Source: https://patents.google.com/patent/JP5990225B2/en
Timestamp: 2020-01-25 14:38:05
Document Index: 718860145

Matched Legal Cases: ['art 7', 'art 7', 'art 7', 'art 9', 'art 7', 'art 9', 'art 7', 'art 7', 'art 7', 'art 7', 'art 9', 'art 7', 'art 9']

JP5990225B2 - Acid gas separation laminate and acid gas separation module comprising the laminate - Google Patents
Acid gas separation laminate and acid gas separation module comprising the laminate Download PDF
JP5990225B2
JP5990225B2 JP2014152716A JP2014152716A JP5990225B2 JP 5990225 B2 JP5990225 B2 JP 5990225B2 JP 2014152716 A JP2014152716 A JP 2014152716A JP 2014152716 A JP2014152716 A JP 2014152716A JP 5990225 B2 JP5990225 B2 JP 5990225B2
JP2014152716A
JP2015044189A (en
岳史 成田
憲一 石塚
2013-07-30 Priority to JP2013157549 priority Critical
2013-07-30 Priority to JP2013157549 priority
2014-07-28 Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
2014-07-28 Priority to JP2014152716A priority patent/JP5990225B2/en
2015-03-12 Publication of JP2015044189A publication Critical patent/JP2015044189A/en
2016-09-07 Publication of JP5990225B2 publication Critical patent/JP5990225B2/en
The present invention relates to an acid gas separation laminate having an acid gas separation function and an acid gas separation module including the laminate.
In recent years, development of technology for selectively separating an acidic gas in a mixed gas has progressed. For example, an acid gas separation module that separates an acid gas from a raw material gas by an acid gas separation membrane that selectively permeates the acid gas has been developed.
The separation membrane utilizes the so-called facilitated transport membrane in which acid gas is transported to the opposite side of the membrane by the carrier in the separation membrane, and the difference in solubility between the acidic gas and the substance to be separated in the membrane and the diffusivity in the membrane. Thus, it is roughly classified into so-called dissolution diffusion membranes that perform separation.
As a separation membrane module provided with such a separation membrane, various types of membrane modules such as a spiral type, a flat membrane type, and a hollow fiber type are used. For example, Patent Document 1 discloses a spiral membrane module in which a separation membrane, a supply-side channel member and a permeation-side channel member are wound around a central tube, and Patent Document 2 includes a flat membrane-type membrane module. It is disclosed.
In general, a spiral membrane module is configured by alternately stacking a leaf having a supply-side flow path member and a permeate-side flow path member while folding a separation membrane in half, and supplying a supply-side fluid and a permeate-side fluid. In order to prevent mixing, an adhesive is applied to three sides of the periphery of the laminate of the separation membrane and the permeate-side channel member to produce a separation membrane unit, and one or more of these units are connected to a central tube (fluid It is manufactured by spirally winding around a collecting pipe) and trimming (end face correction processing) both ends of the obtained cylindrical wound body.
In the flat membrane module, a separation membrane is arranged on one or both sides of the permeate-side channel member, and again, a separation membrane unit is produced by applying an adhesive to three sides of the peripheral edge of the laminate. One side to which no adhesive is applied is joined to the fluid collecting pipe.
In any module, the sealing portion formed by the adhesive is extremely important from the viewpoint of preventing the mixing of the supply side fluid and the permeation side fluid and improving the separation performance.
Since the separation performance is deteriorated if the sealing accuracy by the sealing portion is not sufficient, there are some studies on an accurate sealing method, an adhesive filling rate, and an adhesive width (Patent Documents 3 and 4). etc).
JP-A-11-226366 JP-A-11-216341 JP 2009-18239 A Japanese Patent Laid-Open No. 3-68428
When the separation target substance is a gas (gas), it is much easier to leak than in the case of a liquid during operation. In addition, in an acidic gas separation module equipped with a facilitated transport membrane, it is possible to start from a raw material gas containing water vapor. Since the acidic gas is separated, the viscosity of the separation membrane decreases. Further, the supply gas has a pressure equal to or higher than the atmospheric pressure, and a differential pressure is generated between the supply gas side and the permeate gas side, and the differential pressure is applied to the separation membrane having a reduced viscosity. Furthermore, since the mechanical strength differs between the three sides sealed with the adhesive and the other portions, stress concentration tends to occur at the boundary between them. It can be seen that a large stress is applied to the boundary to cause defects in the separation membrane.
An object of the present invention is to provide an acidic gas separation laminate applied to an acidic gas separation module that can suppress the occurrence of defects in a separation membrane, and an acidic gas separation module including the laminate. To do.
The laminate for acidic gas separation of the present invention comprises a porous support in which a porous membrane and an auxiliary support membrane are laminated,
An acidic gas separation promoting transport membrane having a function of separating the acidic gas in the raw material gas, disposed on the porous membrane side of the porous support;
A laminated body for acidic gas separation, comprising a permeated gas flow path member through which acidic gas that has permeated the acidic gas separation facilitated transport membrane is disposed on the auxiliary support membrane side of the porous support,
Adhesive penetrates into the porous membrane with a width of 5 mm or more at the periphery of the laminate at a penetration rate of 60% or more, and the adhesive penetrates into the auxiliary support membrane and the gas channel member at a penetration rate of 60% or more. A sealing portion formed by
A stress buffering part formed adjacent to the sealing part and having a penetration rate of the adhesive in the porous film of less than 60% and penetrating into the auxiliary support film and the gas flow path member; It is characterized by having.
In the sealing portion, the penetration rate of the adhesive into the auxiliary support film and the gas flow path member is preferably 80% or more.
The width of the stress buffer portion is preferably 0.1% or more and 50% or less of the width of the sealing portion.
The width of the stress buffer portion is more preferably 40% or less of the width of the sealing portion.
In addition, the sealing part does not need to be provided in the whole periphery of a laminated body, and should just be provided in the part which needs to be sealed among the periphery.
Here, the “adhesive penetration rate” means the filling rate of the adhesive with respect to the voids (holes) in each of the porous membrane, the auxiliary support membrane, and the gas flow path member.
For the penetration rate of the adhesive, the SEM (scanning electron microscope) or optical microscope was used to observe the cross section (cross section parallel to the sealing width direction) of the laminate after applying the adhesive, and after applying the adhesive. The ratio of the area of the adhesive filled in the hole to the area of the hole of each film and member is obtained by image processing. Here, the three visual fields means, for example, that three visual fields are observed for each side when the sealing portions are provided on the three peripheral sides. Further, only one sealing portion is included in one field of view. At this time, the range in which the penetration rate from the end of the laminate is 60% or more in each film and member is specified as the sealing portion. And the area | region in which the adhesive agent inside a laminated body (direction opposite to an edge part) has penetrate | infiltrated rather than the sealing part is specified as a stress buffer part. In the present invention, it is assumed that the penetration rate of the adhesive into the auxiliary support film and the gas flow path member in the sealing portion is equal to or higher than the penetration rate of the adhesive into the porous membrane.
Obtain the penetration rate of the adhesive from the filling area of the adhesive with respect to the area of the pores in each part of the porous membrane, the auxiliary support membrane and the permeating gas channel member every 0.01 mm width from the end of the laminate, and from the end The farthest position where the adhesive penetration rate in the porous membrane, auxiliary support membrane, and gas flow path member satisfies 60% or more is specified as the sealing portion, and the distance from the end portion to that position is the width of the sealing portion. It is defined as And from the end of the sealing portion to the position immediately before the adhesive penetration rate in the porous film becomes 0% is specified as the stress buffer portion, and the adhesive penetration rate becomes 0% from the end of the sealing portion. The distance to the immediately preceding position is defined as the width of the stress buffer portion.
That is, the stress buffering portion may be a region where the penetration rate of the adhesive in at least the porous membrane is less than 60% and the adhesive penetrates into the auxiliary support membrane and the permeate side gas flow path member. The adhesive soaking rate of the support membrane and the permeate-side gas flow path member may be 60% or more or less than 60%.
Obtain the width of the sealing portion and the stress buffering portion at each side where the sealing portion is provided for the laminated body after application of the adhesive described above, and calculate the average value of the width of the sealing portion and the stress buffering in the laminated body. The width of the part. In addition, although the width | variety of a sealing part may be non-uniform | heterogenous in the surface direction of a laminated body, it needs to be 5 mm or more in every place. Further, the penetration rate of the adhesive may not be uniform in the laminating direction, but at least in the range of 5 mm or more from the end portion, the filling rate is all in the porous membrane, the auxiliary support membrane, and the permeating gas channel member. It satisfies 60% or more.
The width of the sealing portion may be 5 mm or more. However, the larger the size, the smaller the effective separation area. Therefore, the width is preferably 70 mm or less.
It is preferable that the porous film is made of a fluorine resin material.
The porous membrane is particularly preferably made of polytetrafluoroethylene (PTFE).
The adhesive is preferably made of an epoxy resin.
In the laminated body for acidic gas separation of this invention, it is preferable to have an intermediate | middle layer between a porous membrane and an acidic gas separation promotion transport film.
The intermediate layer is preferably a silicone resin.
The acidic gas separation module of the present invention includes a permeate gas collecting pipe and the laminate for acidic gas separation of the present invention, and a permeate gas flow path member at an end portion where a sealing portion of the laminate is not formed. , And connected to a permeate gas collecting pipe.
The acid gas separation module of the present invention may be a spiral type module or a flat membrane type module.
The laminate for acidic gas separation of the present invention comprises a porous support in which a porous membrane and an auxiliary support membrane are laminated, an acidic gas separation promoting transport membrane, and a permeating gas channel member, and is porous. Adhering to the membrane at a penetration rate of 60% or more, and adjacent to the sealing part formed by penetration of the adhesive into the auxiliary support membrane and the gas flow path member at a penetration rate of 60% or more, At least the penetration rate of the adhesive in the porous membrane is less than 60%, and it is provided with a stress buffer portion formed by the adhesive penetrating into the auxiliary support membrane and the permeating gas flow path member. When it is assembled into a module and used for use, the stress concentration generated at the boundary due to the difference in mechanical strength between the area where the adhesive is soaked and the area where it is not, can be alleviated. Suppress the occurrence of Door can be.
It is a schematic perspective view which shows one Embodiment of the laminated film for acidic gas separation of this invention. It is a figure for demonstrating the effect of the laminated film for acidic gas separation of this invention. It is a figure which shows the example of a shape of the sealing part and stress buffer part of the laminated film for acidic gas separation of this invention. It is a figure which shows the other example of a shape of the sealing part of the laminated film for acidic gas separation of this invention, and a stress buffer part. It is a figure which shows the example of a design change of the laminated film for acidic gas separation of this invention. It is a partial cross section figure which shows the manufacturing process of the laminated film for acidic gas separation. It is a partial cross section figure which shows the manufacturing process of the laminated film for acidic gas separation following FIG. 2A. It is a partial cross section figure which shows the manufacturing process of the laminated film for acidic gas separation following FIG. 2B. It is a figure which shows the coating method of the adhesive agent using a slot die. It is a figure which shows the other application | coating method of the adhesive agent using a slot die. It is a top view which shows the application | coating method of the adhesive agent using a stamp. It is a side view which shows the application method of the adhesive agent using a stamp. It is a partially notched schematic block diagram which shows the spiral type module of one Embodiment of this invention. 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 figure which shows the state before winding a laminated body around a permeation gas collection pipe. It is a figure which shows a spiral type module manufacturing process. It is a figure which shows the spiral type module manufacturing process following FIG. 8A. It is a figure which shows the spiral type module manufacturing process following FIG. 8B (the 3). 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. It is a schematic perspective view which shows the planar module of one Embodiment of this invention. It is the XII-XII sectional view taken on the line of the planar module shown in FIG.
Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the following drawings, members (components) having the same or corresponding functions are denoted by the same reference numerals, and description thereof will be omitted as appropriate.
[Layered product for acid gas separation]
FIG. 1A is a schematic perspective view showing a laminated configuration of an acid gas separating laminate 1 according to an embodiment of the present invention, and FIG. 1B is an enlarged sectional view of an end portion of the laminate 1.
As shown in FIG. 1A, the acid gas separation laminate 1 of this embodiment includes a porous support 4 in which a porous membrane 2 and an auxiliary support membrane 3 are laminated, and a porous support 4. Gas separation comprising a carrier that reacts directly or indirectly with the acidic gas in the source gas (supply gas) and an acidic gas separation-promoting transport membrane 5 containing a hydrophilic compound that carries the carrier, which is arranged on the membrane 2 side Permeate gas flow through which the composite gas (hereinafter referred to as gas separation membrane) 10 and the acidic gas that has permeated the separation support transport membrane 5 and the porous support 4 are disposed on the auxiliary support membrane 3 side of the porous support 4 And a road member 6.
And the sealing part 7 for sealing the inflow of gas to the porous support body 4 and the member 6 for permeate gas passages in three sides except one side among the peripheral edges (four sides) of the rectangular laminate 1. A stress buffering portion 9 is provided adjacent to the sealing portion 7. The sealing part 7 has a function of adhering the separation membrane 10 and the flow path member 6 and preventing mixing of the supply gas and the permeated gas. Further, the stress buffering portion 9 has a function of suppressing the occurrence of defects in the facilitated transport film 5.
The sealing portion 7 is a portion configured by soaking the adhesive 8 into the porous support 4 and the flow path member 6, and 60% or more in the porous film 2 of the porous support 4 in the stacking direction. The adhesive 8 is soaked at the soaking rate, and the auxiliary support film 3 and the channel member 6 are portions where the adhesive 8 is soaked at a soaking rate of 60% or more. The width x of the sealing portion 7 (hereinafter, the sealing width x) is 5 mm or more from the end portion of the stacked body 1. In the sealing part 7, the penetration rate of the adhesive 8 in the auxiliary support film 3 and the channel member 6 is preferably 80% or more, and more preferably 90% or more.
By setting the sealing width x to 5 mm or more, a sufficient gas sealing function can be ensured. Since the adhesive does not necessarily spread with a uniform width, the sealing width x and the width a of the stress buffer portion 9 are changed at each position in the plane direction of the laminate 1 as shown in the schematic diagram of FIG. The smallest sealing width should just be 5 mm or more. On the other hand, when the sealing width x increases, the effective area for gas separation becomes narrow. Therefore, it is better not to be too long as long as the sealing width x is 5 mm or more over the entire region. The sealing width x is preferably 5 mm to 70 mm, and particularly preferably 10 mm to 50 mm.
The stress buffer portion 9 is a portion where at least the penetration rate of the adhesive 8 in the porous film 2 is less than 60%. In the stress buffer 9, in the auxiliary support film 3 and the channel member 6, the penetration rate of the adhesive may be 60% or more or less than 60%, but at least the channel member 6. The penetration rate is preferably 10% or more. Further, in the stress buffer portion 9, it is preferable that the penetration rate in the flow path member 6 is larger than the penetration rate in the porous film 2. The stress buffering portion 9 has a function of suppressing the occurrence of defects in the facilitated transport film 5 but is also a loss portion of the flow path. That is, the larger the region of the stress buffering portion 9, the more the passage of the permeate gas is lost. Therefore, the width a of the stress buffering portion 9 is preferably as short as possible. By setting the width a to less than half (50% or less) of the sealing width x, it is possible to suppress film defects due to stress and to reduce the flow path loss. The width of the stress buffer portion 9 is more preferably 40% or less of the width of the sealing portion.
In this example, the laminated body 1 has a rectangular shape, and a sealing portion 7 and a stress buffering portion 9 adjacent to the sealing portion 7 are formed on three sides excluding one side of the periphery. Note that the shape of the laminated body 1 and the region where the sealing portion 7 is formed can be appropriately set according to the module configuration to which the laminated film is applied.
Although this laminated body 1 is applied to the separation membrane module which isolate | separates acidic gas from the raw material gas (supply gas) containing acidic gas, it is suitable especially when supply gas contains water vapor | steam. When applied to such a separation membrane module, the facilitated transport membrane 5 decreases its viscosity by absorbing moisture. At this time, the facilitated transport film 5 is pressed against the porous membrane side by the pressure (the differential pressure between the supply gas and the permeated gas) S due to the supply gas, and at that time, the region in which the adhesive is infiltrated and the adhesive infiltrate. Since the mechanical strength (rigidity) is different from the unexposed region, stress concentration occurs at the boundary between the two regions, which may cause defects in the facilitated transport film 5 at the boundary. The laminated body 1 which is embodiment of this invention is equipped with the stress buffer part 9 adjacent to the sealing part 7, as shown to an enlarged view in FIG. 1B, and relieve | moderates the stress concentration by this stress buffer part 9. Generation of defects in the facilitated transport film 5 can be suppressed by the function. When performing gas separation by the module, a predetermined pressure S is normally applied to the facilitated transport film 5 from the supply gas side due to the pressure difference (differential pressure) between the supply gas and the permeate gas. At this time, the rigidity of the porous support 4 and the flow path member 6 that supports the facilitated transport film 5 differs depending on the penetration rate of the adhesive (including the presence or absence of the penetration), so that the boundary position between regions having greatly different stiffnesses Stress concentration occurs in a portion of the facilitated transport film 5 indicated by an arrow P in FIG. 1B, for example. When the stress buffering portion 9 is not provided, the sealing portion 7 and the region where no adhesive penetrates are adjacent to each other. Therefore, stress concentration at the boundary increases, and the facilitated transport film 5 is likely to be defective. Since the rigidity can be changed stepwise by providing 9, the stress concentration can be relaxed.
1A and 1B show a state in which the adhesive film 8 is not soaked into the porous film 2 of the stress buffering portion 9 at all. However, as shown in FIG. In the film 2, the soaking area 9a may be gradually changed. Further, in the auxiliary support film 3 and the flow path member 6, the soaking region may have a distance from the end portion changed in the stacking direction.
In addition, as shown in FIG. 1D, the penetration rate of the adhesive is determined by image processing for each region having a width of 0.01 mm from the end portion on the cut surface, for example, for each region c i sandwiched by a dashed line in FIG. 1D. Thus, the ratio of the area filled with the adhesive to the area of the hole of each layer (the porous membrane 2, the auxiliary support membrane 3, and the flow path member 6) is calculated and calculated. Further, the width of the sealing portion and the width of the stress buffer portion are determined from the penetration rate of the adhesive. For each region having a width of 0.01 mm from the end (hereinafter referred to as a measurement unit region), the adhesive penetration rate in the porous membrane is determined, and the end portion of the measurement unit region that satisfies the adhesive penetration rate of 60% or more in the porous membrane most (in FIG. 1D, the region c n) distant measurement unit region is a region a sealing portion 7 up to and including the distant side edge of a stack end of the measuring unit region c n from the end of the stack from The distance to 9b is the width of the sealing portion 7. Since the filling factor becomes smaller toward the adhesive from the end side of the laminate in-plane inwardly of the laminate, infiltration first adhesive region c n + 1 adjacent to the plane direction of the region c n The rate is less than 60%. Then, a region containing up to the measurement unit areas c z-1 of the immediately preceding in the measurement unit region from the edge 9b of the region c z where adhesive soaks rate becomes 0% in the porous membrane of the sealing portion 7 with stress buffer 9 The distance from the end 9b of the sealing portion 7 to the end 9c of the region cz-1 immediately before the adhesive penetration rate becomes 0% is the width of the stress buffering portion 9. As shown in FIG. 1C, the adhesive soaking area may vary greatly depending on the position in the surface direction in which the sealing portion is formed, and therefore the width of the sealing portion and the width of the stress buffering portion are a plurality of locations. The average value of the values obtained in the cross section (for example, three locations) is used.
<Gas separation membrane>
The gas separation membrane 10 includes an acidic gas separation facilitated transport membrane 5 and a porous support 4 that supports the facilitated transport membrane 5 and is provided on the permeate gas flow path member 6 side.
(Acid gas separation facilitating transport membrane)
The acidic gas separation promoting transport membrane 5 contains at least a carrier that reacts directly or indirectly with the acidic gas in the raw material gas and a hydrophilic compound that carries the carrier, and has a function of selectively permeating the acidic gas from the raw material gas. Have.
Since the facilitated transport film 5 generally has higher heat resistance than the dissolution diffusion film, it can selectively permeate acidic gas even under a temperature condition of, for example, 100 ° C. to 200 ° C. Further, even if the source gas contains water vapor, the hydrophilic compound absorbs the water vapor and the facilitated transport film containing the hydrophilic compound retains moisture, so that carriers can be more easily transported. Separation efficiency is increased as compared with the case where a dissolution diffusion membrane is used.
Membrane area facilitated transport membrane 5 is not particularly limited, it is preferably 0.01 m 2 or more 1000 m 2 or less, more preferably 0.02 m 2 or more 750 meters 2 or less, 0.025 m 2 or more 500 meters 2 Even more preferably: Furthermore, the membrane area, from a practical point of view, is preferably 1 m 2 or more 100 m 2 or less.
By setting it as each lower limit or more, an acidic gas can be efficiently isolate | separated with respect to a membrane area. Moreover, workability becomes easy by being below each upper limit.
Although the thickness of the facilitated-transport film | membrane 5 is not specifically limited, It is preferable that it is 1-200 micrometers, and it is more preferable that it is 2-175 micrometers. A thickness in such a range is preferable because sufficient gas permeability and separation selectivity can be realized.
(Hydrophilic compound)
A hydrophilic polymer is mentioned as a hydrophilic compound. The hydrophilic polymer functions as a binder, holds water, and exhibits 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 the acidic gas separation layer has high hydrophilicity (humidity retention) from the viewpoint of having high hydrophilicity (humidity retention). 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 polymer include, for example, polyvinyl alcohol-polyacrylic acid salt, polyvinyl alcohol-polyacrylic acid (PVA-PAA) copolymer, polyvinyl alcohol, polyacrylic, from the viewpoint of hydrophilicity, film-forming property, strength, and the like. Acid, polyacrylate, polyvinyl butyral, poly-N-vinylpyrrolidone, poly-N-vinylacetamide, and polyacrylamide are preferable, and PVA-PAA copolymer is particularly preferable. The PVA-PAA copolymer has a high water absorption capacity and a high strength in a hydrogel state at the time of high water absorption. The content of polyacrylate in the PVA-PAA copolymer is, for example, preferably 5 mol% or more and 95 mol% or less, more preferably 30 mol% or more and 70 mol% or less. 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.).
(Acid gas carrier)
Acid gas carriers are various water-soluble compounds that have an affinity with acid gas (for example, carbon dioxide gas) and show basicity, and indirectly react with acid gas, or itself itself. It reacts with acid gas. Indirect reaction with acid gas includes, for example, reaction with other gas contained in the supply gas to generate a basic compound, and reaction of the basic compound with acid gas. As this type of acid gas carrier, specifically, OH in contact with steam (water vapor) - was released, the OH - is selectively incorporating the CO 2 in the film by reacting with CO 2 Alkali metals and alkali metal compounds that can be used.
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. An aqueous solution to which a ligand is added may be mentioned.
In addition, in this specification, an alkali metal or an alkali metal compound is used in the meaning including its salt and its ion in addition to 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 bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, and cesium bicarbonate.
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 acidic gas.
In the present embodiment, since a hygroscopic facilitated transport film is used, the phenomenon that the facilitated transport film becomes a gel with moisture absorbed during manufacture and the facilitated transport film adheres to each other and other members during manufacture (blocking) is present. It 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 types of carriers, the same type of carriers in the film can be separated from each other, and blocking non-uniformity can be generated and blocking suppression can be achieved.
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, when two or more kinds of alkali metal compounds (first and second alkali metal compounds) are applied as the carrier, the facilitated transport film 5 is a second layer on the surface side opposite to the porous support 4. And a first layer on the porous support 4 side below. 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.
For example, in the facilitated transport film 5, 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 can be spread below the second layer. It is not limited. For example, the interface between the two layers may not be clear and may be divided in a state in which the concentration of the two changes in an inclined manner. In addition, the interface is not planar and may have a gentle undulation.
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.
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 with respect to 100 parts by mass of the second alkali metal compound, and 100 parts by mass. More preferably, it is at least part. As an upper limit, it is preferable that it is 100000 mass parts or less, and it is more preferable that it is 80000 mass parts or less. 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.
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 1, an alkali metal compound is indicated by the name of an alkali metal, but a salt or ion thereof may be used.
The content of the acidic gas carrier in the facilitated transport membrane as a whole depends on the ratio to the amount of the hydrophilic compound and the type of acidic gas carrier, but prevents salting out before coating and ensures the separation function of acidic gas. In order to exhibit, it is preferably 0.3% by mass to 30% by mass, more preferably 0.5% by mass to 25% by mass, and particularly preferably 1% by mass to 20% 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 determined based on the total amount of solids such as a 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 kinds 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.
Examples of the nitrogen-containing compound include 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. For example, amino acids such as glycine, alanine, serine, proline, histidine, taurine, diaminopropionic acid, hetero compounds such as pyridine, histidine, piperazine, imidazole, triazine, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine , Alkanolamines such as dipropanolamine and tripropanolamine, cyclic polyetheramines such as cryptand [2.1] and cryptand [2.2], cryptand [2.2.1] and cryptand [2.2 .2] and the like, porphyrins, phthalocyanines, 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.
The facilitated transport membrane may contain other components (additives) other than the hydrophilic polymer, the acidic gas carrier and water as long as the separation characteristics are not adversely affected. As an optional component, for example, in the process of applying an aqueous solution (coating solution) for forming a facilitated transport film containing a hydrophilic polymer and an acidic gas carrier onto a porous support and drying it, the coating liquid film is cooled. A gelling agent that controls the so-called set property, a viscosity adjusting agent that adjusts the viscosity at the time of coating when the coating solution is coated with a coating device, a crosslinking agent for improving the film strength of the facilitated transport film, Examples include acid gas absorption accelerators, surfactants, catalysts, auxiliary solvents, membrane strength modifiers, and detection agents for facilitating the inspection of the formed facilitated transport membrane for defects.
<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 there is an effect that wrinkles do not occur even when handled by a coating machine or the like, and productivity can be improved.
(Porous membrane)
The porous membrane 2 has an acid gas permeability such as carbon dioxide which is a gas to be separated.
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.
In the present invention, the porous membrane 2 is a porous resin sheet made of a resin material such as polyester, polyolefin, polyamide, polyimide, polysulfonamide, polysulfone, polycarbonate, polyacrylonitrile or the like.
The acidic gas separation module to which the laminated body for acidic gas separation according to the present invention is applied is used, for example, under a high temperature of about 130 ° C. and humidification using steam, although the use temperature varies depending on the application. There are many cases. 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 to reinforce the porous membrane 2 and is not particularly limited as long as the strength, stretch resistance and gas permeability are good, and a nonwoven fabric, a woven fabric, a knitted 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. The fibers constituting the nonwoven fabric, woven fabric, and knitted fabric include fibers made of modified polyamides such as polypropylene and aramid, fluorine-containing resins such as polytetrafluoroethylene and polyvinylidene fluoride, which are excellent in durability and heat resistance. preferable. 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.
(Permeate gas channel member)
The permeate gas channel member 6 is a member through which the acidic gas that has reacted with the carrier and permeated the gas separation membrane 10 flows. The permeate gas flow path member 6 has a function as a spacer, has a function of flowing an acidic gas to the permeate gas collecting pipe side, and further has a function of permeating an adhesive described later. The member 6 is preferably an uneven member with a gap. Examples include tricot knitting and plain weaving. Further, assuming that a raw material gas containing water vapor flows at a high temperature, it is preferable that the permeate gas flow path member has moisture and heat resistance, like the gas separation membrane.
Specific materials used for the permeating gas flow path member are preferably polyesters such as epoxy-impregnated polyester, polyolefins such as polypropylene, fluorines such as polytetrafluoroethylene, and metals such as wire mesh.
The thickness of the permeating gas channel member 6 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.
Further, the permeating gas channel member may be the same type or a single type, but the same type or a plurality of types may be laminated.
In the present invention, the adhesive 8 used for the sealing portion 7 and the stress buffering portion 9 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-acrylonitrile. 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 resin, Examples include silicone resins and urea formamide resins.
Particularly preferred is an epoxy resin.
In order to improve the wettability of the adhesive, it may contain a solvent or a surfactant.
As the laminate 1, the porous membrane 2 is a PTFE porous sheet, the auxiliary support membrane 3 is a porous support 4 made of PP nonwoven fabric, the flow path member 6 is made of PP woven fabric, and the sealing portion 7 It is a particularly preferable form to use an epoxy resin as the adhesive 8 used in the above.
The gas separation membrane 10 having the facilitated transport membrane 5 on the support 4 may have another layer other than the facilitated transport membrane 5 on the support 4. Examples of other layers include an undercoat layer provided between the porous support 4 and the facilitated transport film 5, an intermediate layer, and a protective layer (eg, a carrier elution preventing layer) provided on the facilitated transport film 5. Can be mentioned.
FIG. 1E is a schematic perspective view showing a laminated configuration of the acid gas separation laminate 11 of the design modification example of the embodiment. In the laminate 11 of this example, in the laminate 1 described above, the acidic gas separation membrane 17 includes an intermediate layer 15 between the porous support 4 and the facilitated transport membrane 5.
As described above, since the facilitated transport film needs to retain a large amount of moisture in the film in order for the carrier to function sufficiently, a hydrophilic compound having extremely high water absorption and water retention is used. In addition, in the facilitated transport membrane, as the content of a carrier such as a metal carbonate increases, the water absorption increases and the separation performance of the acid gas improves. For this reason, the facilitated transport membrane is often a gel membrane or a low-viscosity membrane. Accordingly, the porous membrane of the acid gas separation membrane has hydrophobicity at least on the surface in contact with the facilitated transport membrane from the viewpoint of suppressing the penetration of the facilitated transport material when forming the facilitated transport membrane. Is preferred. However, even with a hydrophobic porous membrane, a source gas having a temperature of 100 to 130 ° C. and a humidity of about 90% is supplied at a pressure of about 1.5 MPa at the time of separation of the acidic gas. The facilitated transport membrane gradually enters the porous support, and the acid gas separation ability tends to decrease with time.
Therefore, the acidic gas separation membrane includes an intermediate layer 15 between the porous membrane and the facilitated transport membrane that more effectively suppresses the penetration of the facilitated transport material (membrane) into the porous membrane. Is preferred.
The intermediate layer 15 is not particularly limited as long as it is a hydrophobic layer having gas permeability, but preferably has a gas permeability and is denser than the porous membrane. By providing the intermediate layer 15, it is possible to prevent the facilitated transport film 5 having high uniformity from entering the porous film 2.
The intermediate layer 15 only needs to be formed on the porous film 2, but may have a soaked region that is soaked in the porous film 2. The smaller the permeation area, the better the adhesiveness between the porous membrane 2 and the intermediate layer 15 within the range.
The intermediate layer 15 is preferably a polymer layer having a siloxane bond in the repeating unit. Examples of such a polymer layer include silicone-containing polyacetylene such as organopolysiloxane (silicone resin) and polytrimethylsilylpropyne. Specific examples of the organopolysiloxane include those represented by the following general formula.
In the above general formula, n represents an integer of 1 or more. Here, from the viewpoints of availability, volatility, viscosity, and the like, the average value of n is preferably in the range of 10 to 1,000,000, and more preferably in the range of 100 to 100,000.
R 1n , R 2n , R 3 , and R 4 are each a group consisting of a hydrogen atom, an alkyl group, a vinyl group, an aralkyl group, an aryl group, a hydroxyl group, an amino group, a carboxyl group, and an epoxy group. Indicates which one is selected. Note that n R 1n and R 2n may be the same or different. In addition, the alkyl group, aralkyl group, and aryl group may have a ring structure. Further, these alkyl groups, vinyl groups, aralkyl groups, and aryl groups may have a substituent, and the substituents are alkyl groups, vinyl groups, aryl groups, hydroxyl groups, amino groups, carboxyl groups, epoxy groups. Or selected from fluorine atoms. These substituents may further have a substituent if possible.
The alkyl group, vinyl group, aralkyl group, and aryl group selected from R 1n , R 2n , R 3 , and R 4 are each an alkyl group having 1 to 20 carbon atoms or vinyl from the viewpoint of availability. Group, an aralkyl group having 7 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms are more preferable.
In particular, R 1n , R 2n , R 3 , and R 4 are preferably methyl groups or epoxy-substituted alkyl groups. For example, epoxy-modified polydimethylsiloxane (PDMS) can be suitably used.
The silicone resin layer is preferably formed by coating. The coating solution used for film formation (silicone coating solution) contains a monomer, dimer, trimer, oligomer, prepolymer, or mixture of compounds that form a silicone resin layer, and further includes a curing agent, a curing accelerator, and a crosslinking agent. , Thickeners, reinforcing agents and the like may be included.
The intermediate layer 15 is a film having gas permeability, but if it is too thick, the gas permeability may be significantly reduced. The intermediate layer 15 may be thin as long as it covers the entire surface of the porous film 2 without passing through. Considering this point, the film thickness of the intermediate layer 15 is preferably 0.01 μm or more and 30 μm or less, and more preferably 0.1 μm or more and 15 μm or less.
[Method for producing laminate for acid gas separation]
Next, the manufacturing method of the laminated body 1 is demonstrated easily with reference to FIG. 2A-FIG. 2C. 2A to 2C are partially enlarged cross-sectional views showing manufacturing steps.
First, a porous support 4 in which a porous film 2 and an auxiliary support film 3 are laminated is prepared.
Moreover, the coating composition for formation of an acidic gas separation promotion transport film is adjusted. The coating liquid composition is prepared by adding the above-mentioned hydrophilic polymer, acidic gas carrier (for example, carbon dioxide carrier), and water, and, if necessary, other additives such as a gelling agent and a crosslinking agent in appropriate amounts. Add to water (room temperature water or warm water) and stir well. If necessary, heat with stirring to promote dissolution. In addition, a hydrophilic polymer, an acidic gas carrier, and other components may be added separately to water, or those previously mixed may be added.
As shown in FIG. 2A, this coating solution composition is applied onto the porous film 2 of the porous support 4 and dried to form the facilitated transport film 5 on the porous support 4. The gas separation composite membrane of the porous support 4 and the facilitated transport membrane 5 is the gas separation membrane 10.
Next, as shown in FIG. 2B, the adhesive 8 is applied to three sides of the peripheral edge so that the auxiliary support film 3 becomes the upper surface (see FIG. 4A).
Next, as shown in FIG. 2C, the gas separation membrane 10 is placed on the flow path member 6 so that the application surface of the adhesive 8 of the gas separation membrane 10 is in contact (or the adhesive of the gas separation membrane 10). The adhesive 8 is permeated into the auxiliary support film 3 and the eyes (holes) of the channel member 6 by applying tension in the film surface direction (with the channel member 6 placed on the application surface).
As a result, as shown in FIG. 2C, the sealing portion 7 formed by continuously infiltrating the adhesive 8 in the stacking direction of the porous membrane 2, the auxiliary support membrane 3, and the gas flow path member 6, and this example Then, the adhesive 8 does not permeate into the porous membrane 2, and adhesive spreading portions 9 and 19 formed by permeating the adhesive 8 only into the auxiliary support membrane 3 and the gas flow path member 6 are formed. In FIG. 2C, the spreading portions 9 and 19 are shown as being symmetric, but they are not necessarily formed symmetrically. Finally, the end portion shown in FIG. 2C is cut at, for example, the position of the line C-C, and so-called trimming (end face correction processing) is performed to obtain the laminate 1. At this time, the relationship between the width x of the sealing portion 7 and the width a of the adhesive spreading portion 9 (in this example, the spreading portion forms the stress buffering portion 9) satisfies a ≦ 0.5x. Cut at the position.
Here, in the stress buffer portion 9, it is assumed that the adhesive does not penetrate into the porous film 2, but as described with reference to FIG. 1C, the porous film 2 has a filling rate of less than 60%. The adhesive may penetrate.
As a method for applying the adhesive 8, a slot die 60 can be used as shown in FIGS. 3A and 3B. As shown in FIG. 3A, the separation membrane 10 may be conveyed in the A direction by using a conveyance roll 65, and the adhesive 8 may be applied by the slot die 60. Alternatively, as shown in FIG. The adhesive 8 may be applied while being transported in a direction B perpendicular to 60.
Alternatively, as shown in a plan view in FIG. 4A and a side view in FIG. 4B, a stamp 70 provided with a sponge 72 having a shape corresponding to the coating area is used, and the sponge 72 soaked with the adhesive 8 is used as a separation membrane. You may use the method of apply | coating the adhesive agent 8 by pressing on 10 surface (auxiliary support film surface).
Alternatively, a method may be used in which the adhesive 8 is applied by impregnating the brush with an adhesive using a brush-like jig and applying the brush onto the surface of the separation membrane 10.
If these adhesive coating methods are used, it is easy to automate the manufacturing process, and uniform coating can be performed by controlling the coating amount and coating width.
[Module for acid gas separation]
The acidic gas separation laminate of the present invention is used by being incorporated in an acidic gas separation module. The module for separating acidic gas of the present invention comprises a permeate gas collecting pipe and the laminated film of the present invention connected to the collecting pipe. The acid gas separation module can take various module forms such as a spiral type and a flat membrane type.
The above-described laminate shown in FIG. 1 has the minimum unit configuration of the present invention, but the laminate of the present invention can be used by appropriately changing the configuration according to the applied module configuration.
Hereinafter, a specific acidic gas separation module to which the acidic gas separation laminate of the present invention is applied will be described.
<Spiral acid gas separation module>
FIG. 5 is a partially cutaway view showing a spiral acid gas separation module 100 (hereinafter referred to as a spiral type module 100) which is a first embodiment of the acid gas separation module of the present invention. FIG.
As shown in FIG. 5, the spiral module 100 has a basic structure in which the outermost periphery is covered with a coating layer 16 in a state where one or more laminated bodies 14 described later are wound around the permeating gas collecting pipe 12. The telescope prevention plates 18 are attached to both ends of these units, respectively. When the raw material gas 20 containing an acidic gas is supplied to the laminated body 14 from the one end portion 100A side, the module 100 having such a configuration is configured so that the raw material gas 20 is mixed with the acidic gas 22 and the remainder by the constitution of the laminated body 14 to be described later. The gas 24 is separated and discharged separately to the other end 100B side.
6 is a perspective view showing a state before the laminated body 14 is wound around the permeate gas collecting pipe 12, and FIG. 7 shows a part of a cylindrical wound body in which the laminated body is wound around the permeate gas collecting pipe. It is sectional drawing.
The permeate gas collecting pipe 12 is a cylindrical pipe having a plurality of through holes 12A formed in the pipe wall. The one end side (one end 100A side) of the permeate gas collecting pipe 12 is closed, the other end side (the other end 100B side) of the permeate gas collecting pipe 12 is opened, and the carbon dioxide collects from the through hole 12A through the laminate. A discharge port 26 from which acidic gas 22 such as gas is discharged is provided.
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 100. This blocking material preferably further has heat and humidity resistance. Here, “heat resistance” in the heat and humidity resistance means having a 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 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.
The laminated body 14 is formed by laminating a permeated gas flow path member 6 on a leaf 50 formed by sandwiching a supply gas flow path member 30 inside an acidic gas separation membrane 10 in which the facilitated transport film 5 is folded inward. Composed. The acidic gas separation membrane 10 includes a porous support 4 formed by laminating a porous membrane 2 and an auxiliary support membrane 3, and at least a hydrophilic compound and a raw material disposed on the porous membrane 2 side of the porous support 4 An acidic gas separation promoting transport film 5 including an acidic gas carrier that reacts with acidic gas in the gas is provided. The acidic gas separation membrane 10 and the permeating gas flow path member 6 include a sealing portion 7 and a stress buffering portion 9 on three sides of the periphery of the laminate 14. Instead of the acidic gas separation membrane 10, an acidic gas separation membrane 17 having an intermediate layer 15 between the porous support 4 and the facilitated transport membrane 5 may be used.
This laminated body 14 is one form of the above-mentioned laminated body for acid gas separation of the present invention. That is, the sealing part 7 has a width of 5 mm or more, the penetration rate of the adhesive into the porous membrane 2 is 60% or more, and the penetration rate into the auxiliary support membrane 3 and the permeating gas channel member 6 is 60% or more. And a stress buffering portion 9 having a width a of 50% or less of the sealing width x is provided adjacent to the sealing portion 7. The details of the sealing part and the stress buffering part are the same as in the case of the laminate 1 in FIG.
The number of the laminated bodies 14 wound around the permeate gas collecting pipe 12 is not particularly limited, and may be single or plural, but the film area of the facilitated transport film 5 can be improved by increasing the number (number of laminated layers). 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.
Moreover, when there are a plurality of laminates 14, the number is preferably 50 or less, more preferably 45 or less, and even more 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, More preferably, 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 10 can be secured 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.
In the spiral type module, as shown in FIG. 6, the laminated body 14 is wound around the permeate gas collecting pipe 12 and the collecting pipe 12 is wound in the direction of arrow C, and as shown in FIG. The laminated body 14 is stacked on the wound permeate gas channel member 6. The laminated bodies 14 are bonded to each other via the sealing portions 7 at both ends. In this configuration, the raw material gas 20 including the acidic gas 22 is supplied from the end of the supply gas flow path member 30, and the acidic gas 22 that has been separated through the acidic gas separation membrane 10 is used for the permeated gas flow path. The gas is collected in the permeate gas collecting pipe 12 through the member 6 and the through-hole 12 </ b> A, and is collected from the discharge port 26 connected to the permeated gas collecting pipe 12. The residual gas 24 separated from the acid 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 100. It is discharged from the end of the member 30.
As shown in FIG. 6, when the permeate gas collecting pipe 12 is rotated in the direction of arrow C in the figure to cover the through-hole 12A with the permeate gas flow path member 6, and the laminate 14 is wound around the permeate gas collective pipe in multiple layers. Further, the acid gas separation membrane 10 and the permeate gas passage member 6 are bonded to each other by the adhesive 8 applied to the front and back surfaces of the gas separation membrane 10 folded in half with the supply gas passage member 30 in between. The sealing part 7 is formed.
The sealing portion 7 is not provided at the end of the collecting gas 12 along the permeate gas collecting tube 12 between the acidic gas separation membrane 10 at the beginning of winding and the permeating gas flow path member 6, and is surrounded by the sealing portion 7. In these regions, flow paths P1 and P2 are formed in which the acidic gas 22 that has passed through the acidic gas separation membrane 10 flows to the through hole 12A.
Each element of the laminated body 14 applied to the acidic gas separation module is the same as the constituent elements denoted by the same reference numerals in the acidic gas separation laminated body 1 described above. The acidic gas separation module laminate 14 further includes a supply gas flow path member 30.
(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, it is preferable that the supply gas flow path member 30 has a heat and moisture resistance like the gas separation membrane 10.
The material of the supply gas flow path member 30 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 Preferred examples include ether ether ketone and polyvinylidene fluoride.
In addition, preferred materials from the viewpoint of heat and humidity resistance include inorganic materials such as ceramics, glass and metal, 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.
Although the thickness of the member 30 for supply gas flow paths is not specifically limited, 100 micrometers or more and 1000 micrometers or less are preferable, More preferably, they are 150 micrometers or more and 950 micrometers or less, More preferably, they are 200 micrometers or more and 900 micrometers or less.
<Manufacturing method of spiral type module>
Next, a method for manufacturing the acid gas separation module having the above-described configuration will be described. 8A to 8C are manufacturing process diagrams of the acid gas separation module.
In the method for manufacturing the acidic gas separation module 100, first, as shown in FIG. 8A, the distal end portion of the elongate permeate gas channel member 6 is provided along the axial direction of the permeate gas collecting pipe 12. Insert into slit (not shown). According to this configuration, even when the laminate 14 including the permeate gas flow path member 6 is wound around the permeate gas collecting pipe 12, the inner circumferential surface of the permeate gas collecting pipe 12 The permeate gas channel member 6 does not come out of the slit due to friction with the permeate gas channel member 6, that is, the permeate gas channel member 6 is kept fixed. When the permeate gas collecting pipe 12 is not provided with a slit, the tip of the permeate gas flow path member is a fixing member such as Kapton tape or an adhesive, and the perimeter of the permeate gas collective pipe 12 (outer peripheral surface). What is necessary is just to fix to.
Next, as shown in FIG. 8B, a long supply gas flow path member 30 is sandwiched between a long acidic gas separation membrane 10 in which the acidic gas separation promoting transport membrane 5 is folded inward to form a leaf 50. To do. When the acidic gas separation membrane 10 is folded in two, the acidic gas separation membrane 10 may be divided into two as shown in FIG.
Next, the adhesive 8 is applied to both ends in the width direction and one end in the longitudinal direction of the one surface 50 a of the leaf 50.
Next, as shown in FIG. 8C, the leaf 50 is placed so that the surface 50 a coated with the adhesive 8 is in contact with the surface of the permeate gas flow path member 6 fixed to the permeate gas collecting pipe 12. At this time, the folded portion of the leaf 50 to which the adhesive 8 is not applied is set to the gas collecting pipe 12 side. As a result, the end portion on the collecting pipe 12 side along the permeate gas collecting pipe 12 between the acidic gas separation membrane 10 at the beginning of winding of the leaf 50 and the permeating gas flow path member 6 is opened, and the sealing section 7 is opened. A flow path P1 (see FIG. 6) in which the acidic gas 22 that has permeated the acidic gas separation membrane 10 flows to the through hole 12A is formed in the region surrounded by.
Next, an adhesive 38 is applied to the other surface 50b of the leaf 50 placed on the permeating gas channel member 6 at both ends in the width direction and one end in the longitudinal direction of the membrane.
Next, as schematically shown in FIG. 9, the permeate gas collecting pipe 12 is wound around the permeate gas collecting pipe 12 so as to cover the through hole 12A with the permeate gas flow path member 6 by rotating the permeate gas collecting pipe 12 in the direction of arrow C. The leaf 50 is further wound around the permeating gas channel member 6. At this time, by applying tension in the film direction, the adhesive 8 applied to one surface 50a of the leaf permeates the flow path member 6 and the porous support 4 to form the sealing portion 7, and Similarly, the adhesive 38 applied to the other surface 50b of the leaf 50 permeates the permeating gas channel member 6 and the porous support 4 to form the sealing portion 7. In this example, when the sealing portion 7 is formed, the adhesive partially spreads inside the laminated body to form the stress buffering portion 9. 7, the sealing portion 7 formed by the adhesive 8 or 38 penetrating into the ends of the collecting tube 12 in the length direction, and the stress buffering portion 9 adjacent to the sealing portion 7. Can be obtained.
A plurality of leaves 50 and permeate gas flow path members 6 sandwiching the supply gas flow path member 30 with the acidic gas separation membrane 10 folded in two are alternately stacked. As a result, as shown in FIG. A plurality of 14 may be overlapped and wound around the permeate gas collecting pipe in a multiple manner. In addition, when stacking a plurality of stacked bodies, it is preferable that the stacks are gradually shifted and stacked as shown in FIG. 10 so as not to increase the level difference 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. By covering and attaching the telescope prevention plates 18 to both ends, the acid gas separation module 100 shown in FIG. 5 is obtained.
<Flat membrane acid gas separation module>
FIG. 11 is a schematic perspective view showing a flat membrane type acidic gas separation module 110 (hereinafter referred to as a flat membrane type module 110) which is a second embodiment of the acidic gas separation module of the present invention. 12 is a cross-sectional view taken along line XII-XII in FIG.
As shown in FIGS. 11 and 12, the flat membrane module 110 includes a permeate gas collecting pipe 112 and a laminate 114 including separation membranes 10 and 10A on both surfaces of the permeate gas flow path member 6. .
The laminated body 114 is an embodiment of the acidic gas separation laminated body of the present invention, and the porous support 4 in which the porous film 2 and the auxiliary support film 3 are laminated, and the porous support 4 is porous. An acidic gas separation membrane 10 comprising an acidic gas separation promoting transport membrane 5 including at least a hydrophilic compound and an acidic gas carrier that reacts with an acidic gas in a raw material gas, disposed on the membrane 2 side; A permeating gas flow path member 6 is provided on the auxiliary support membrane 3 side, through which acidic gas that reacts with the acidic gas carrier and permeates the acidic gas separation promoting transport membrane 5 flows. In the present embodiment, another acidic gas separation membrane 10A that faces the acidic gas separation membrane 10 with the permeating gas flow path member 6 interposed therebetween is provided. Here, instead of the acidic gas separation membranes 10 and 10A, an acidic gas separation membrane 17 having an intermediate layer 15 between the porous support 4 and the facilitated transport membrane 5 may be used.
And the sealing part 7 formed by infiltrating the adhesive 8 in the laminating direction of the porous membrane 2, the auxiliary support membrane 3 and the permeating gas channel member 6 with a width of 5 mm or more on the periphery of the laminate 114, Adjacent to the auxiliary support membrane 3 and the permeating gas channel member 6 is provided a stress buffering portion 9 formed by infiltrating the adhesive 8 only. The sealing part 7 and the stress buffering part 9 are provided on three sides of the periphery of the laminate 114, and the end part where the sealing part 7 and the stress buffering part 9 are not provided is connected to the permeate gas collecting pipe 112. ing. A region surrounded by the sealing portion 7 is a flow path through which the acidic gas 22 that has passed through the acidic gas separation membrane 10 flows to the permeated gas collecting pipe 112.
The flat membrane module 110 is arranged in a container to which a raw material gas is supplied, and the acidic gas 22 in the raw material gas 20 reacts with the carrier of the facilitated transport film 5 and is taken into the laminated body 114 to be promoted transport film 5 and porous. The permeate gas support member 4 passes through the permeate gas passage member 6, is collected in the permeate gas collecting pipe 112, and is collected from a gas discharge port (not shown) connected to the permeate gas collecting pipe 112.
Also in the flat membrane type module of this embodiment, since the laminated body 114 includes the stress buffering portion 9 adjacent to the sealing portion 7, it occurs at the boundary between the sealing portion 7 and a portion other than the sealing portion. Damage to the facilitated transport film 5 due to stress concentration can be suppressed.
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.
A PTFE / PP nonwoven fabric (manufactured by GE) was used as a porous support composed of a laminated film of a porous film and an auxiliary support film. The thickness of PTFE was about 30 μm, and the thickness of the PP nonwoven fabric was about 200 μm.
(Preparation of carbon dioxide separation promoting transport membrane coating solution composition)
Polyvinyl alcohol-polyacrylic acid copolymer crustomer AP-20 (manufactured by Kuraray Co., Ltd.): 3.3% by mass, 25% glutaraldehyde aqueous solution (manufactured by Wako): Add 1M hydrochloric acid to an aqueous solution containing 0.016% by mass After the crosslinking, an aqueous 40% cesium carbonate (manufactured by rare metal company) aqueous solution as a carrier was added so that the cesium carbonate concentration was 6.0% by mass. Further, 1% lapizole A-90 (manufactured by NOF Corporation) was added so as to be 0.004% by mass, and after heating, the mixture was stirred and degassed to obtain a coating composition.
This coating composition was coated on a PTFE / PP nonwoven PTFE membrane and dried to form a separation membrane.
As a supply gas flow path member, a polypropylene net having a thickness of 0.44 mm is sandwiched between separation membranes whose carbon dioxide separation membrane surface is folded inward. Reinforce with double kapton tape. The folds were firmly folded so that the membrane surface was not damaged, curled, and leaves were formed.
Adhesive E120HP (made by Henkel Japan Co., Ltd.) made of epoxy resin on the three sides of one side of the perimeter of the permeate gas flow path member made of polypropylene fabric with a thickness of 0.5 mm fixed to a collecting tube with partitions ) Is applied so that one surface is in contact with the permeate gas channel member, and adhesive is applied to three sides of the periphery in the same manner on the other surface of the leaf placed on the channel member. Apply, place a new permeate gas channel member on it, and then repeat the process of placing a new leaf coated with adhesive. From the combination of one leaf and one permeate gas channel member 3 units were stacked and wound around the collecting pipe. After side cutting, aligning both ends, attaching a telescoping prevention plate made of PPS (40% glass), and reinforcing the periphery with FRP (Fiber Reinforced Plastics), a spiral separation membrane module was obtained. The design membrane area of the spiral-type separation membrane module of Example 1 was 1.2 m 2 . According to the measurement method described later, the sealing width of the sealing portion was 10 mm, and the width of the stress buffering portion was 30% of the sealing width.
Examples 2 to 6 and Comparative Example, except that the sealing width, the ratio of the width of the stress buffer portion to the sealing width, and the penetration rate of the adhesive in the stress buffer portion are as shown in Table 2 below. Modules of Examples 1 and 2 were respectively produced.
In Example 1, a laminate including an intermediate layer between the porous membrane and the facilitated transport membrane was produced as Example 7.
As an intermediate layer coating solution for forming the intermediate layer, epoxy-modified polydimethylsiloxane (KF-102 manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silicone resin, and 4-isopropyl-4′- manufactured by Tokyo Chemical Industry Co., Ltd. as a curing agent. Prepared by adding methyldiphenyliodonium tetrakis (pentafluorophenyl) borate. At this time, 0.5 wt% of a curing agent was added to the silicone resin 100. This intermediate layer coating solution was applied to the surface of the porous support by a roll-to-roll method, and the intermediate layer coating solution was cured by irradiating ultraviolet rays with a curing device to form an intermediate layer made of a silicone resin on the support. . The carbon dioxide separation-promoting transport membrane coating solution composition was coated on the support having the intermediate layer to obtain a laminate for acid gas separation in Example 7.
"Evaluation of spiral module for carbon dioxide separation"
The following evaluation was performed for the obtained carbon dioxide separation spiral modules of Examples and Comparative Examples, and the results are shown in Table 2 below.
<Seal width, ratio of stress buffer portion to seal width and penetration rate of adhesive>
After the module factor evaluation described later, the module is disassembled, the sealed portion is frozen and cut to obtain a cross section, the cross section is observed with a scanning electron microscope (SEM), the width of the sealing portion and the stress buffering portion The width of was measured. Specifically, three different cross-sections are taken out, and image processing is used for each cross-section, and each part of the porous membrane, the auxiliary support membrane, and the permeating gas channel member every 0.01 mm width from the end of the laminate. The adhesive penetration rate was determined from the adhesive filling area relative to the hole area in the porous membrane, the adhesive penetration rate in the porous membrane was 60% or more, and the adhesive penetration rate in the auxiliary support membrane and the permeating gas channel member was any As a sealing portion, a penetration rate of the adhesive in the porous membrane 2 is less than 60%, and a portion where the adhesive permeates at least the permeating gas channel member is used as a stress buffering portion. The width | variety of the sealing part and the width | variety of the stress buffer part were calculated | required. The average value of the ratio of the width of the sealing portion and the width of the stress buffer portion to the sealing width for the three cross sections is shown in Table 2 as the ratio of the width of the sealing portion of the module and the width of the stress buffer portion to the sealing width. Yes.
<Module factor>
The module factor of the module for carbon dioxide separation according to each of the produced examples and comparative examples was evaluated under the following conditions for each of the acidic gas separation module and the acidic gas separation promoting transport membrane on the porous support used in the module. And calculated.
(Measurement of separation factor of acid gas separation module)
A source gas (flow rate: 2.2 L / min) of H 2 : CO 2 : H 2 O = 45: 5: 50 is supplied to each carbon dioxide separation module at a temperature of 130 ° C. and a total pressure of 301.3 kPa as a supply gas. Ar gas (flow rate 0.9 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.
(Measurement of separation factor of acid gas separation promoting transport membrane itself on porous support)
A feed gas of H 2 : CO 2 : H 2 O = 45: 5: 50 as a supply gas (flow rate 0.32 L / min) is supplied to each carbon dioxide separation membrane at a temperature of 130 ° C. and a total pressure of 301.3 kPa, 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.
The module factor was determined based on the following formula.
Module factor = α of acid gas separation module / α of acid gas separation promoting transport membrane on porous support
As shown in Table 2, it was confirmed that the spiral module provided with the acid gas separation laminate of the present invention had a module factor of 0.5 or more in both the initial stage and the day after. Furthermore, in Examples 1 to 3 and 5 to 7 in which the ratio of the width of the stress buffer portion to the sealing width was 50% or less, a more preferable module factor of 0.6 or more could be obtained. This is considered to be because a larger effective area can be secured by suppressing the width of the stress buffer portion. Further, as shown in Example 7, by having the intermediate layer, it was possible to raise the stress buffering ability of the laminate while maintaining gas permeability, and it was possible to show a high module factor from the initial performance. On the other hand, Comparative Example 1 is a module in which the ratio of the width of the stress buffer portion to the sealing width is 0%, that is, a module that does not have the stress buffer portion, and a defect easily occurs, and the module factor can be measured after one day. could not. Comparative Example 2 had a small sealing width and could not be sufficiently sealed, and after one day, the part that was initially sealed was peeled off, and the module factor could not be measured.
In addition, the module of Example 1 had a high module factor in evaluation under high pressure (2.0 MPa).
DESCRIPTION OF SYMBOLS 1, 14, 114 Acid gas separation laminated body 2 Porous membrane 3 Auxiliary support membrane 4 Porous support 5 Acid gas separation promotion transport film 6 Permeate gas flow path member 7 Sealing portion 8, 38 Adhesive 9, 39 Stress buffer 10, 10A Acid gas separation membrane 12, 112 Permeate gas collecting pipe 20 Raw material gas 22 Acid gas 30 Supply gas flow path member 100 Spiral acid gas separation module 110 Flat membrane acid gas separation module
A porous support formed by laminating a porous film and an auxiliary support film, a carrier that is disposed on the porous film side of the porous support and reacts with an acid gas in a source gas, and supports the carrier A composite membrane comprising an acidic gas separation facilitating transport membrane containing a hydrophilic compound, and an acidic gas that has been laminated facing the auxiliary support membrane of the porous support and has passed through the composite membrane flows A laminated body for acid gas separation comprising a permeating gas channel member,
Permeation rate of the adhesive into the porous membrane , which is a laminated portion of the porous membrane, the auxiliary support membrane, and the permeating gas flow channel member with a width of 5 mm or more at the periphery of the laminate for acidic gas separation A sealing portion that is infiltrated at 60% or more and has a region in which the adhesive permeates into the auxiliary support membrane and the permeating gas channel member at a penetration rate of 60% or more,
A laminated portion of the porous membrane, the auxiliary support membrane, and the permeating gas channel member adjacent to the sealing portion, and at least the penetration rate of the adhesive in the porous membrane is less than 60%. and acid gases separation laminate, characterized in that it comprises a region where the adhesive to at least said permeable gas flow channel member is penetrated as stress buffer.
The laminate for acidic gas separation according to claim 1, wherein a width of the stress buffer portion is 0.1% to 50% of the width of the sealing portion.
The laminate for acidic gas separation according to claim 1 or 2, wherein the porous membrane is made of a fluorine resin material.
The laminate for acidic gas separation according to claim 3, wherein the porous membrane is made of polytetrafluoroethylene.
The laminate for acidic gas separation according to any one of claims 1 to 4, wherein the adhesive is made of an epoxy resin.
The laminated body for acidic gas separation of any one of Claim 1 to 5 which has an intermediate | middle layer between the said porous membrane and the said acidic gas separation promotion transport film.
The laminate for acidic gas separation according to claim 6, wherein the intermediate layer is a silicone resin layer.
A permeating gas collecting tube;
A laminate for acid gas separation according to any one of claims 1 to 7,
The acidic gas separation module, wherein the permeated gas channel member at the end of the acidic gas separation laminate where the sealing portion is not formed is connected to the permeate gas collecting pipe.
9. The acidic gas separation module according to claim 8, which is a spiral type module.
9. The acidic gas separation module according to claim 8, which is a flat membrane module.
JP2014152716A 2013-07-30 2014-07-28 Acid gas separation laminate and acid gas separation module comprising the laminate Active JP5990225B2 (en)
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JP2014152716A JP5990225B2 (en) 2013-07-30 2014-07-28 Acid gas separation laminate and acid gas separation module comprising the laminate
PCT/JP2014/003992 WO2015015803A1 (en) 2013-07-30 2014-07-30 Acidic gas separation laminate and acidic gas separation module provided with laminate
TW103126093A TW201511958A (en) 2013-07-30 2014-07-30 Acid gas separation laminate and acid gas separation module
US15/006,918 US9457319B2 (en) 2013-07-30 2016-01-26 Acidic gas separation laminate and acidic gas separation module provided with laminate
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JP5990225B2 true JP5990225B2 (en) 2016-09-07
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JP2014152716A Active JP5990225B2 (en) 2013-07-30 2014-07-28 Acid gas separation laminate and acid gas separation module comprising the laminate
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