JP2014039901A - Method for manufacturing carbon dioxide separation complex, carbon dioxide separation complex, and method for manufacturing carbon dioxide separation module using the same, as well as carbon dioxide separation module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a carbon dioxide separation complex, configured to stably manufacture the carbon dioxide separation complex at high productivity, the complex having a carbon dioxide isolation layer on a gas permeable support, while conveying a belt-shaped support.SOLUTION: A method for manufacturing a carbon dioxide separation complex comprises: a carbon dioxide separation layer forming step of forming a carbon dioxide isolation layer by applying and drying a coating liquid for forming the carbon dioxide separation layer containing a water absorbing polymer, carbon dioxide carrier and water on a temporary support; a transfer step of transferring the carbon dioxide isolation layer on a gas permeable support obtained in the carbon dioxide separation layer forming step; and a peeling step of forming a laminate having the carbon dioxide isolation layer on a porous support, by peeling the temporary support of the carbon dioxide separation layer surface transferred on the porous support.

Description

  The present invention relates to a method for producing a composite for carbon dioxide separation, a composite for carbon dioxide separation, a method for producing a module for carbon dioxide separation using the same, and a module for carbon dioxide separation.

  In recent years, a technology for selectively separating carbon dioxide in a mixed gas has been developed. For example, as a global warming countermeasure, carbon dioxide in exhaust gas is collected and concentrated, or by steam reforming, hydrocarbons are reformed to hydrogen and carbon monoxide (CO), and carbon monoxide and steam are reacted. This is a composite for carbon dioxide separation, which is used to produce gas for fuel cells and the like mainly composed of hydrogen by generating carbon dioxide and hydrogen and excluding carbon dioxide with a membrane that selectively permeates carbon dioxide. Technology to form the body has been developed. A carbon dioxide separation module closely packed with a carbon dioxide complex to process more gas in a small volume is a support for a gas-permeable channel material and carbon dioxide separation containing a carbon dioxide carrier. The layer and a porous membrane having gas permeability are provided, and carbon dioxide in the gas is separated and removed by the function of the carbon dioxide separation layer while the gas passes through the gap of the support.

  For example, in the following Patent Document 1, an uncrosslinked vinyl alcohol-acrylate copolymer aqueous solution is applied in a film form on a carbon dioxide permeable support, and then heated to crosslink to insolubilize the water. A method of producing a carbon dioxide separation gel membrane by absorbing a carbon dioxide carrier aqueous solution into a water-insolubilized material and making it gel is disclosed.

  In the following Patent Document 2, water or an aqueous solution of a substance having an affinity for carbon dioxide is substantially contained in a support film formed of a solvent-soluble polymer material having a bulky structural portion and a hydrophilic functional group in a repeating unit. A water-containing gel-like gas separation membrane that is uniformly held in the water is disclosed.

Japanese Patent Publication No. 7-102310 JP-A-6-210145

In Patent Document 1, a carbon dioxide separation gel membrane can be formed with a small area (for example, an effective area of 9.62 cm ² ). However, the carbon dioxide separation gel membrane is almost formed on a carbon dioxide permeable support having a large area. It is difficult to form stably with a uniform film thickness. Similarly in Patent Document 2, it is difficult to stably form a hydrogel gas separation membrane with a large area and a substantially uniform film thickness.

For this reason, the invention described in Patent Documents 1 and 2, for example, continuously conveys a belt-like support having a large area, and forms a carbon dioxide separation gel membrane or a water-containing gel-like gas separation membrane on the support. Even if it applies to the structure which does, it is difficult to manufacture a carbon dioxide separation gel membrane or a water-containing gel-like gas separation membrane stably with a substantially uniform film thickness.
As described above, it is common to form a gel film on a gas permeable support having insufficient strength. However, neither the gas permeable support nor the gel film has sufficient strength and is continuous. In production, it was difficult to produce in a roll-to-roll (Roll-to-Roll, hereinafter sometimes abbreviated as “RtoR”) method using a belt-like support (base film). In particular, according to the study of the present inventor, when the gas permeable support is a porous resin sheet, the carbon dioxide separation layer formed on the surface changes in dimensions due to the tensile stress during transportation. There is a concern that the film thickness uniformity may decrease, and when a laminated body in which a nonwoven fabric is bonded to a porous resin sheet as a reinforcing material is used as a support, the physical properties of the laminated sheets differ, so curling It has been found that there is a problem that film thickness uniformity and productivity are reduced due to occurrence of wrinkles or wrinkles due to heating.

  The present invention has been made in consideration of such a situation. A composite for carbon dioxide separation having a carbon dioxide separation layer having excellent film thickness uniformity on a gas-permeable support is obtained with high productivity. A method for producing a composite for carbon dioxide separation that can be stably produced, a composite for carbon dioxide separation that is excellent in film thickness uniformity of a carbon dioxide separation layer obtained by the production method, and a dioxide that uses the composite It is an object of the present invention to provide a method for producing a carbon separation module and a carbon dioxide separation module.

Means for solving the above problems are as follows.
<1> Carbon dioxide separation layer formation in which a carbon dioxide separation layer forming coating solution containing a water-absorbing polymer, a carbon dioxide carrier, and water is applied onto a temporary support and dried to form a carbon dioxide separation layer. The carbon dioxide separation layer obtained in the step and the carbon dioxide separation layer forming step is adhered to the gas permeable support, and then the temporary support on the carbon dioxide separation layer adhered to the porous support is peeled off. And a transfer step of transferring the carbon dioxide separation layer onto the porous support.
<2> The gas permeable support is a porous resin sheet or nonwoven fabric having a maximum pore diameter of 0.05 μm or more and 0.5 μm or less, and a porous resin sheet or nonwoven fabric having a maximum pore diameter of 0.05 μm or more and 0.5 μm or less. It is a manufacturing method of the composite_body | complex for carbon dioxide separation as described in <1> which is a support body selected from these laminated bodies.
<3> The method for producing a composite for carbon dioxide separation according to <1> or <2>, wherein at least the surface of the gas permeable support on the side in contact with the carbon dioxide separation layer is a hydrophobic surface.
<4> The carbon dioxide according to any one of <1> to <3>, wherein the carbon dioxide separation layer is adhered to the gas permeable support by a heating roller having a surface temperature of 70 ° C. to 120 ° C. It is a manufacturing method of the composite_body | complex for isolation | separation.
<5> Any one of <1> to <4>, wherein the gas permeable support is a porous resin sheet formed by including a resin selected from the group consisting of polypropylene and a fluorine-containing resin. The manufacturing method of the composite_body | complex for carbon dioxide separation as described in above.

<6> A composite for carbon dioxide separation obtained by the method for producing a composite for carbon dioxide separation according to any one of <1> to <5>.
<7> For carbon dioxide separation, comprising a step of spirally winding a carbon dioxide separation composite obtained by the method for producing a carbon dioxide separation composite according to any one of <1> to <5> It is a manufacturing method of a spiral module.
<8> A carbon dioxide separation spiral module comprising the composite for carbon dioxide separation according to <6> or obtained by the method for producing a spiral module for carbon dioxide separation according to <7>.

  According to the production method of the present invention, a temporary support excellent in dimensional stability even when the support excellent in gas permeability is easily stretched against tensile stress or curled easily. First, a carbon dioxide separation layer is formed on the top, then transferred to a gas-permeable support, and the temporary support is peeled off to form a carbon dioxide separation layer with high efficiency and excellent film thickness uniformity. Therefore, compared with the conventional method of forming a carbon dioxide separation layer directly on a gas-permeable support, a composite for carbon dioxide separation can be produced with high productivity by a continuous method such as RtoR. Furthermore, according to the production method of the present invention, there is an advantage that the non-woven fabric for reinforcing the gas permeable support, which is usually used for reinforcing the gas permeable support, need not be particularly laminated.

According to the present invention, carbon dioxide separation capable of stably producing a carbon dioxide separation composite having a carbon dioxide separation layer excellent in film thickness uniformity on a gas permeable support with high productivity. A method for producing a composite is provided.
In addition, according to the present invention, a carbon dioxide separation complex excellent in film thickness uniformity of the carbon dioxide separation layer obtained by the production method of the present invention and a method for producing a carbon dioxide separation module using the same. As well as a module for carbon dioxide separation.

It is a block diagram which shows the manufacturing apparatus of the composite_body | complex for carbon dioxide separation which concerns on one Embodiment. It is an expanded sectional view which shows the one aspect | mode of the composite_body | complex for carbon dioxide separation obtained by the manufacturing method of this invention. It is a schematic block diagram which provides one part cutout which shows one Embodiment of the carbon dioxide separation module incorporating the composite_body | complex for carbon dioxide separation obtained by the manufacturing method of this invention.

<Method for producing composite for carbon dioxide separation>
Hereinafter, the manufacturing method of the composite for carbon dioxide separation which is one Embodiment of this invention and the manufacturing apparatus used suitably for this manufacturing method are demonstrated, referring FIG.1 and FIG.2.

  The present inventor considered that the RtoR method using a belt-like support (base film) is suitable for producing a carbon dioxide separation composite with high efficiency (high speed and low cost). When employing water-based coating in RtoR, in order to prevent a part of the coating film from being blown or a variation in film thickness when the drying air is applied in the drying process, the coating film is dried before drying. Must be set (fixed). Further, in the conventional method, such a coating film is applied to the gas permeable support. However, the gas permeable support is likely to be deformed or broken by a tensile stress, and therefore, a resin sheet having fine voids. Therefore, reinforcing materials such as non-woven fabrics are laminated in advance, or a laminated body having a small area is produced in a batch system. Therefore, the present inventor previously applied a coating film on the temporary support while transporting the belt-shaped temporary support excellent in strength and dimensional stability in a certain direction, and dried, thereby making the film thickness uniformity. And carbon dioxide separation layer with excellent gas separation characteristics, and then transferred to a gas permeable support to produce a carbon dioxide separation composite having a carbon dioxide separation layer with excellent film thickness uniformity It was found that it can be manufactured with high performance.

(Overall configuration of manufacturing equipment)
FIG. 1 shows the overall configuration of a carbon dioxide separation complex manufacturing apparatus. The carbon dioxide separation complex manufacturing apparatus shown in FIG. 1 includes at least a coating apparatus 16 and a drying apparatus 20 for manufacturing a laminate 40 in which a carbon dioxide separation layer 42 is formed on a temporary support 12. Prepare.
Furthermore, a pair of transfer roller 50, temporary support 12, and heating roller 50A and support roller 50B for laminating the surface of carbon dioxide separation layer 42 of the obtained laminate 40 in close contact with gas permeable support 44, A peeling blade 52 for peeling the temporary support from the laminate 45 of the carbon dioxide separation layer 42 and the gas permeable support 44, a temporary support winding roller 54 for winding the peeled temporary support 12, and gas permeability A carbon dioxide separation composite take-up roller 22 for winding a carbon dioxide separation composite 46 having a carbon dioxide separation layer 42 on a support 44 is provided.
In the embodiment shown in FIG. 1, the peeling blade 52 is used, but the peeling method of the temporary support 12 is not limited to this. For example, a carbon dioxide separation layer 42 is applied on the temporary support 12. When forming, a coating film is formed at the tip of the temporary support 12 by sandwiching a tape or a spacer between the temporary support 12 and the coating film made of the composition for forming a carbon dioxide separation layer at the tip at the time of application. An uncoated region is formed, and the region can be directly wound around the temporary support winding roller 54 using the trigger as a trigger (tip of winding of the temporary support). The manufacturing apparatus may take a form in which a guide roller that guides the temporary support 12 to the temporary support winding roller 54 is provided along the transport direction of the stacked body 40.
Here, a pair of transfer rollers 50 including a heating roller 50A and a support roller 50B is used for transfer, but the present invention is not limited to this mode, and an adhesive supply device is provided downstream of the heating and drying zone 20. And the gas permeable support 44 and the carbon dioxide separation layer 42 may be brought into close contact with each other through an adhesive layer. In this case, the heating roller 50A is not necessary, and a pair of pressure rollers is sufficient. .
In the manufacturing apparatus shown in FIG. 1, a pair of heating rollers 50 are provided to bring the carbon dioxide separation layer 42 and the gas permeable support 44 in the laminate 40 having the carbon dioxide separation layer 42 on the temporary support 12 into intimate contact. However, the present invention is not limited to this embodiment. For example, an adhesive application device is provided downstream of the feed roller 56 for feeding the gas permeable support 44, and an adhesive layer is provided on the surface of the gas permeable support 44. After the formation, a member having an adhesion roller for closely attaching the gas permeable support 44 to the surface of the carbon dioxide separation layer 42 through the adhesive layer is disposed to continuously form the carbon dioxide separation composite 46. You may take a method. In this case, the contact roller does not necessarily require a heating means.
As shown in FIG. 1, the carbon dioxide separation complex manufacturing apparatus 10 includes a feeding roller 14 as an example of a conveying unit that feeds a belt-like temporary support 12 in a fixed direction, and a plurality of temporary supports 12. The back surface support roller 24 is provided. The delivery roller 14 is provided with a shaft portion 14A around which the temporary support body 12 is wound. The temporary support body 12 is delivered by the shaft portion 14A rotating in the direction of the arrow. And the temporary support body 12 is conveyed in a fixed direction in the state in which the back surface side of the temporary support body 12 was wound around the back surface support roller 26.

  In addition, the carbon dioxide separation complex manufacturing apparatus 10 includes carbon dioxide, which will be described later, on the surface of the temporary support 12 in order from the upstream side to the downstream side along the conveyance direction of the temporary support 12 sent from the feed roller 14. The coating device 16 for applying the coating liquid for forming the separation layer and the coating film formed by the coating liquid for forming the carbon dioxide separation layer applied on the temporary support 12 are dried in a non-contact state to separate carbon dioxide. And a drying unit 20 as an example of a drying apparatus for obtaining a layer. In addition, when using the coating liquid composition containing the gelatinizer which gelatinizes at low temperature, the cooling unit as an example of the cooling device which cools in a non-contact state and obtains a gel film upstream of the drying unit 20 You may have.

  Further, the carbon dioxide separation composite manufacturing apparatus 10 includes a carbon dioxide separation laminate in which a carbon dioxide separation layer 42 is formed on the temporary support 12 on the downstream side of the drying unit 20 in the transport direction of the support 12. 40 is provided with a pair of heating rollers 50 that closely contact the gas permeable support 44 supplied from the delivery roller 56 of the gas permeable support 44. The heating roller 50 is a heating roller 50A. And a support roller 50B. Therefore, the carbon dioxide separation layer 42 is transferred to the surface of the gas permeable support 44. Thereafter, the temporary support 12 is peeled off by a peeling blade 52, and a carbon dioxide separation layer 42 is formed on a take-up roller 54 as an example of a conveying means for winding the temporary support 12 and a gas permeable support 44. And a take-up roller 22 for taking up the carbon dioxide separating composite 46. The winding rollers 54 and 22 are respectively provided with shaft portions 54A and 22A for winding the carbon dioxide separation composite 40 or the temporary support 12, and the shaft portions 54A and 22A are moved in the direction of the arrows by a motor (not shown). By rotating, the temporary support 12 and the carbon dioxide separating composite 46 are conveyed in a predetermined direction (arrow direction) at a predetermined speed.

(Temporary support)
The temporary support 12 supports the carbon dioxide separation layer 42 until the carbon dioxide separation layer 42 is transferred to the gas permeable support 44 which is the present support, and is used for forming a carbon dioxide separation layer on the surface. Any sheet may be used as long as it can stably hold the carbon dioxide separation layer 42 until the coating liquid composition is applied, dried, and then transferred to the transfer step.
However, since the temporary support 12 may be heated in a subsequent transfer step, the resin film has good thermal stability, that is, a resin that hardly undergoes deformation such as dimensional change or curl due to heating. Preferably, the film is made of
As the temporary support 12, it is preferable to use an inexpensive general-purpose resin film from the viewpoint of the uniformity of the formed coating film and the availability, and more specifically, polyethylene terephthalate (PET), polyethylene naphthalate. Examples thereof include olefin resin films such as phthalate (PNT), polyamides, modified polyamides, high-density polyethylene, triacetylcellulose (TAC), polylactic acid, and the like. Among these, a PET film is preferable from the viewpoint of thermal stability.
The temporary support preferably has physical properties that are resistant to deformation, and the elongation at a load of 5 N is preferably 5% or less. Elongation under load is measured using a test tensile tester. In the test tensile test, a temporary support was cut to a width of 10 mm and a length of 50 mm to prepare a test piece, and the test piece was used with a tensile tester (manufactured by Shimadzu Corporation, Autograph AGS-J: trade name). A test piece was set with a distance between chucks of 20 mm, and a tensile test was performed at a speed of 10 mm / min. At this time, the said elongation is measured by measuring the elongation at the time of load 5N. The test is performed at room temperature (25 ° C.).

Although the size (area) of the temporary support 12 is not limited, the larger the temporary support 12 is, the more easily the film thickness of the coating film varies and the more easily the holes having no gas selectivity such as pinholes are formed. However, in the present invention, a good gel film can be formed to effectively prevent variations in film thickness and generation of holes. Further, from the viewpoint of productivity, the area of the temporary support 12 is preferably 30 cm ² or more.

The transport speed of the temporary support 12 depends on the type of the temporary support 12 and the viscosity of the coating liquid composition, but if the transport speed of the temporary support is too high, the film thickness uniformity of the coating film in the coating process decreases. If it is too late, the productivity is lowered, and the viscosity of the coating liquid composition is increased before the cooling step, and the uniformity of the coating film may be lowered. The conveyance speed of the temporary support 12 may be determined according to the type of the temporary support 12 and the viscosity of the coating liquid (aqueous composition) in consideration of the above points, but is preferably 20 m / min or more, and preferably 30 m / min. Min to 200 m / min is preferable.
Since the temporary support 12 is peeled off from the carbon dioxide separation layer 42 later, the surface of the temporary support 12 (surface on which the carbon dioxide separation layer 42 is formed) forms a hydrophobic treatment or an easy peel layer. Pretreatment such as treatment is also preferable.

(Coating solution for carbon dioxide separation layer formation)
The coating solution (aqueous composition) for forming a carbon dioxide separation layer applied to the surface of the support 12 by the coating device 16 is configured by adding an appropriate amount of at least a water-absorbing polymer and a carbon dioxide carrier to water. . The coating liquid for forming the carbon dioxide separation layer may contain at least a water-absorbing polymer that holds the coating film, a carbon dioxide carrier, and water, and various known additives may be used in combination as necessary. For example, for the purpose of improving the coating uniformity, a gelling agent for adjusting the viscosity of the coating solution may be used in combination.

1. Water-absorbing polymer The water-absorbing polymer contained in the coating liquid composition of the present invention functions as a binder, and when used in a carbon dioxide separation layer, retains moisture and exhibits a function of separating carbon dioxide by a carbon dioxide carrier. Let The water-absorbing polymer can be dissolved in water to form a coating solution, and the carbon dioxide separation layer preferably has a high water absorption from the viewpoint of having a high water absorption (moisturizing property). It is preferable to have.

Examples of the water-absorbing polymer contained in the coating liquid (aqueous composition) of the present invention include, for example, polyvinyl alcohol-polyacrylic acid (PVA-PAA) copolymer and polyvinyl from the viewpoint of water absorption, film-forming property, strength, and the like. Alcohol, polyacrylic acid, polyacrylate, polyvinyl butyral, poly-N-vinylpyrrolidone, poly-N-nylacetamide, and polyacrylamide are preferred, and PVA-PAA copolymer is particularly preferred. The PVA-PAA copolymer has a high water absorption capacity and a high hydrogel strength even at high water absorption. The content of the polyacrylate in the PVA-PAA copolymer is, for example, 5 to 95 mol%, preferably 30 to 70 mol%. Examples of polyacrylic acid salts include alkali metal salts such as sodium salt and potassium salt, as well as ammonium salts and organic ammonium salts.
Examples of commercially available PVA-PAA copolymers include Clastomer-AP20 (trade name: manufactured by Kuraray Co., Ltd.).

  The content of the water-absorbing polymer in the coating liquid (aqueous composition) is 1 mass from the viewpoint of forming a film as a binder and allowing the carbon dioxide separation layer to sufficiently retain moisture, depending on the type. % To 30% by mass is preferable, and 2% to 15% by mass is more preferable.

2. Carbon dioxide carrier The carbon dioxide carrier contained in the coating liquid (aqueous composition) of the present invention is not particularly limited as long as it has an affinity for carbon dioxide and exhibits water solubility. The carbon dioxide carrier in this case is a substance having an affinity for carbon dioxide, and various water-soluble inorganic and organic substances showing basicity are used. For example, alkali metal carbonate, alkali metal bicarbonate, and alkali metal hydroxide can be used.

Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate.
Examples of the alkali metal bicarbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate.
Examples of the alkali metal hydroxide include cesium hydroxide and rubidium hydroxide.
Among these, alkali metal carbonates are preferable, and compounds containing cesium and rubidium are preferable.
Moreover, you may use a carbon dioxide carrier in mixture of 2 or more types.

  The content of the carbon dioxide carrier in the coating liquid (aqueous composition) is 0.5 mass in order to prevent salting out before coating and to ensure the function of separating carbon dioxide, depending on the type. % To 30% by mass, more preferably 3% to 20% by mass, and particularly preferably 5% to 15% by mass.

3. Other components The coating liquid for forming a carbon dioxide separation layer used in the present invention (hereinafter also simply referred to as a coating liquid composition) is within a range that does not adversely affect the film-forming properties (coating properties, set properties) and gas separation properties. A water-absorbing polymer, a carbon dioxide carrier, and other components (additives) other than water can be included.
Components that can be used arbitrarily include, for example, a gelling agent for controlling the setting property and viscosity of the coating film, a crosslinking agent for improving the film strength, a surfactant, a catalyst, an auxiliary solvent, a film strength adjusting agent, and a defect. Examples include detection agents.
3-1. Gelling agent The gelling agent contained in the coating liquid composition according to the present invention is a coating formed by applying a coating liquid obtained by adding a gelling agent to an aqueous solution containing a water-absorbing polymer and a carbon dioxide carrier on a support. What is necessary is just to use what can form a gel film (set film | membrane) with high film thickness uniformity, when forming a film | membrane or cooling this.
Examples of the gelling agent that does not depend on temperature include thickeners such as carboxymethylcellulose, and examples of the gelling agent that can form a gel film by cooling include thickening polysaccharides, more specifically, agars. Is mentioned. As such a polysaccharide, agar is preferable from the viewpoint of film forming property, availability, cost, film strength and the like, and commercially available products include Inagar Agar UP-37, UM-11S, SY-8, ZY-4, ZY-6 (above, manufactured by Inagar Co., Ltd.), Agarose H, Agarose S (above, manufactured by Nippon Gene Co., Ltd.) and the like.
As a gelling agent capable of forming a gel film by cooling, specifically, a coating liquid composition containing a water-absorbing polymer, a carbon dioxide carrier, a gelling agent, and water is prepared at 50 ° C. or higher. Examples thereof include gelling agents having a property that gels within 120 seconds under a temperature condition of 12 ° C. at a film thickness of 1 mm or less and the liquid does not fall due to gravity.

The content of the gelling agent in the coating liquid composition depends on the type, but if the content is too large, the coating liquid may become highly viscous in a short time and difficult to apply. From the viewpoint of suppressing a decrease in thickness uniformity, it is preferably 10% by mass or less, more preferably 0.1 to 8% by mass, and most preferably 0.3 to 5% by mass.
In the production method of the present invention, in the carbon dioxide separation layer forming step, the carbon dioxide separation layer is applied on a temporary support having no aperture and having high dimensional stability, and then formed through a photosensitive step. Therefore, unlike the conventional method of coating directly on a gas-permeable support, a gelling agent is not necessarily required for the coating liquid composition, and it is an optional component used in combination for improving film uniformity and coating properties. is there.

3-2. Cross-linking agent A water-absorbing polymer may be formed with a cross-linked structure to improve the strength of the carbon dioxide separation layer. do it. Among these, a crosslinked structure is formed using a crosslinking agent having two or more functional groups (also referred to as crosslinkable functional groups) that can be thermally crosslinked by reacting with a water-absorbing polymer such as a polyvinyl alcohol-polyacrylate copolymer. From the viewpoint of improving the film strength, the crosslinking agent having two or more crosslinkable functional groups that can be used for this purpose includes polyvalent glycidyl ether, polyhydric alcohol, polyvalent isocyanate, polyvalent aziridine, haloepoxy compound, polyvalent Examples include aldehydes and polyvalent amines.

3-3. Other components (preparation of coating solution composition)
Preparation of the coating liquid composition was carried out by adding the above-mentioned water-absorbing polymer, carbon dioxide carrier, and water, and if necessary, other additives such as a gelling agent and a crosslinking agent in water (room temperature water or warm water). ) And stirring sufficiently, and if necessary, heating is performed with stirring to promote dissolution. In addition, you may add a water absorbing polymer, a carbon dioxide carrier, and another component separately to water, and you may add what was mixed beforehand.
It is preferable that the preparation temperature of a coating liquid composition is performed at 50 to 90 degreeC from a uniform viewpoint.

(CO2 separation layer formation process)
In this step, a coating liquid composition for forming a carbon dioxide separation layer, which is preferably prepared at 50 ° C. or higher and 90 ° C. or lower, is applied to the surface of the temporary support 12 conveyed in a certain direction by the coating device 16. It is a step of forming a carbon dioxide separation layer by drying.
1. Application of Coating Solution Composition When the temperature of the coating solution composition in the coating process by the coating device 16 decreases, the water-absorbing polymer precipitates (salts out), making uniform coating on the temporary support difficult. There is a risk that the variation of the Therefore, after preparing the coating liquid composition of the present invention, it is preferable to keep the temperature so that salting-out does not occur until it is applied. The temperature of the coating liquid composition in the coating process may be determined so as not to cause gelation or salting out depending on the composition or concentration. However, if the temperature is too high, a large amount of water evaporates from the coating liquid composition. Since the concentration may change or gelation may proceed locally, the temperature is usually 50 ° C. or higher and 90 ° C. or lower, preferably about 60 ° C. to 85 ° C.

  The coating device 16 according to this embodiment includes a storage portion 16A in which the prepared coating liquid for forming a carbon dioxide separation layer is stored, and the coating liquid stored in the storage portion 16A flows out, and the back support roller 26 is applied during coating. An application die 36 is provided. The coating die 36 can freely adjust the flow rate of the coating solution and the width of the gap between the coating body and the coating die 36, and can be coated at various thicknesses on various thicknesses of the supporting body. Although not shown, the reservoir 16A is provided with a heater that controls the temperature of the coating liquid composition and a stirring device that stirs the coating liquid.

  The coating device 16 is not limited to the above configuration, and examples thereof include a curtain flow coater, an extrusion die coater, an air doctor coater, a blade coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, and a bar coater. It is selected appropriately. In particular, an extrusion die coater is preferable from the viewpoint of film thickness uniformity, coating amount, and the like.

The coating amount depends on the composition and concentration of the coating liquid composition, but if the coating amount per unit area is too small, pores are formed in the coating film during the drying process, or the strength as a carbon dioxide separation layer is insufficient. There is a risk of becoming. On the other hand, if the coating amount is too large, the variation in film thickness may increase, or the film thickness of the carbon dioxide separation layer obtained may become too large, resulting in a decrease in carbon dioxide permeability.
From these viewpoints, the thickness of the coating film is 30 μm or more, more preferably 50 μm or more, particularly preferably 100 μm or more, and the thickness of the carbon dioxide separation layer obtained after the heating step is 5 μm to 50 μm, more preferably The coating amount is preferably adjusted so as to be 10 μm to 40 μm, particularly preferably 15 μm to 30 μm.

2. Drying of Coating Film The drying process is a process of obtaining a carbon dioxide separation layer 42 by drying the coating film of the coating liquid composition formed on the temporary support 12 in the drying unit 20. At this time, thermal crosslinking may be performed simultaneously if desired. For example, the coating film on the temporary support 12 conveyed to the drying unit 20 is dried by applying hot air, but when the coating liquid composition contains a cross-linking agent, the cross-linking reaction proceeds by this hot air heating. .
The wind speed is preferably set to a speed at which the coating film can be dried quickly and the coating film does not collapse, for example, 1 m / min to 80 m / min, and more preferably 6 m / min to 70 m / min. Further, 10 m / min to 40 m / min is particularly preferable.
The temperature of the wind is preferably set to 20 ° C. to 80 ° C., and more preferably 30 ° C. to 70 ° C., so that deformation of the support does not occur and the coating film can be dried quickly. Furthermore, 40 to 60 degreeC is especially preferable.

  When the coating liquid composition contains a crosslinking agent, drying and crosslinking in the drying step may be performed simultaneously or separately. For example, the coating film may be dried by applying warm air to the coating film and then crosslinked by heating means such as an infrared heater, or may be crosslinked together with drying by warm air. Thermal crosslinking can be performed by heating to about 100 ° C. to 150 ° C., for example.

  The drying unit 20 of the present embodiment includes a housing 20A into which the temporary support 12 is carried in and out, and a plurality of hot air heaters 32 that are disposed in the housing 20A and dry the coating film on the surface of the temporary support 12; A plurality of halogen heaters 34. The hot air heater 32 is disposed at a predetermined interval with respect to the surface of the temporary support 12, and the coating on the temporary support 12 is dried by blowing hot air onto the surface of the temporary support 12. Let

  The halogen heater 34 is disposed at a predetermined interval with respect to the surface of the temporary support 12, and dries the coating film on the support 12 with heat. In the present embodiment, a plurality of hot air heaters 32 and halogen heaters 34 are alternately arranged, and the gel film on the surface of the support 12 is dried and thermally cross-linked by these hot air heaters 32 and halogen heaters 34. A carbon separation layer 42 (see FIG. 2) is obtained. In the present embodiment, a plurality of hot air heaters 32 and halogen heaters 34 are alternately arranged. However, the present invention is not limited to this configuration. For example, a configuration including only the plurality of hot air heaters 32 may be used.

  Further, in the carbon dioxide separation complex manufacturing apparatus 10, if necessary, the carbon dioxide separation layer 42 formed on the surface of the support 12 is disposed on the downstream side of the drying unit 20 in the transport direction of the support 12. A coating device (not shown) and a drying device (not shown) for forming a carrier elution preventing layer may be provided.

  As shown in FIG. 1, in the carbon dioxide separation complex manufacturing apparatus 10, the belt-like temporary support 12 is sent out by the feed roller 14 and the temporary support 12 is supported by the back support roller 24. Conveyed in the direction. The temporary support 12 delivered from the delivery roller 14 is transported to a position facing the coating device 16, and the coating solution for forming a carbon dioxide separation layer prepared by the coating device 16 at 50 ° C. or higher is applied to the surface of the temporary support 12. To be applied. As a result, a coating film having a substantially uniform thickness is formed on the support 12.

Thereafter, the temporary support 12 is conveyed to the drying unit 20.
In the drying unit 20, hot air is blown from the plurality of hot air heaters 32, and the coating film formed on the surface of the temporary support 12 is dried and thermally cross-linked by the heat of the halogen heater 34. As a result, as shown in FIG. 2A, a laminate 40 in which a carbon dioxide separation layer 42 is formed on the surface of the temporary support 12 is obtained.

(Transfer process)
1. The carbon dioxide separation layer is closely attached to the gas permeable support. The surface of the carbon dioxide separation layer 42 of the laminate 40 formed by the coating and drying process is overlapped with the gas permeable support 44 fed from the feed roller 56. Thus, the carbon dioxide separation layer 42 and the gas permeable support 44 are brought into close contact with each other, and a laminate 45 in which the carbon dioxide separation layer 42 and the gas permeable support 44 are laminated is formed on the temporary support 12. .
Any method may be used to bring the carbon dioxide separation layer 42 into close contact with the gas permeable support 44, but a heating press method using a heating roller or a hot plate is preferable from the viewpoint of productivity. In FIG. 1, heat pressing is performed by a pair of heating rollers 50 including a heating roller 50A and a support roller 50B. The heating temperature is not particularly limited as long as it is in a temperature range that does not affect the carbon dioxide separation layer 42 or the gas permeable support 44.
In addition, when heating temperature is too high, there exists a possibility that gas permeability may fall significantly, when the porous resin sheet and nonwoven fabric used as the gas-permeable support body 44 are heat-compressed. Therefore, as long as the carbon dioxide separation layer 42 is stably transferred, it is preferable to transfer at a low temperature and a low pressure.
According to the study of the present inventor, when the polytetrafluoroethylene porous membrane described in detail below is used as the gas permeable support 44, the gas permeable support 44 becomes transparent under a heating and pressurizing condition exceeding 120 ° C. and has air permeability. It has been found that there is a possibility of significant reduction. In consideration of this, it is preferable that the heating temperature, in the present specification, the surface temperature of the heating roller is in the range of 70 ° C to 120 ° C. By setting the heating temperature within the above range, the carbon dioxide separation layer 42 is in close contact with the gas permeable support 44 without greatly affecting the shape and gas permeability of the gas permeable support. In the case of heating, a heating roller press with a surface temperature of 70 ° C. to 120 ° C. is preferable, and a range of 80 ° C. to 110 ° C. is more preferable from the viewpoint that adhesion is good and shape change of the support is suppressed. . The surface temperature of the heating roller can be measured with a known thermometer of contact type or non-contact type.
It is possible to adjust the roller surface temperature as appropriate according to the heat resistance and thickness of the temporary support 12 and the gas permeable support 44 to be used. The rollers may have the same temperature condition or different temperature conditions, or only one of the rollers may be provided with a heater, and the other may be a support roller. At this time, the other support roller having no heater may be a metal roll, or a rubber roll or an elastic roll having a soft resin layer on the surface.
Further, means for improving the adhesion and transferability of the carbon dioxide separation layer 42 by heating the gas permeable support 44 in advance before transfer or forming an easy-adhesion layer (adhesive layer) on the surface. You may take
In this transfer step, a gas permeable support 44 is superimposed on the surface of the carbon dioxide separation layer 42 of the laminate 40, and the carbon dioxide separation layer 42 and the gas permeable support 44 are provided on the support 12. Get 45.

2. Separation of Temporary Support from Laminate In the peeling step, carbon dioxide separation complex 46 having carbon dioxide separation layer 42 on gas permeable support 44 by peeling temporary support 12 from laminate 45. It is the process of obtaining.
FIG. 2B is an enlarged cross-sectional view showing one embodiment of a carbon dioxide separation composite 46 having a carbon dioxide separation layer 42 on a gas permeable support 44 obtained by the production method of the present invention. .
That is, the gas permeable support 44 is laminated on the surface of the laminate 40 shown in FIG. 2A, and then the temporary support 12 is peeled off to obtain the carbon dioxide separation composite 46 of the present invention.
The carbon dioxide separation composite 46 may have a layer other than the carbon dioxide separation layer 42 on the gas permeable support 44. Other layers include, for example, an undercoat layer provided between the gas permeable support 44 and the carbon dioxide separation layer 42, an intermediate layer, and a protective layer provided on the carbon dioxide separation layer 42 (for example, a carrier elution prevention layer). ) And the like.

(Gas permeable support)
In this step, the gas permeable support 44 used for forming the carbon dioxide separation composite 46 by being superimposed on the carbon dioxide separation layer 42 is not particularly limited as long as it has gas permeability, in particular, carbon dioxide permeability. .
As the material of the gas permeable support, paper, fine paper, coated paper, cast coated paper, synthetic paper, cellulose, polyester, polyolefin, polyamide, polyimide, polysulfone, aramid, polycarbonate, metal, glass, ceramics, etc. are suitable. Can be used for More specifically, resin materials such as polyethylene, polystyrene, polyethylene terephthalate, polytetrafluoroethylene, polyethersulfone, polyphenylene sulfide, polysulfone, polypropylene, polyetherimide, polyetheretherketone, and polyvinylidene fluoride are preferable. It is done.
Further, as the form of the support, the carbon dioxide separation layer is immersed, specifically, the viscosity is reduced by gas separation use in a humid environment, the shape change under a high pressure environment, etc. From the viewpoint of preventing the material contained in 42 from being laid, a porous resin sheet is most preferable, and a composite of a porous resin sheet and a nonwoven fabric is also a preferable embodiment. In the case of a composite of a porous resin sheet and a nonwoven fabric, the carbon dioxide separation layer 42 is more preferably transferred and formed on the membrane surface side of the porous resin sheet.
As a porous resin sheet, it is preferable that the pore diameter of a porous resin sheet is small from a viewpoint of suppressing permeation of the carbon dioxide separation layer material. Specifically, the maximum pore diameter is preferably 0.05 μm or more and 0.5 μm or less, and more preferably 0.2 μm or less. From the viewpoint of availability, the most suitable range is 0.05 μm to 0.2 μm.
In addition, the maximum pore diameter of the porous membrane in the present invention is measured by the following method.
About the maximum hole diameter, the maximum hole diameter (bubble point) was measured by the bubble point method. As a measuring device, a palm porometer manufactured by PMI (based on JIS K3832) is used. Specifically, a porous film cut out in 3 cm square is immersed in a surfactant solution (Gulwick solution). After taking out and lightly wiping off the excess surfactant solution, it is sandwiched between two metal meshes and set in the measuring cell of the apparatus. A Gullwick liquid was used as the measurement liquid, and it was gradually pressurized with air at room temperature (25 ° C.) to measure the bubble point.

Moreover, it is preferable that at least the surface of the gas permeable support 44 on the side in contact with the carbon dioxide separation layer 42 is a hydrophobic surface. If the surface is hydrophilic, the carbon dioxide separation layer 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 100 ° to 130 °.

As the porous resin sheet, generally, a film body having a high self-supporting property and a high porosity can be suitably used. Especially, the porous resin sheet formed including resin selected from the group which consists of a polypropylene and a fluorine-containing resin is preferable.
More specifically, the stretched porous membrane of polyphenylene sulfide, polysulfone, polytetrafluoroethylene, polyvinylidene fluoride, high molecular weight polyethylene, etc. has a high porosity, small diffusion inhibition of carbon dioxide, and from the viewpoint of strength and suitability for production. preferable.

Among these, from the viewpoint of heat resistance and durability, as a resin material, polytetrafluoroethylene (PTFE), polyethersulfone, polyphenylene sulfide, polysulfone, polypropylene, polyetherimide, polyetheretherketone, and polyvinylidene fluoride (PVDF) At least one kind is preferred, and polytetrafluoroethylene can be used particularly preferably from the viewpoint of stability over time.
The carbon dioxide separation composite 46 obtained by the production method of the present invention is often used, for example, at a high temperature of about 130 ° C. and humidification using steam, although the use temperature varies depending on the application. Therefore, it is preferable that the gas permeable support 44 is made of a material having heat resistance with little change in pore structure even at 130 ° C. and less hydrolyzable. From such a viewpoint, 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 preferable, and the most preferable support The form of the body is a PTFE porous membrane.
Although these porous resin sheets can be used alone, a composite membrane integrated with a reinforcing membrane, for example, a non-woven fabric excellent in breathability for reinforcement is laminated on the side not in contact with the carbon dioxide separation layer 42. An integrated composite membrane can also be used suitably.
In a general manufacturing method, since the carbon dioxide separation layer 42 is formed on the surface of the porous membrane 44 by a coating method, the gas permeable support 44 used in such a method has a predetermined strength and stretch resistance. However, in the production method of the present invention, the gas permeable support 44 is arranged on the gas permeable support 44 by transferring the carbon dioxide separation layer 42 formed in advance on the temporary support 12. Therefore, the gas permeable support 44 does not require strength or stretch resistance, and therefore, the gas permeable support 44 does not require a reinforcing non-woven fabric, and is a porous resin sheet. The fact that can be used alone is also a great feature of the production method of the present invention, and this makes it possible to further simplify the process of preparing the composite film.

  The gas permeable support 44 preferably has a thickness in the range of 30 μm to 500 μm from the viewpoint of combining gas permeability and strength. When the thickness is 500 μm or less, the gas permeability is good, and when it is 30 μm or more, the strength is good. Furthermore, 50 micrometers-300 micrometers are more preferable, and 50 micrometers-200 micrometers are still more preferable.

In the manufacturing apparatus 10 and the method for manufacturing the carbon dioxide separation composite 46 used for manufacturing the carbon dioxide separation composite 46, the temporary support 12 is conveyed while the belt-shaped temporary support 12 is conveyed in a certain direction. A carbon dioxide separation layer 42 having a substantially uniform film thickness can be stably produced with high productivity, and this can be transferred to the surface of the gas permeable support 44 to easily combine the carbon dioxide separation layer 42. A body 46 is obtained.
That is, the laminated body 40 having the carbon dioxide separation layer 42 that is thick to some extent on the temporary support 12 that is inexpensive and excellent in strength can be formed with a large area in a short time by a simple method. Further, since the carbon dioxide separation layer 42 in the laminate 40 is superimposed on the surface of the gas permeable support 44 by RtoR by transfer, the carbon dioxide separation complex 46 is mass-produced. By a simple method, the carbon dioxide separation complex 46 having excellent carbon dioxide separation ability can be obtained continuously and efficiently.

<Method for producing carbon dioxide separating spiral module and carbon dioxide separating spiral module obtained thereby>
The carbon dioxide separation composite 46 obtained by the production method of the present invention is used by being incorporated into a carbon dioxide separation layer module. There is no restriction | limiting in particular in the kind of carbon dioxide separation module incorporated, It uses suitably for a well-known apparatus. In the embodiment described below, a spiral module will be described as an example, but the present invention is not limited to this.
The method for producing a carbon dioxide separation spiral module of the present invention includes a step of winding the carbon dioxide separation complex 46 obtained by the production method of the present invention in a spiral manner by overlapping with an appropriate flow path material.
FIG. 3 is a schematic configuration diagram showing one embodiment of a carbon dioxide separation module 60 using the carbon dioxide separation composite 46 obtained by the production method of the present invention, with a partly cutout.
As a basic structure, the carbon dioxide separation spiral module 60 is configured by winding a single or a plurality of carbon dioxide separation composites 46 and flow passage materials 64 around a perforated hollow central tube 62. . The periphery of the carbon dioxide separating region formed by the carbon dioxide separating composite 46 is covered with a coating layer 66 formed of a material capable of blocking a fluid such as a gas passing through the module.
Here, the carbon dioxide separation composite 46 is a laminate composed of the carbon dioxide separation layer 42 and the gas permeable support 44 obtained by the production method of the present invention described above. The channel material 64 is superimposed on this.
(Channel material)
Since the flow path material has a function of allowing gas to pass and preferably causes turbulent flow in the fluid, a net-like shape selected from a resin net and a monofilament mesh having an opening of 30 μm to 2000 μm. A support is preferably used. Since the flow path of the fluid changes depending on the shape of the net, the shape of the unit cell of the net is selected from shapes such as a rhombus and a parallelogram according to the purpose.
In addition, non-woven fabrics, woven fabrics, knitted fabrics and the like can be used as long as they have sufficient air permeability and resistance to tensile stress.

As the material, for example, the composite for carbon dioxide separation part obtained by the production method of the present invention may be used at a temperature of 100 ° C. or higher, for example, about 130 ° C. Materials are preferably used.
Examples of the material of the support include resins such as polyester, polypropylene, polyamide, polyphenylene sulfide, polytetrafluoroethylene, polyetheretherketone, and polyvinylidene chloride. Furthermore, inorganic materials such as ceramics, metal, and glass are used. May be used.
In addition, non-woven fabrics, woven fabrics, knitted fabrics, etc., using fibers, monofilaments, cords and the like made of the above-described resins and inorganic materials are also preferably used.

Since the shape of the channel material 66 is mass-produced by RtoR, it is preferably a long strip-like sheet or fabric.
When the opening of the resin net and monofilament mesh is within the above range, sufficient strength to withstand conveyance can be achieved, web handling suitability can be achieved, and the coating solution penetrates into the opening before it hardens due to the opening being too large. Is suppressed.
The resin net can be formed by any method as long as the resin net has the above-mentioned preferred openings. However, a resin net obtained by extrusion molding is preferred from the viewpoint of simplicity of the manufacturing method and uniformity of the openings. The material constituting the resin net is arbitrarily selected from the resin materials described above. Among them, polypropylene, polyphenylene sulfide, polytetrafluoroethylene are preferable from the viewpoint that heat resistance is good and water decomposition does not occur. Etc. are preferred.
The extrusion molding net preferably used as the support in the present invention is also available as a commercial product. For example, a general-purpose commercial net such as Nartex or Netron Net manufactured by delstar may be used.
The monofilament mesh is one in which monofilaments are knitted in a net shape, and the mesh size of the mesh is preferably 30 μm or more and 2000 μm or less as in the case of the resin net.
Examples of the material of the monofilament constituting the mesh include polypropylene, polyphenylene sulfide, polytetrafluoroethylene and the like as the organic material, and metal monofilament having a knitting diameter as the inorganic material, and the metal monofilament A wire mesh made of or the like is preferably used, but is not particularly limited.
When a metal material is used as the monofilament, a metal material excellent in rust prevention property is selected from the viewpoint of durability, or the surface of which is subjected to rust prevention treatment is preferable.

As described above, in this embodiment, the carbon dioxide separation spiral module 60 is disposed around the perforated hollow center tube 62 for recovering the separated carbon dioxide, and the carbon dioxide separation layer 42 and the gas permeable layer. The carbon dioxide separation complex 46, which is a laminate with the conductive support 44, and a region for separating carbon dioxide formed by the process of overlapping and winding the flow path material 64 are provided, and the periphery thereof is fluid-impermeable. It coat | covers with the property coating layer 66. FIG.
The gas containing carbon dioxide is supplied from the end portion 68 of the carbon dioxide separation composite 46 and is divided by the coating layer 66, and is provided with the carbon dioxide separation composite 46 obtained by the production method of the present invention. When passing through the region for separating carbon, the carbon dioxide separated through the carbon dioxide separation layer 42 is accumulated in the hollow central tube 62 and recovered from the opening 70 connected to the hollow central tube 62. Is done. Further, the remaining gas from which carbon dioxide has been separated that has passed through the gap of the gas permeable support 44 and the gap of the flow path member 64 in the carbon dioxide separation composite 46 is separated in the carbon dioxide separation spiral module 60 by the dioxide dioxide. It is discharged from the end 72 of the carbon dioxide separation member on the side where the opening 58 for carbon recovery is provided.
A carrier gas selected from an inert gas or the like may be supplied to the hollow central tube 62 for carbon dioxide recovery.

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.
Unless otherwise specified, “%” and “part” described below mean “% by mass” and “part by mass”, respectively.

[Example 1]
<Preparation of coating solution composition for carbon dioxide separation layer>
Water was added to a polyvinyl alcohol-polyacrylic acid copolymer (Clastomer AP-22, manufactured by Kuraray Co., Ltd.) with stirring. Next, an aqueous cesium carbonate solution (solid content concentration: 40% by mass) was added, and the mixture was sufficiently stirred at a temperature of 25 ° C., so that the concentration of polyvinyl alcohol-polyacrylic acid copolymer as a water-soluble polymer was 2. An aqueous solution with 5% by mass and a cesium carbonate concentration of 6.0% by mass as a carbon dioxide carrier was prepared and defoamed to obtain a coating liquid composition (1) for forming a carbon dioxide separation layer.

(Formation of laminate)
As a temporary support, on the surface of a polyethylene terephthalate (PET) film (T60: trade name, manufactured by Toray Industries, Inc., film thickness: 100 μm), the coating liquid composition for forming a carbon dioxide separation layer (1) obtained above is applied to a roll coater. And dried by passing through the drying zone 20 of the production apparatus shown in FIG. 1 to obtain a laminate 40 having a carbon dioxide separation layer 42 on the surface of the temporary support 12. The coating speed was 10 m / min, and the drying temperature (hot air temperature in the drying zone) was 60 ° C.
(Manufacture of composites for carbon dioxide separation)
On the surface of the carbon dioxide separation layer 42 of the PET film 12 on which the carbon dioxide separation layer 42 is formed, supported PTFE (manufactured by Nakao Filter, Tetratox 7008, 200 μm thickness, maximum pore diameter 0.1 μm) as a gas permeable support 44 is provided. The thermal transfer process was performed using the laminating apparatus provided with the heating roller.
Lamination is performed at a roller heating temperature of 100 ° C. and a clearance between the rollers of 250 μm. After lamination, the PET film 12 is peeled off and wound up, and a carbon dioxide separation layer having a carbon dioxide separation layer 42 on the surface of the gas permeable support 44 is obtained. A composite 46 was obtained.

  The elongation of the temporary support 12 is determined by cutting the temporary support 12 into a width of 10 mm and a length of 50 mm to produce a test piece. The test piece is then subjected to a tensile tester (manufactured by Shimadzu Corporation, Autograph AGS). -J: trade name), the test piece was set at a distance between chucks of 20 mm, and the elongation at a load of 5 N was measured at 25 ° C. at a speed of 10 mm / min. It can be seen that the elongation is 2% and the shape stability is excellent.

(Evaluation of complex for carbon dioxide separation)
1. Appearance evaluation Regarding the obtained composite for carbon dioxide separation, visually observe the appearance of the carbon dioxide separation layer, and determine whether the transferred carbon dioxide separation layer is well transferred or has defects on the surface. Evaluation based on the criteria. Note that pinholes and membrane breakage that penetrate the carbon dioxide separation layer are defects in performance of the carbon dioxide separation composite and are not allowed.
A: The surface is smooth and a carbon dioxide separation layer without pinholes or film breakage is formed. B: Although irregularities are observed on the surface, defects that cause practical problems such as pinholes and film breakage are None C: Pinholes and film tears that can be visually observed were observed.

2. Evaluation of penetration of carbon dioxide separation layer into gas permeable support Further, the cross section of the carbon dioxide separation composite was observed with SEM (scanning electron microscope: Hitachi High-Tech, SU3500, magnification: 500 times), and gas permeation was observed. The infiltration state of the carbon dioxide separation layer into the voids of the conductive support was observed and evaluated according to the following criteria.
A: The carbon dioxide separation layer does not enter into the holes or irregularities of the gas permeable support B: The carbon dioxide separation layer enters into the holes or irregularities of the gas permeable support.

3. Gas permeability test Each sample of Examples 1 to 5 was cut to a diameter of 47 mm, and a gas permeability test was carried out using two PTFE membrane filters (pore diameter 0.10 μm, manufactured by ADVANTEC) sandwiched from both sides of the membrane. . As a test gas, a mixed gas of CO ₂ / H ₂ : 10/90 (volume ratio) was used with each sample (effective area 2.40 cm ² ) at a relative humidity of 70%, a flow rate of 100 ml / min, a temperature of 130 ° C., and a total pressure of 3 atm. ) And Ar gas (flow rate 90 ml / min) was allowed to flow on the permeate side. The permeated gas was analyzed with a gas chromatograph, and the CO ₂ permeation rate and the separation factor were calculated.
The results are also shown in Table 1.
In the following gas permeability test, the unit of permeation speed Q is as shown below.
1 × 10 −6 cm ³ (STP) / (s · cm ² · cmHg)
The separation coefficient α is calculated based on the following criteria.
α = [Q (CO ₂ ) / Q (H ₂ )]

[Example 2]
A composite for carbon dioxide separation was obtained by the same production method as in Example 1 except that the roller heating temperature during the thermal transfer treatment using the laminating apparatus was changed from 100 ° C. to 70 ° C. Evaluated.
Example 3
A composite for carbon dioxide separation was obtained by the same production method as in Example 1 except that the roller heating temperature during the thermal transfer treatment using the laminating apparatus was changed from 100 ° C. to 120 ° C., and the same as in Example 1. Evaluated.
[Comparative Example 1]
A coating solution composition for forming a carbon dioxide separation layer (1) prepared by the method <Preparation of coating solution composition for carbon dioxide separation layer> was used as a supported PTFE (manufactured by Nakao Filter, Tetratox 7008, 200 μm thickness, maximum pore size) 0.1 μm) was applied directly. The coating speed was 10 m / min, and the drying temperature (hot air temperature in the drying zone) was 60 ° C.

Example 4
The gas permeable support used was changed from a PET film to a polypropylene (PP) non-woven fabric (manufactured by Hirose Paper, HOP60), and the roller heating temperature during the thermal transfer treatment was changed from 100 ° C. to 70 ° C. The composite for carbon dioxide separation was obtained by the same production method as in Example 1 and evaluated in the same manner as in Example 1.
The results are shown in Table 2 below.
Example 5
The gas permeable support used was changed from a PET film to a polypropylene (PP) non-woven fabric (manufactured by Hirose Paper, HOP60), and the roller heating temperature during the thermal transfer treatment was changed from 100 ° C. to 120 ° C. The composite for carbon dioxide separation was obtained by the same production method as in Example 1 and evaluated in the same manner as in Example 1.
[Comparative Example 2]
The coating solution composition for forming a carbon dioxide separation layer (1) prepared by the method <Preparation of coating solution composition for carbon dioxide separation layer> is directly applied to a nonwoven fabric made of polypropylene (PP) (manufactured by Hirose Paper, HOP60). did. The coating speed was 10 m / min, and the drying temperature (hot air temperature in the drying zone) was 60 ° C.

As shown in Table 1, the composite for carbon dioxide separation obtained by the production method of the present invention has good surface properties of the formed carbon dioxide separation layer, no defects, and the gas permeable support. An excellent composite for carbon dioxide separation that does not penetrate the carbon dioxide separation layer is obtained.
In addition, it can be seen that all of the carbon dioxide composites of the examples have good gas permeation acceleration and separation coefficient, and are excellent in carbon dioxide separation ability.

Example 6
The gas permeable support used was supported PTFE (manufactured by Nakao Filter, Tetratox 7008, 200 μm thickness, maximum pore size 0.1 μm) to supported PTFE (manufactured by Nakao Filter, Tetratox 7008, 200 μm thickness, maximum pore size 0). The composite for carbon dioxide separation was obtained by the same production method as in Example 1 except that it was changed to .2 μm) and evaluated in the same manner as in Example 1.
Furthermore, the cross section of the composite for carbon dioxide separation was observed with an SEM scanning electron microscope (manufactured by Hitachi High-Tech, SU3500, magnification: 500 times), and the infiltration state of the carbon dioxide separation layer into the gas permeable support gap was observed. did.
The results are shown in Table 2 below.
Example 7
The gas permeable support used was supported PTFE (manufactured by Nakao Filter, Tetratox 7008, 200 μm thickness, maximum pore diameter 0.1 μm) to supported PTFE (manufactured by Nakao Filter, Tetratox 7008, 200 μm thickness, maximum pore diameter 0). The composite for carbon dioxide separation was obtained by the same production method as in Example 1 except that the thickness was changed to 0.5 μm) and evaluated in the same manner as in Example 1 and Example 7.

[Comparative Example 3]
A coating solution composition for forming a carbon dioxide separation layer (1) prepared by the method <Preparation of coating solution composition for carbon dioxide separation layer> was used as a supported PTFE (manufactured by Nakao Filter, Tetratox 7008, 200 μm thickness, maximum pore size) 0.2 μm). The coating speed was 10 m / min, and the drying temperature (hot air temperature in the drying zone) was 60 ° C.
[Comparative Example 4]
A coating solution composition for forming a carbon dioxide separation layer (1) prepared by the method <Preparation of coating solution composition for carbon dioxide separation layer> was used as a supported PTFE (manufactured by Nakao Filter, Tetratox 7008, 200 μm thickness, maximum pore size) 0.5 μm) was applied directly. The coating speed was 10 m / min, and the drying temperature (hot air temperature in the drying zone) was 60 ° C.

(Evaluation of film thickness uniformity)
A cross section of the composite for carbon dioxide separation was observed with an SEM (scanning electron microscope: manufactured by Hitachi High-Tech, SU3500, magnification: 500 times), and the film thickness distribution in the 300 mm width direction of the carbon dioxide separation layer was measured at five locations in the width direction. The film thickness was measured and evaluated by calculating the maximum value and the minimum value with respect to the average value.
The results are shown in Table 3 below.

From the results in Table 3, it can be seen that the carbon dioxide separation layer on the carbon dioxide separation composite obtained by the production method of the present invention is excellent in film thickness uniformity.
In addition, the manufacturing method of the composite for carbon dioxide separation which concerns on this invention, and the composite for carbon dioxide separation obtained by the manufacturing method are not restricted to the above-mentioned embodiment, Various, without deviating from the summary of this invention Of course, it is possible to adopt the following configuration.

DESCRIPTION OF SYMBOLS 10 Carbon dioxide separation production apparatus 12 Temporary support 14 Delivery roller (conveying means)
16 Coating device 18 Cooling unit (cooling device)
20 Drying unit (drying equipment)
22 Winding roller (conveying means)
24 Back support roller (roller)
26 Back support roller (roller)
30 Heat exchanger (cooling device)
32 Hot air heater (drying equipment)
34 Halogen heater (drying equipment)
40 Laminate (Laminate of support and carbon dioxide separation layer)
42 Carbon dioxide separation layer 44 Gas permeable support 46 Carbon dioxide separation composite 50 Heating roller (transfer means)
54 Temporary Support Winding Roller 56 Gas Permeable Support Feeding Roller 60 Spiral Module for Carbon Dioxide Separation

Claims (8)

A carbon dioxide separation layer forming step in which a carbon dioxide separation layer forming coating solution containing a water-absorbing polymer, a carbon dioxide carrier, and water is applied on a temporary support and dried to form a carbon dioxide separation layer;
The carbon dioxide separation layer obtained in the carbon dioxide separation layer forming step is adhered to a gas permeable support, and then the temporary support on the carbon dioxide separation layer adhered to the porous support is peeled off. And a transfer step of transferring the carbon dioxide separation layer onto the porous support.   The gas-permeable support is a porous resin sheet or nonwoven fabric having a maximum pore diameter of 0.05 μm or more and 0.5 μm or less, and a laminate of the porous resin sheet and nonwoven fabric having a maximum pore diameter of 0.05 μm or more and 0.5 μm or less The manufacturing method of the composite_body | complex for carbon dioxide separation of Claim 1 which is a support body selected from a body.   The method for producing a composite for carbon dioxide separation according to claim 1 or 2, wherein at least the surface of the gas permeable support on the side in contact with the carbon dioxide separation layer is a hydrophobic surface.   The carbon dioxide separation layer according to any one of claims 1 to 3, wherein the carbon dioxide separation layer is adhered to a gas permeable support by a heating roller having a surface temperature of 70C to 120C. A method for producing a composite.   The said gas-permeable support body is a porous resin sheet formed including the resin selected from the group which consists of a polypropylene and fluorine-containing resin, Any one of Claims 1-4. Of producing a composite for carbon dioxide separation.   A composite for carbon dioxide separation obtained by the method for producing a composite for carbon dioxide separation according to any one of claims 1 to 5.   A spiral module for separating carbon dioxide, comprising a step of spirally winding a complex for separating carbon dioxide obtained by the method for producing a complex for separating carbon dioxide according to any one of claims 1 to 5. Production method.   A carbon dioxide separation spiral module comprising the composite for carbon dioxide separation according to claim 6 or obtained by the method for producing a spiral module for carbon dioxide separation according to claim 7.