permeate gas collecting pipe 12. The formed angle θ will be described with reference to FIG. In FIG. 3, the central axis 12 </ b> C of the permeate gas collecting pipe 12 is shown with an arrow in the downstream direction of the raw material gas 20 in the acidic gas separation module.

As shown in FIG. 3, the angle θ formed by the central axis 12C of the permeate gas collecting pipe 12 and the groove 36R is based on the illustrated 0 degree, and the permeate gas collecting pipe 12 side is a positive angle.
FIG. 4A is a schematic top view showing the arrangement of the permeate gas collecting pipe 12 and the permeate gas flow path member 36 used in the conventional spiral gas separation module described in the section “Background Art”. . As shown in the drawing, the conventional permeating gas flow path member also includes a plurality of elongated protrusions 36W and grooves 36R, but the angle θ formed by the groove 36R and the central axis of the permeating gas collecting pipe 12 is substantially the same. It is 90 °.

  FIG. 4B is a schematic top view showing the arrangement of the permeate gas collecting pipe 12 and the permeate gas flow path member 36 in the acidic gas separation module 10 of the present embodiment. As shown in the drawing, the groove 36R and the central axis of the permeate gas collecting pipe 12 form an angle having a component from the upstream side to the downstream side of the raw material gas.

  The present inventors have proposed a facilitated transport membrane in an acidic gas separation module 10 for separating an acidic gas from a raw material gas containing water vapor using a facilitated transport membrane having an acidic gas carrier that reacts with an acidic gas in the presence of water. In view of the magnitude of the influence on the separation performance due to the presence or absence of water in the inside and the easy permeability of water, the angle θ formed by the groove 36R and the central axis of the permeate gas collecting pipe 12 is 0 ° or more and 75 °. It has been found that by setting the following angle range, water can be retained well in the facilitated transport membrane, and separation performance comparable to that of a flat membrane can be realized even in a module form.

  The angle θ formed can be appropriately designed according to the water vapor content of the raw material gas, the flow rate, and the like. As the water vapor content of the raw material gas 20 is larger and the flow velocity is faster, the supply gas flow path member 30 can hold the water vapor to the downstream region, so the angle θ formed has a larger angle. It's okay. Moreover, it is preferable to design the angle θ to be closer to 0 ° as the pressure of the supplied raw material gas is higher. Considering the amount of water vapor contained in the flue gas discharged from a power plant or the like, the angle θ formed is preferably 45 ° or less.

  The material of the permeating gas channel member 36 is not particularly limited as long as it has the above-described configuration, but is preferably a knitted fabric with a gap, and is knitted with synthetic fibers so as to have irregularities (grooves). The synthetic knitted fabric is preferably a tricot knitted fabric. The tricot knitted fabric includes a plurality of wales formed substantially in parallel. Therefore, the plurality of wales are suitable as the elongated protrusions 36W of the permeating gas channel member, and the groove 36R is formed by two adjacent wales.

  The permeate gas flow path member 36 is a flow path of the permeate gas 22 that has permeated the acidic gas separation layer 1 and therefore preferably has low resistance. Specifically, the permeate gas flow path member 36 has a high porosity and is pressurized. It is desirable that the deformation is small and the pressure loss is small. The porosity is preferably 30% or more and 95% or less, more preferably 35% or more and 92.5% or less, and further preferably 40% or more and 90% or less. The porosity can be measured as follows. First, water is sufficiently infiltrated into the gap portion of the permeating gas channel member by using ultrasonic waves or the like to remove excess moisture on the surface, and then the mass per unit area is measured. The value obtained by subtracting this mass from the dry mass is the volume of water that has entered the gap of the permeating gas flow path member, and can be measured by the density of water to measure the void volume and thus the void ratio. At this time, when water is not sufficiently infiltrated, the measurement can be performed using a solvent having a low surface tension such as an alcohol.

The deformation when the pressure is applied can be approximated by the elongation when the tensile test is performed, and the elongation when a load of 10 N / 10 mm width is applied is preferably within 5%, and is within 4%. It is more preferable.
In addition, the pressure loss can be approximated to the flow loss of the compressed air that flows at a constant flow rate, and the loss within 7.5 L / min when flowing through the 15 cm square permeating gas channel member 36 at room temperature for 15 L / min. It is preferable that the loss is within 7 L / min.

  As a raw material of the fibers forming the knitted fabric, it is preferable to have moisture and heat resistance, assuming that a raw material gas containing water vapor flows at a high temperature. Specific materials are preferably polyesters such as epoxy-impregnated polyester, polyolefins such as polypropylene, and fluorines such as polytetrafluoroethylene.

  In the present specification, “heat resistance” in heat and humidity resistance means having heat resistance of 80 ° C. or higher. Specifically, the heat resistance of 80 ° C. or higher means that the shape before storage is maintained even after being stored for 2 hours under a temperature condition of 80 ° C. or higher, and curling that can be visually confirmed by heat shrinkage or heat melting does not occur. Means that. In addition, “moisture resistance” of the heat and humidity resistance is a curl that can be visually confirmed by heat shrinkage or heat melting even after being stored at 40 ° C. and 80% RH for 2 hours. It means not occurring.

  The thickness of the permeating gas channel member is not particularly limited, but is preferably 100 μm or more and 1000 μm or less, more preferably 150 μm or more and 950 μm or less, and further preferably 200 μm or more and 900 μm or less.

  As described above, the acidic gas separation module 10 that separates the acidic gas from the raw material gas containing water vapor using the facilitated transport film including the acidic gas carrier that reacts with the acidic gas in the presence of water includes the raw material gas 20 The influence on the separation performance due to the partial pressure difference with the permeate gas 22 is small compared to the presence or absence of water in the facilitated transport membrane, but considering the easy permeability of water, one end of the permeate gas collecting pipe 12, that is, acidic The source gas 20 is supplied from the inlet 10A side of the gas separation module 10 to the supply gas passage member 30 in the length direction of the permeate gas collecting pipe 12, and the other end of the permeate gas collecting pipe 12, that is, for acid gas separation. It is preferable that the acidic gas is taken out from the outlet 10B side of the module 10 and used in parallel flow.

  The acidic gas separation module 10 is a spiral module that uses a facilitated transport membrane that includes an acidic gas carrier that reacts the raw material gas 20 containing at least an acidic gas and water vapor in the presence of the acidic gas in the raw material gas with water. As the gas flow path member 36, at least the surface on the facilitated transport membrane side is provided with a plurality of grooves 36 </ b> R whose angle θ formed with the central axis of the permeate gas collecting pipe 12 is 0 ° or more and 75 ° or less. . According to this configuration, since the plurality of grooves 36R for guiding the permeated gas in the permeate gas flow path member 36 have the components in the downstream direction of the supply gas, easily permeable water vapor is allowed to flow in the permeate gas flow path member. The water component can be supplied to the facilitated transport membrane adjacent to the permeate gas flow path member 36 within a wide range in the length direction. Therefore, according to the present invention, high separation performance can be realized in the spiral acidic gas separation module including the facilitated transport membrane including the acidic gas carrier that reacts with the acidic gas in the presence of water.

  Hereinafter, components other than the permeate gas flow path member 36 constituting the acidic gas separation module 10 will be described with reference to FIGS. 1, 5, and 6.

<Permeate gas collecting pipe, coating layer, telescope prevention plate>
As shown in FIG. 1, the permeate gas collecting pipe 12 is a cylindrical pipe having a plurality of through holes 12A formed in the pipe wall. The permeate gas collecting pipe 12 is normally configured to be open at both ends. However, when the one end opposite to the exhaust port 26 is closed, the permeate gas 22 gathered from the through hole 12A flows toward the exhaust port 26. It is easy to make and is preferable. As shown in FIG. 1, when the permeate gas is taken out in a parallel flow, an embodiment in which one end on the side to which the raw material gas 20 is supplied is closed is preferable. When a plurality of acid gas separation modules 10 are connected in series, only the acid gas separation module 10 disposed at the end opposite to the side where the permeate gas 22 is collected is connected to the discharge port 26. The opposite end is preferably closed.
A fluid other than the permeate gas 22 may be flowed into the permeate gas collecting pipe 12 for the purpose of improving the efficiency of recovery of the permeate gas 22 or modifying the permeate gas 22 easily. In such a case, it may be better that one end opposite to the discharge port 26 is not closed.

  The ratio (opening ratio) of the through-holes 12A to the surface area of the permeate gas collecting pipe 12 is preferably 1.5% or more and 80% or less, more preferably 3% or more and 75% or less, and further 5% It is preferable that it is 70% or less. Furthermore, the aperture ratio is preferably 5% or more and 25% or less from a practical viewpoint. By setting each lower limit value or more, the acidic gas 22 can be efficiently collected. Moreover, the intensity | strength of a pipe | tube can be raised and it can fully ensure processability by setting it as each upper limit or less.

  Although the shape of 12 A of through-holes is not specifically limited, It is preferable that the circular hole of 0.5-20 mmphi is opened. Moreover, it is preferable that the through holes 12 </ b> A are arranged uniformly with respect to the surface of the permeate gas collecting pipe 12.

  The covering layer 16 is formed of a blocking material capable of blocking the raw material gas 20 passing through the acidic gas separation module 10. This blocking material preferably further has heat and humidity resistance.

The telescope prevention plate 18 has an outer peripheral annular portion 18A, an inner peripheral annular portion 18B, and a radial spoke portion 18C, and each is preferably formed of a heat and moisture resistant material.
Specifically, the telescope prevention plate 18 is made of a metal material (for example, SUS, aluminum, aluminum alloy, tin, tin alloy, etc.), a resin material (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), and the like, and fiber reinforced plastics of these resins (for example, fibers are glass fiber, carbon fiber, stainless steel fiber, aramid fiber, etc.), and long fibers are particularly preferable. , For example long glass fiber reinforced polypropylene, long glass fiber-reinforced polyphenylene sulfide), as well as ceramics (such as zeolite, alumina, etc.) and the like.

<Laminated body>
The laminated body 14 is demonstrated with reference to FIG.1 and FIG.5. In the laminated body 14, the supply gas flow path member 30 is sandwiched inside the acid gas separation membrane 1 folded in half, and the acid gas separation membrane 1 is attached to the permeate gas flow path member 36 on the inner side in the radial direction. It is configured to be sealed through a penetrating sealing portion (not shown in FIG. 1).

  The number of the laminated body 14 wound around the permeate gas collecting pipe 12 is not particularly limited and may be single or plural, but by increasing the number (number of laminated layers), the membrane area of the acidic gas separation membrane can be improved. Thereby, the quantity which can isolate | separate the acidic gas 22 with one module can be improved. Moreover, in order to improve a film area, you may make the length of the laminated body 14 longer.

  When the number of the laminated bodies 14 is plural, it is preferably 50 or less, more preferably 45 or less, and further preferably 40 or less. When the number is less than or equal to these numbers, it is easy to wind the laminate 14 and the workability is improved.

  Although the width | variety of the laminated body 14 is not specifically limited, It is preferable that they are 50 mm or more and 10,000 mm or less, It is more preferable that they are 60 mm or more and 9000 mm or less, Furthermore, it is preferable that they are 70 mm or more and 8000 mm or less. Furthermore, it is preferable that the width | variety of the laminated body 14 is 200 mm or more and 2000 mm or less from a practical viewpoint. By setting it to each lower limit value or more, an effective area of the acidic gas separation membrane 1 can be ensured even when resin is applied (sealed). Moreover, by setting it as each upper limit value or less, the horizontality of the winding core can be maintained and the occurrence of winding deviation can be suppressed.

FIG. 5 is a cross-sectional view showing a part of a cylindrical wound body in which a laminated body is wound around a permeating gas collecting pipe.
As shown in FIG. 5, the spiral module has a configuration in which the laminate 14 is wound around the permeate gas collecting pipe and the laminate 14 is stacked on the permeate gas collecting pipe 12 in a cross section. The laminated bodies 14 are bonded to each other via bonding portions 40 at both ends.

As shown in FIG. 5, the laminate 14 includes a permeate gas flow path member 36, an acid gas separation membrane 1, a supply gas flow path member 30, and an acid gas separation membrane 1 in order from the permeate gas collecting pipe 12 side. Laminated. The acidic gas separation membrane 1 includes a porous support 4 in which a porous membrane 2 and an auxiliary support membrane 3 are laminated, and an acidic gas in the raw material gas that is disposed on the porous membrane 2 side of the porous support 4. An acidic gas separation promoting transport film 5 having a function of separating gas is provided. A sealing portion 34 for sealing inflow of gas is provided at the end of the laminated body of the porous support 4 and the permeating gas channel member 36.
<< Supply gas channel member >>
The supply gas flow path member 30 is a member to which a source gas containing an acid gas is supplied from one end of the acid gas separation module, has a function as a spacer, and causes a turbulent flow in the source gas. Therefore, a net-like member is preferably used. Since the gas flow path changes depending on the shape of the net, the shape of the unit cell of the net is selected from shapes such as rhombus and parallelogram according to the purpose. Assuming that a raw material gas containing water vapor is supplied at a high temperature, the supply gas flow path member preferably has moisture and heat resistance in the same manner as the acidic gas separation layer described later.

  The material of the supply gas flow path member is not limited in any way, but paper, fine paper, coated paper, cast coated paper, synthetic paper, cellulose, polyester, polyolefin, polyamide, polyimide, polysulfone, aramid, polycarbonate Inorganic materials such as resin materials such as metals, glass and ceramics. The resin materials include polyethylene, polystyrene, polyethylene terephthalate, polytetrafluoroethylene (PTFE), polyethersulfone (PES), polyphenylene sulfide (PPS), polysulfone (PSF), polypropylene (PP), polyimide, polyetherimide, poly Suitable examples include ether ether ketone and polyvinylidene fluoride.

  In addition, preferable materials from the viewpoint of heat and humidity resistance include inorganic materials such as ceramics, glass, and metals, organic resin materials having heat resistance of 100 ° C. or higher, high molecular weight polyester, polyolefin, heat resistant polyamide, polyimide, and the like. Polysulfone, aramid, polycarbonate, metal, glass, ceramics and the like can be suitably used. More specifically, at least one selected from the group consisting of ceramics, polytetrafluoroethylene, polyvinylidene fluoride, polyethersulfone, polyphenylene sulfide, polysulfone, polyimide, polypropylene, polyetherimide, and polyetheretherketone. It is preferable that it is comprised including these materials.

  The thickness of the supply gas channel member is not particularly limited, but is preferably 100 μm or more and 1000 μm or less, more preferably 150 μm or more and 950 μm or less, and further preferably 200 μm or more and 900 μm or less.

<< Acid gas separation membrane >>
(Acid gas separation facilitating transport membrane)
The acidic gas separation facilitated transport membrane 5 (hereinafter simply referred to as the facilitated transport membrane 5) includes a hydrophilic compound and an acidic gas carrier.
((Acid gas carrier))
The acid gas carrier refers to a substance that reacts indirectly with the acid gas or a substance that itself reacts directly with the acid gas. Indirect reaction with an acid gas includes, for example, a reaction with another gas contained in the supply gas, showing basicity, and a reaction between the basic compound and the acid gas. As this type of acid gas carrier, and more specifically, by reacting with steam OH ^- to the release, the OH ^- can be incorporated selectively CO ₂ in the film by reacting with CO ₂ Such alkali metal compounds are mentioned.
Examples of the acid gas carrier that directly reacts with the acid gas include basic compounds such as nitrogen-containing compounds and sulfur oxides.

Examples of the alkali metal compound include at least one selected from the group consisting of an alkali metal carbonate, an alkali metal bicarbonate, and an alkali metal hydroxide, and a polydentate that forms a complex with an alkali metal ion in an aqueous solution containing the alkali metal compound. Examples include aqueous solutions to which a ligand is added, ammonia, ammonium salts, various linear and cyclic amines, amine salts, ammonium salts, and the like. These water-soluble derivatives can also be preferably used. Since carriers that can be retained in the facilitated transport film for a long period of time are useful, amine-containing compounds that are difficult to evaporate, such as amino acids and betaines, are particularly preferred.
In addition, in this specification, an alkali metal compound is used in the meaning containing the salt and its ion other than alkali metal itself.

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

  Here, in this embodiment, since the hygroscopic facilitated transport membrane is used as the carbon dioxide gas separation membrane, the facilitated transport membrane becomes a gel due to moisture absorbed during production, and the facilitated transport membrane is formed between the membranes and other membranes during production. The phenomenon of sticking to the member (blocking) is likely to occur. When this blocking occurs, when the facilitated transport film is peeled off, the facilitated transport film may cause defects due to the sticking, resulting in gas leakage. Therefore, in this embodiment, it is preferable to prevent blocking.

Therefore, in this embodiment, the carrier preferably contains two or more alkali metal compounds. This is because, by using two or more kinds of carriers, blocking of the same kind of carriers in the film can be created by creating a non-uniformity of blocking by separating the distances.
Furthermore, it is more preferable that the carrier contains a first alkali metal compound having deliquescence and a second alkali metal compound having a lower deliquescence and a lower specific gravity than the first alkali metal compound. Specifically, the first alkali metal compound includes cesium carbonate, and the second alkali metal compound includes potassium carbonate.
Since the carrier contains the first alkali metal compound and the second alkali metal compound, the second alkali metal compound having a small specific gravity is arranged on the film surface side of the facilitated transport film (that is, unevenly disposed on the surface side of the facilitated transport film). The first alkali metal compound having a large specific gravity is disposed inside the facilitated transport membrane (that is, unevenly disposed on the porous support side of the facilitated transport membrane). And since the 2nd alkali metal compound arrange | positioned at the film surface side has lower deliquescence property than a 1st alkali metal compound, compared with the case where a 1st alkali metal compound is arrange | positioned at the film surface side, a film surface is sticky. Therefore, blocking can be suppressed. In addition, since the first alkali metal compound having high deliquescence is disposed inside the membrane, blocking is suppressed and the separation efficiency of carbon dioxide gas is reduced as compared with the case where the second alkali metal compound is simply disposed over the entire membrane. Can be increased.

  Specifically, in the acidic gas separation layer 10, when two or more kinds of alkali metal compounds (first and second alkali metal compounds) are applied as carriers, the facilitated transport film 5 is opposite to the porous support 4. The second layer on the surface side of the substrate and the first layer on the porous support 4 side below the second layer. The facilitated transport film 5 is composed of a hydrophilic compound (hydrophilic polymer) as a whole, and the second layer mainly contains a second alkali metal compound having low deliquescence and low specific gravity. ing. In the first layer, a first alkali metal compound having mainly deliquescence exists. The thickness of the second layer is not particularly limited, but is preferably 0.01 to 150 μm and more preferably 0.1 to 100 μm in order to exhibit a sufficient deliquescent function.

  In the facilitated transport film 5, in the illustrated state, the second layer containing the second alkali metal compound is unevenly distributed on the surface side, and the first layer containing the first alkali metal compound is spread below the second layer. However, the present invention is not limited to this. For example, the interface between the two layers may not be clear, and the two layers may be separated in a state in which both change in an inclined manner. Further, the interface is not constant and may be in a meandering state.

  The deliquescence of the membrane is suppressed by the action of the second layer containing the second alkali metal compound having low deliquescence and low specific gravity. The reason why the second alkali metal compound is unevenly distributed is considered to be due to the difference in specific gravity between two or more alkali metals. That is, by setting one of two or more types of alkali metals to a low specific gravity, it is possible to localize a lighter specific gravity in the coating solution at the time of film formation. Then, while maintaining the high transport force such as carbon dioxide of the first alkali metal compound having the deliquescence contained in the first layer inside the film, the surface of the second layer film is more crystalline than the second alkali metal compound has. Condensation and the like can be prevented due to the property of being easily converted. Thereby, while blocking can be suppressed, the separation efficiency of a carbon dioxide gas can be improved.

  Since the second alkali metal compound only needs to be on the film surface side in order to suppress blocking, the second alkali metal compound is preferably contained in a smaller amount than the first alkali metal compound. Thereby, the amount of the first alkali metal compound having high deliquescence is relatively large in the entire membrane, and the carbon dioxide separation efficiency can be further increased.

  Here, the number of types of two or more types of alkali metal compounds is determined by the type of alkali metal, and even if the counter ions are different, it is not counted as one type. That is, even if potassium carbonate and potassium hydroxide are used in combination, it is counted as one type.

As a combination of two or more kinds of alkali metal compounds, those shown in Table 1 below are preferable. In Table 0, an alkali metal compound is indicated by the name of alkali metal, but it may mean a salt or ion thereof.

  The content of the entire carrier in the hydrophilic compound layer depends on the type of the carrier, but in order to prevent salting out before coating and to reliably exhibit the function of separating acidic gas, it is 0.3 to 80% by mass. It is preferable that it is 0.5 to 70% by mass, more preferably 1 to 65% by mass.

  When two or more kinds of alkali metal compounds are applied as the carrier, the content of the two or more kinds of alkali metal compounds is the total solid content of the hydrophilic compound and two or more kinds of alkali metal compounds that are the main components of the film. In terms of mass, the mass ratio of two or more alkali metal compounds is preferably 25% by mass or more and 85% by mass or less, and more preferably 30% by mass or more and 80% by mass or less. By setting this amount within the above range, the gas separation function can be sufficiently exhibited.

  Among the two or more types of alkali metal compounds, the second alkali metal compound (alkali metal compound unevenly distributed on the surface side of the facilitated transport film 5) having lower deliquescence and lower specific gravity than the first alkali metal compound, It is preferably 0.01% by mass or more and 0.02% by mass or more with respect to the total mass (typically, the total mass of the separated layer after drying) of two or more kinds of alkali metal compounds and the like. It is more preferable that Although there is no upper limit in particular, it is preferable that it is 10 mass% or less, and it is more preferable that it is 7.5 mass% or less. If this amount is too small, blocking may not be prevented, and if it is too large, handling may not be possible.

  The ratio of the second alkali metal compound to the first alkali metal compound is not particularly limited, but the first alkali metal compound is preferably 50 parts by mass or more and 100 parts by mass or more with respect to 100 parts by mass of the second alkali metal compound. More preferred. As an upper limit, 100000 mass parts or less are preferable, and 80000 mass parts or less are more preferable. By adjusting the ratio of the two in this range, it is possible to achieve both blocking properties and handling properties at a high level.

Examples of nitrogen-containing compounds include amino acids such as glycine, alanine, serine, proline, histidine, taurine, and diaminopropionic acid, hetero compounds such as pyridine, histidine, piperazine, imidazole, and triazine, monoethanolamine, diethanolamine, and triazine. Alkanolamines such as ethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, cyclic polyetheramines such as cryptand [2.1] and cryptand [2.2], cryptand [2.2.1] Bicyclic polyetheramines such as cryptand [2.2.2], porphyrin, phthalocyanine, ethylenediaminetetraacetic acid and the like can be used.
As the sulfur compound, for example, amino acids such as cystine and cysteine, polythiophene, dodecylthiol and the like can be used.

((Hydrophilic compound))
The hydrophilic compound functions as a binder and retains water when used for the facilitated transport film 5 to exhibit the function of separating the acidic gas by the acidic gas carrier. The hydrophilic compound can be dissolved in water or dispersed in water to form a coating solution, and from the viewpoint that the facilitated transport film 5 has high hydrophilicity (moisturizing property), the hydrophilic compound has high hydrophilicity. It is preferable to absorb water having a mass of 5 to 1000 times the mass of the hydrophilic compound itself.

Examples of the hydrophilic compound include, for example, agar, polyvinyl alcohol-polyacrylate, polyvinyl alcohol-polyacrylic acid (PVAPAA) copolymer, polyvinyl alcohol, polyacrylic, from the viewpoint of hydrophilicity, film-forming property, strength, and the like. Hydrophilic polymers such as acids, polyacrylates, polyvinyl butyral, poly-N-vinyl pyrrolidone, poly-N-nylacetamide, and polyacrylamide are preferred, and PVA-PAA copolymers are particularly preferred. The PVA-PAA copolymer has a high water absorption capacity and a high hydrogel strength even at high water absorption. The content of the polyacrylate in the PVAPAA copolymer is preferably, for example, from 5 mol% to 95 mol%, and more preferably from 30 mol% to 70 mol%. Examples of polyacrylic acid salts include alkali metal salts such as sodium salt and potassium salt, as well as ammonium salts and organic ammonium salts.
Examples of commercially available PVA-PAA copolymers include Clastomer-AP20 (trade name: manufactured by Kuraray Co., Ltd.).

  The content of the acidic gas carrier in the facilitated transport film 5 depends on the ratio to the amount of the hydrophilic compound and the type of the acidic gas carrier, but functions as an acidic gas carrier and is acidic in the use environment. From the viewpoint of excellent stability as a gas separation layer, it is preferably 0.1% by mass or more and 80% by mass or less, more preferably 0.2% by mass or more and 70% by mass or less, and further preferably 0.3% by mass. It is particularly preferable that the content is not less than mass% and not more than 65 mass%.

  The facilitated transport membrane 5 may contain other components (additives) other than the hydrophilic compound, the acidic gas carrier, and water as long as the separation characteristics are not adversely affected. As an optional component, for example, the coating liquid film is cooled in the process of applying an aqueous solution (coating liquid) for forming a facilitated transport film 5 containing a hydrophilic compound and an acidic gas carrier on the porous support and drying it. Gelling agent for controlling the so-called setting property, viscosity adjusting agent for adjusting the viscosity at the time of application when applying the coating liquid with a coating apparatus, and crosslinking for improving the film strength of the facilitated transport film 5 Agents, acid gas absorption accelerators, other surfactants, catalysts, auxiliary solvents, membrane strength modifiers, and detection agents for facilitating the inspection of the formed acid gas separation layer for defects. Can be mentioned.

  The average thickness of the facilitated transport membrane 5 is preferably 1 μm or more and 200 μm or less, more preferably 3 μm or more and 150 μm or less, and particularly preferably 5 μm or more and 120 μm or less from the viewpoint that an acid gas separation layer having excellent performance can be obtained. .

(Porous support membrane)
The porous support 4 that supports the facilitated transport film 5 is formed by laminating the porous film 2 and the auxiliary support film 3. By providing the auxiliary support film 3, the mechanical strength can be improved, and even when handled by a coating machine or the like, there is an effect that wrinkles do not occur, and productivity can be improved.

((Porous membrane))
The porous membrane 2 is permeable to acidic gases such as carbon dioxide, which is a gas to be separated, and water vapor.
The porous membrane 2 preferably has a small pore diameter from the viewpoint of suppressing penetration of the facilitated transport material during formation of the facilitated transport film. The maximum pore size is preferably 1 μm or less. The lower limit of the pore diameter is not particularly limited, but is about 0.001 μm.

Here, the maximum pore diameter means a value measured and calculated by the bubble point method. For example, it can measure by the bubble point method (based on JISK3832) using the palm porometer made from PMI as a measuring apparatus. Here, the maximum pore size is the largest pore size value in the pore size distribution of the porous membrane.
The thickness of the porous membrane 2 is preferably 1 μm or more and 100 μm or less.

Moreover, it is preferable that at least the surface of the porous membrane 2 on the side in contact with the facilitated transport membrane 5 is a hydrophobic surface. If the surface is hydrophilic, the facilitated transport film containing moisture in the use environment is likely to penetrate into the porous portion, and there is a concern that the film thickness distribution and performance deterioration with time may occur.
Here, the term “hydrophobic” means that the contact angle of water at room temperature (25 ° C.) is about 80 ° or more.
However, this is not limited as long as the thickness of the hydrophilic porous membrane is equal to or less than the thickness of the facilitated transport membrane.

  In the present invention, the porous membrane 2 is a porous resin sheet made of a resin material such as polyester, polyolefin, polyamide, polyimide, polysulfone aramid, polysulfone, polycarbonate, polyacrylonitrile or the like.

  Although the use temperature differs depending on the application application, the acid gas separation module is often used at a high temperature of, for example, about 130 ° C. and under humidification using steam. Therefore, it is preferable that the porous membrane is made of a material having heat resistance with little change in pore structure even at 130 ° C. and having low hydrolyzability. From such a point of view, those formed by including a resin selected from the group consisting of fluorine-containing resins such as polypropylene, polytetrafluoroethylene (PTFE), and polyvinylidene fluoride (PVDF) are preferred and most preferred. Is a PTFE porous membrane.

((Auxiliary support membrane))
The auxiliary support membrane 3 is provided for reinforcement of the porous membrane 2, and is not particularly limited as long as the strength, stretch resistance and gas permeability are good, and the nonwoven fabric, woven fabric, woven fabric, and A mesh having a maximum pore diameter of 0.001 μm or more and 500 μm can be appropriately selected and used.
The thickness of the auxiliary support film 3 is preferably 50 μm or more and 300 μm or less.

The auxiliary support membrane 3 is also preferably made of a material having heat resistance and low hydrolyzability, like the porous membrane 2 described above. Non-woven fabrics, woven fabrics, and knitted fabrics that have excellent durability and heat resistance include modified polyamides such as polypropylene and aramid (trade name), fluorine-containing resins such as polytetrafluoroethylene and polyvinylidene fluoride, etc. The fiber consisting of is preferred. It is preferable to use the same material as the resin material constituting the mesh.
Of these materials, it is particularly preferable to use a nonwoven fabric made of polypropylene (PP) which is inexpensive and has high mechanical strength.

  FIG. 6 is a diagram schematically showing a state before the laminated body is wound around the permeating gas collecting pipe, and represents one embodiment of the formation region of the bonding portions 34 and 40 (hereinafter sometimes referred to as an adhesive). FIG. As shown in FIG. 6, the adhesive portion 40 covers the through hole 12A with the permeate gas flow path member 36, and the acidic gas separation is performed with the laminate 14 wound around the permeate gas collecting pipe 12 in the direction of arrow C in the figure. The membrane 1 and the permeating gas channel member 36 are bonded and sealed. On the other hand, the adhesive portion 34 bonds and seals the acidic gas separation membrane 1 and the permeate gas flow path member 36 before the laminate 14 is wound around the permeate gas collecting pipe 12. In FIG. 6, the acidic gas separation membrane 1 and the permeate gas flow path member 36 bonded by the bonding portion 34 before being wound are shown separately.

  Both the bonding portions 34 and 40 have a so-called envelope shape in which an end portion in the circumferential direction between the acid gas separation membrane 1 at the start of winding and the permeating gas flow path member 36 is opened. And in the area | region enclosed by the adhesion part 34, the flow path P1 through which the permeated gas 22 which permeate | transmitted the acidic gas separation membrane 1 flows to 12 A of through-holes is formed. Similarly, a flow path P2 in which the permeated gas 22 that has permeated the acidic gas separation membrane 1 flows to the through-hole 12A is formed in the region surrounded by the bonding portion 40.

The adhesive used for the bonding portions 34 and 40 has heat and humidity resistance.
The material is not particularly limited as long as it has heat and humidity resistance. For example, epoxy resin, vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylic. Nitrile copolymer, butadiene-acrylonitrile copolymer, polyamide resin, polyvinyl butyral, polyester, cellulose derivative (nitrocellulose, etc.), styrene-butadiene copolymer, various synthetic rubber resins, phenol resin, melamine resin, phenoxy Resins, silicon resins, urea formamide resins and the like can be mentioned.
Particularly preferred is an epoxy resin.
In order to improve the wettability of the adhesive, it may contain a solvent or a surfactant.

<Manufacturing method of spiral type module>
Next, a method for manufacturing the acid gas separation module having the above-described configuration will be described.
7A to 7C are manufacturing process diagrams of the acid gas separation module. In the method of manufacturing the acidic gas separation module 10, first, as shown in FIG. 7A, a permeate gas collecting pipe is connected to the distal end portion of the elongate permeate gas flow path member 36 with a fixing member 55 such as Kapton tape or adhesive. It fixes to 12 tube walls (outer peripheral surface). Here, it is preferable that the tube wall is provided with a slit (not shown) along the axial direction. In this case, the tip of the permeate gas flow path member 36 is inserted into the slit and fixed to the inner peripheral surface of the permeate gas collecting pipe 12 by the fixing member 55. According to this configuration, even when the laminate 14 including the permeate gas flow path member 36 is wound around the permeate gas collecting pipe 12, the inner circumferential surface of the permeate gas collecting pipe 12 can be The permeate gas flow path member 36 does not come out of the slit due to friction with the permeate gas flow path member 36, that is, the permeate gas flow path member 36 is fixed.

  Next, as shown in FIG. 7B, the long supply gas flow path member 30 is sandwiched between the long acidic gas separation membrane 1 in which the acidic gas separation promoting transport membrane 5 is folded inward. When the acidic gas separation membrane 1 is folded in two, the acidic gas separation membrane 1 may be divided into two as shown in FIG.

  Next, with respect to one outer surface (the surface of the auxiliary support membrane 3 of the porous support 4) of the outer surfaces of the acid gas separation membrane 1 folded in half, both ends in the width direction and one end in the longitudinal direction of the membrane Apply adhesive (apply envelope).

  Next, as shown in FIG. 7C, the acidic gas separation membrane in which the supply gas flow path member 30 is sandwiched between the surface of the permeate gas flow path member 36 fixed to the permeate gas collecting pipe 12 via the adhesive 34. 1 is pasted. When the acidic gas separation membrane 1 is pasted, it is pasted so that one end where the adhesive 34 is not applied is on the gas collecting pipe 12 side. As a result, the end portion in the circumferential direction between the acid gas separation membrane 1 at the beginning of winding and the permeating gas flow path member 36 is opened as the entire bonding portion 34, and acid gas separation is performed in the region surrounded by the bonding portion 34. A flow path P1 through which the permeate gas 22 that has passed through the membrane 1 flows to the through hole 12A is formed.

  Next, with respect to the surface of the acidic gas separation membrane 1 attached to the permeating gas flow path member 36 (the surface of the auxiliary support membrane 3 of the porous support 4 opposite to the attached surface), the membrane Adhesive 40 is applied to both ends in the width direction and one end in the longitudinal direction.

Next, as schematically shown in FIG. 8, the permeate gas collecting tube 12 is rotated in the direction of arrow C, so that the laminated body 14 covers the through hole 12 </ b> A with the permeate gas flow path member 36. The tube 12 is wrapped around multiple times. At this time, it is preferable to wind the laminate 14 while applying tension.
The supply gas flow path member 30 sandwiched between the two folded acidic gas separation membranes 1 is regarded as one unit, and this unit and the permeate gas flow path member 36 are alternately stacked. As a result, FIG. As shown in FIG. 4, a plurality of the laminated bodies 14 may be stacked (in this example, 3 units) and wound around the permeating gas collecting pipe in a multiple manner. In addition, when a plurality of units are overlapped, they are gradually shifted and overlapped as shown in FIG. 9 so as not to increase the step after being wound around the collecting pipe.

A cylindrical winding body is obtained through the above steps, and after trimming both end portions of the obtained cylindrical winding body (end face correction processing), the outermost periphery of the cylindrical winding body is covered with a coating layer 16. The acid gas separation module 10 shown in FIG. 1 is obtained by covering and attaching the telescope prevention plates 18 to both ends.
Hereinafter, the acid gas separation module of the present invention will be described in more detail with reference to examples.

  The present invention will be described more specifically with reference to the following examples. In addition, the material, usage-amount, ratio, processing content, processing procedure, etc. which are shown in the following Examples can be changed suitably unless it deviates from the meaning of this invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

(Examples 1 to 3, Comparative Example 1)
Clastomer AP-20 (manufactured by Kuraray Co., Ltd.): 2.4% by mass, 25% glutaraldehyde aqueous solution (manufactured by Wako): To an aqueous solution containing 0.01% by mass, 1M hydrochloric acid was added until pH 1, and after crosslinking, A 40% aqueous cesium carbonate solution (manufactured by Rare Metal Co., Ltd.) as a carrier was added so that the concentration of cesium carbonate was 3.66% by mass, and then an aqueous 40% potassium carbonate solution (manufactured by Wako) was added at a potassium carbonate concentration of 0. Add 1% lapizole A-90 (manufactured by NOF Corporation) as a blocking inhibitor to 0.003% by mass, stir and degas after heating. Then, a separately prepared agar aqueous solution was added to obtain a coating composition.

This coating composition was applied to a PTFE porous membrane (manufactured by GE) having a pore diameter of 0.1 μm and a thickness of 30 μm, cured, and then folded in half. Three-way end faces with lines arranged at an angle shown in Table 1 toward a 19 mmφ permeating gas collecting pipe and a polypropylene net (wire diameter: 50 μm, mesh opening: 500 μm) as a supply-side channel agent A unit in which an adhesive was applied to was prepared.
After three sets of these units were laminated, they were attached to a permeating gas collecting tube to produce a spiral separation membrane module.

(Evaluation)
The produced spiral-type separation membrane module is housed in a cylindrical sealed container, and a mixed gas mixed at a ratio of CO ₂ / H ₂ = 10/90 is supplied as a test gas at 10000 ml / min, and this is supplied under saturated steam. The module was supplied at a pressure of 2 atm and a temperature of 130 ° C., the flow rate of the permeate gas was measured with a soap flow meter, and the composition was analyzed by gas chromatography.

Table 2 shows the evaluation results. In Table 2, the gas permeability is A when the permeate gas flow rate is 100 ml / min or more, B when it is 50 ml / min or more and less than 100 ml / min, and C when it is less than 50 ml / min. In addition, CO ₂ / H ₂ selectivity (separation coefficient) was calculated. The separation coefficient α indicating CO ₂ / H ₂ selectivity is the ratio of the permeation coefficient Q (m ³ / m ² s Pa) of each component in a steady state (standard temperature / standard pressure: STP). It was calculated from the flow rate and the composition ratio.
α = Q (CO ₂ ) / Q (H ₂ )
In this example and the comparative example, the case where α is 100 or more is A, the case where α is 30 or more and less than 100 is B, and the case where α is less than 30 is C.
As shown in Table 2, by arranging the angle θ formed by the groove of the permeate gas channel member and the central axis of the permeate gas collecting pipe to have the angle shown in the embodiment, the gas permeability and CO Both the _two selectivity results were better than those of Comparative Example 1, which is a conventional arrangement, indicating the effectiveness of the present invention.

1 Acid Gas Separation Membrane 2 Porous Membrane 3 Auxiliary Support Membrane 4 Porous Support 5 Acid Gas Separation Promoted Transport Membrane 10 Acid Gas Separation Module 12 Permeate Gas Collecting Tube 14 Acid Gas Separation Laminate 20 Raw Material Gas 22 Permeated Gas 30 Supply gas channel member 36 Permeate gas channel member 36R Groove 34, 40 Sealing portion

Claims (5)

A member for supplying a gas flow path including at least a source gas acid gas and water vapor is supplied,
A facilitated transport membrane comprising at least a hydrophilic compound and an acidic gas carrier that reacts in the presence of water with the acidic gas in the source gas supplied to the supply gas channel member;
A laminated body in which a permeating gas channel member that reacts with the acidic gas carrier and flows through the facilitated transport film flows through the acidic gas;
The laminate is an acid gas separation module wound around a permeating gas collecting pipe having a through-hole formed in a pipe wall,
The permeating gas channel member has at least a plurality of grooves on the surface of the facilitated transport membrane side;
An acidic gas separation module in which an angle θ formed by the plurality of grooves and the central axis of the permeating gas collecting pipe is 0 ° or more and 45 ° or less. Claim 1 Symbol placement acid gas separation module of the permeate gas flow path member is made of synthetic fibers knitted. The permeate gas flow path member is made of tricot knitted fabric, two claim 1 or 2 acid gas separation module according composed is formed by wales of the groove adjacent the tricot knitted fabric. The module for acidic gas separation according to any one of claims 1 to 3 , wherein the acidic gas carrier contains an alkali metal compound. The source gas is supplied from one end side of the permeate gas collecting pipe to the supply gas flow path member in the length direction of the permeate gas collecting pipe, and the acid gas is taken out from the other end of the permeate gas collecting pipe. The acidic gas separation module according to any one of claims 1 to 4 .