Support structure

Abstract

A support structure 10 disclosed herein is for supporting an active substance, and comprises a resin matrix 20 and porous particles 30 having a plurality of fine pores 32. The resin matrix 20 has a three-dimensional network structure including fine pores 22, and the porous particles 30 are disposed in the fine pores 22 of the resin matrix 20.

Description

Carrier Structure

[0001] The present invention relates to a support structure for supporting an active substance such as an adsorbent or a catalyst. This international application claims priority based on Japanese Patent Application No. 2023-140985 filed on August 31, 2023, the entire contents of which are incorporated herein by reference.

[0002] Exhaust gases emitted from thermal power plants, factories, automobiles, etc. contain various harmful components, and there is a need to develop materials and technologies that can selectively separate and capture them. For example, carbon dioxide (CO ２ ) are greenhouse gases, and therefore, a significant reduction in emissions is required. In order to efficiently separate and recover such components, materials are used that include an active substance such as an adsorbent or a catalyst, and a carrier that supports the active substance. Examples of related technologies include Patent Documents 1 and 2.

[0003] Special table No. 2014-533195 Publication No. 2018-505071

[0004] Examples of carriers that support active substances such as adsorbents and catalysts include those that use a honeycomb structure or a nonwoven fabric as a substrate. These carriers have the problem that the amount of active substance supported per volume is small because the carrier is disposed only on the surface of the substrate.

[0005] Another example of a support for supporting an active substance such as an adsorbent or a catalyst is a structure composed of support particles. Support particles with a high specific surface area or pore volume can be used to increase the amount of support. A structure composed of such support particles is formed by firing the support particles or densifying them by pressing. Therefore, even if support particles with a high specific surface area or pore volume are used, the specific surface area or pore volume decreases during the process of forming the structure. As a result, there is a problem in that the amount of active substance supported is reduced. According to the results of the inventors' studies, it was found that a support structure with a structure excellent in water absorption can increase the amount of active substance supported, such as an adsorbent or a catalyst, introduced.

[0006] The present invention has been made in view of the above circumstances, and a main object of the present invention is to provide a carrier structure having excellent water absorption properties.

[0007] The carrier structure disclosed herein is a carrier structure for supporting an active substance, and comprises a resin matrix and porous particles having a plurality of mesopores, wherein the resin matrix has a three-dimensional network structure including pores, and the porous particles are disposed in the pores of the resin matrix.

[0008] According to this configuration, the mesopores of the porous particles remain without being crushed or filled with the resin, and thus the water absorption of the carrier structure is suitably improved. In addition, the water absorption of the carrier structure is suitably improved by the pores of the resin matrix. This makes it possible to realize a carrier structure that can increase the amount of active substance supported.

[0009] In a preferred embodiment of the carrier structure disclosed herein, the average pore diameter A of the resin matrix is ​​0.5 μm or more and 10 μm or less. In another preferred embodiment, the average pore diameter B of the porous particles is 10 nm or more and 50 nm or less. In a particularly preferred embodiment, the average pore diameter A of the resin matrix is ​​0.5 μm or more and 5 μm or less, and the average pore diameter B of the porous particles is 10 nm or more and 40 nm or less. According to the above configuration, the water absorption of the carrier structure can be more suitably improved.

[0010] In a preferred embodiment of the carrier structure disclosed herein, the ratio (A / B) of the average pore diameter A of the resin matrix to the average pore diameter B of the porous particles is 20 or more and 200 or less. With this configuration, a carrier structure with more excellent water absorbency can be realized.

[0011] In a preferred embodiment of the carrier structure disclosed herein, the porosity based on Archimedes' method is 75% or more and 90% or less. With this configuration, a carrier structure having suitable water absorption properties can be provided.

[0012] In a preferred embodiment of the carrier structure disclosed herein, the water absorption rate based on Archimedes' method is 145% or more and 350% or less. With this configuration, a carrier structure is realized that can improve the recovery rate and separation performance of harmful components.

[0013] In a preferred embodiment of the carrier structure disclosed herein, the carrier structure has hot water resistance of 120° C. or more and 250° C. or less. According to this configuration, a carrier structure having excellent hot water resistance can be provided.

[0014] In a preferred embodiment of the carrier structure disclosed herein, the resin matrix contains a resin having a glass transition temperature of 70° C. or higher and 250° C. or lower. This configuration can suitably improve the heat resistance of the carrier structure.

[0015] In a preferred embodiment of the support structure disclosed herein, the porous particles include at least one selected from the group consisting of silica particles, alumina particles, ceria particles, zirconia particles, and titania particles. This configuration allows for more suitable support of active substances such as adsorbents and catalysts.

[0016] Fig. 1 is a diagram schematically showing the structure of a support structure according to one embodiment. Fig. 2 is a cross-sectional FE-SEM image (1000x magnification) showing a cross section of the support sheet of Example 3. Fig. 3 is a cross-sectional FE-SEM image (2000x magnification) showing a cross section of the support sheet of Example 3.

[0017] Preferred embodiments of the technology disclosed herein are described below. Matters necessary for implementation other than those specifically mentioned in this specification can be understood based on the technical content taught by this specification and the general technical common sense of a person skilled in the art. The technology disclosed herein can be implemented based on the content disclosed in this specification and the general technical common sense of a person skilled in the art. In this specification, the expression "A to B" indicating a range means A or more and B or less.

[0018] <Carrier Structure> FIG. 1 is a diagram schematically illustrating the structure of the carrier structure disclosed herein. As shown in FIG. 1, the carrier structure 10 disclosed herein includes a resin matrix 20 and porous particles 30. The carrier structure 10 disclosed herein is a carrier structure capable of supporting active substances such as various adsorbents and catalysts. The active substance is preferably carbon dioxide (CO ２ ) to chemically adsorb CO ２ It is preferable that the CO ２ Specific examples of the adsorbent include amine compounds having primary to tertiary amino groups, such as aminoorganosilanes, aliphatic amines, and aliphatic polyamines. ２ Amine compounds capable of absorbing CO ２ By supporting the adsorbent, CO ２ It can be suitably used as an adsorption material.

[0019] The support structure 10 can be formed into a sheet shape, a rectangular parallelepiped shape, a cube shape, a prism shape, a cylinder shape, a sphere shape, or the like. Although not particularly limited, the support structure 10 is preferably a support sheet formed into a sheet shape. When the support structure 10 is in a sheet shape, it is preferable that the thickness thereof is, for example, 0.3 mm or more and 5 mm or less.

[0020] The resin matrix 20 contained in the support structure 10 disclosed herein has a three-dimensional network structure including pores 22, as shown in FIG. 1 . The resin matrix 20 can function as a skeleton in the support structure 10. The resin matrix 20 can be formed, for example, by bonding crystalline particles of a resin. The pores 22 may be interconnected pores. A plurality of porous particles 30 are arranged in the pores 22. The porous particles 30 each have a plurality of pores 32. It is preferable that the majority of the porous particles 30 are present in the pores 22, separated from the resin matrix 20. Whether the support structure 10 has the resin matrix 20 and the porous particles 30 can be confirmed, for example, by observing the surface or cross section of the support structure 10 with a scanning electron microscope (SEM).

[0021] The carrier structure 10 disclosed herein has favorable improved water absorption properties due to the porous particles 30 being disposed in the pores 22 of the resin matrix 20. This allows a larger amount of active substance to be supported than conventional carriers, increasing the amount supported per volume and improving the recovery and separation performance of harmful components. While not intending to limit the technology disclosed herein, the reason for this effect is presumed to be as follows. In the carrier structure 10, the porous particles 30 are disposed in the pores 22 of the resin matrix 20, allowing the porous particles 30 to exist in a state where the pores 32 of the porous particles 30 are not crushed or filled with resin. Furthermore, because the resin matrix 20 also has favorable pores 22, the active substance can also be supported in these pores 22. As a result, the carrier structure 10 disclosed herein can achieve high water absorption properties.

[0022] As described above, the carrier structure 10 has a high water absorption rate. Although not particularly limited, the water absorption rate of the carrier structure 10 disclosed herein based on Archimedes' method is preferably 140% or more, more preferably 145% or more, even more preferably 147% or more, and may be 190% or more, or may be 200% or more. When the carrier structure 10 has a high water absorption rate, the amount of active substance carried per volume increases, and the separation and recovery performance of harmful components can be improved. From this perspective, a higher water absorption rate is preferable, and there is no particular limit on the upper limit. For example, the water absorption rate of the carrier structure 10 based on Archimedes' method may be 400% or less, 370% or less, or 350% or less. The "water absorption rate of the carrier structure" can be calculated based on Archimedes' method. More specifically, the dry weight W of the carrier structure Ａｉｒ , underwater weight W Ａｑ , water content W ａ＋ｗ The water absorption rate (Aw) can be calculated based on the following formula (1): Aw (%) = (W ａ＋ｗ -W Ａｉｒ ) / W Ａｉｒ ×100 (1)

[0023] Although not particularly limited, the porosity of the carrier structure 10 disclosed herein based on the Archimedes method is preferably 65% ​​or more, more preferably 70% or more, and even more preferably 75% or more. This allows the components to be recovered (e.g., CO ２ ) can be suitably brought into contact with an active substance (e.g., an amine compound). The porosity of the support structure 10 based on Archimedes' method is preferably, for example, 90% or less, and may be 86% or less. The "porosity of the support structure" can be calculated based on Archimedes' method. More specifically, the dry weight W of the support structure Ａｉｒ , underwater weight W Ａｑ , water content W ａ＋ｗ The porosity (P) can be calculated based on the following formula (2): P (%) = (W ａ＋ｗ -W Ａｉｒ ) / (W ａ＋ｗ -W Ａｑ ) x 100 (2)

[0024] Furthermore, although not particularly limited, it is preferable that the carrier structure 10 has high hot water resistance. The hot water resistance of the carrier structure 10 is preferably 120°C or higher, more preferably 140°C or higher, and may be 150°C or higher, or may be 160°C or higher. This allows the carrier structure 10 disclosed herein to be suitably used in environments exceeding 100°C or in relatively humid environments. The hot water resistance of the carrier structure 10 is preferably 250°C or lower, and may be 200°C or lower, for example. The "hot water resistance of the carrier structure" can be evaluated by immersing the carrier structure in hot water in an autoclave, drying it, and measuring its strength using a conventionally known tensile test.

[0025] The resin matrix 20 has a three-dimensional network structure including a plurality of pores 22. The average pore diameter A of the resin matrix 20 is preferably 0.4 μm or more, more preferably 0.5 μm or more, even more preferably 0.56 μm or more, and may be 1 μm or more. This can suitably improve the water absorption of the carrier structure 10. If the average pore diameter A of the resin matrix 20 is too large, the porous particles 30 may be detached from the resin matrix 20. From this viewpoint, the average pore diameter A of the resin matrix 20 is, for example, preferably 10 μm or less, more preferably 7 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The "average pore diameter of the resin matrix" can be determined by mercury intrusion porosimetry using a commercially available mercury porosimeter.

[0026] The resin matrix 20 contains a resin and can be formed by bonding crystalline particles of the resin. Although not particularly limited, the resin matrix 20 preferably contains a resin having a glass transition temperature (Tg) of 70°C or higher. This improves the heat resistance of the carrier structure 10. The glass transition temperature of the resin contained in the resin matrix 20 is preferably 70°C or higher, and may be 100°C or higher, or may be 120°C or higher. The glass transition temperature of the resin contained in the resin matrix 20 may be, for example, 260°C or lower, or 250°C or lower. The "glass transition temperature of the resin" can be measured according to conventionally known methods such as differential scanning calorimetry (DSC) measurement or dynamic viscoelasticity measurement (DMA).

[0027] Furthermore, although not particularly limited, it is preferable that the resin matrix 20 contains a resin having high hot water resistance. This can improve the hot water resistance of the carrier structure 10. The hot water resistance of the resin contained in the resin matrix 20 is preferably 120°C or higher, more preferably 140°C or higher, and may be 150°C or higher, or may be 160°C or higher. The hot water resistance of the resin contained in the resin matrix 20 is, for example, preferably 300°C or lower, and may be 250°C or lower, or may be 200°C or lower. Note that the nominal value (catalog value) of each manufacturer or the like may be used for the "hot water resistance of the resin."

[0028] The resin content is not particularly limited, but is preferably 30% by mass or more and 80% by mass or less, more preferably 35% by mass or more and 70% by mass or less, even more preferably 40% by mass or more and 60% by mass or less, and may be 40% by mass or more and 50% by mass or less, when the total mass of the support structure 10 is 100% by mass. This makes it possible to suitably improve the water absorption of the support structure 10. Furthermore, from the viewpoint of further suitably improving the water absorption rate of the support structure 10, it is preferable that the content ratio of the porous particles 30 is higher than that of the resin constituting the resin matrix 20. From this viewpoint, the resin content may be less than 50% by mass, for example, 40% by mass or more and 48% by mass or less.

[0029] Although not particularly limited, examples of resin components contained in the resin matrix 20 include acrylic resins, cellulose resins, and resins classified as super engineering plastics. The resin matrix 20 may contain any one of the above resins alone or a combination of two or more of them.

[0030] Acrylic resins encompass polymers containing alkyl (meth)acrylate as a constituent monomer component and their derivatives. In this specification, the term "(meth)acrylate" is used to refer collectively to acrylate and / or methacrylate. Examples of acrylic resins include polymers containing alkyl (meth)acrylate as the main monomer (a component accounting for 50% by mass or more of the total monomers) and copolymers containing such a main monomer and a secondary monomer copolymerizable with the main monomer. Specific examples include poly(meth)acrylic acid, poly(meth)acrylamide, and polymethyl methacrylate (PMMA). Among these, the resin matrix 20 preferably contains methacrylic acid or PMMA.

[0031] The cellulose-based resin encompasses all compounds derived from cellulose (cellulose derivatives). Specific examples include ethyl cellulose (EC), hydroxyethyl cellulose (HEC), ethyl methyl cellulose (EMC), hydroxyethyl methyl cellulose (HEMC), nitrocellulose, and diacetyl cellulose. Among these, it is preferable that the resin matrix 20 contains ethyl cellulose.

[0032] Super engineering plastics are thermoplastic resins with extremely high heat resistance and mechanical strength. Specific examples of super engineering plastics include fluororesins such as polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluorovinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), chlorotrifluoroethylene homopolymer (PCTFE), tetrafluoroethylene-ethylene copolymer (ETFE), chlorotrifluoroethylene-ethylene copolymer (ECTFE), and vinylidene fluoride homopolymer (PVDF); thermoplastic polyimides such as polybenzimidazole (PBI), polyimide (PI), polyetherimide (PEI), and polyamideimide (PAI); polyethersulfone (PES), polyetheretherketone (PEEK), polyethersulfide, and polyphenylene sulfide. Among these, the resin matrix 20 preferably contains PEI, PES, or PVDF.

[0033] The porous particles 30 may be any inorganic porous material capable of supporting an active substance such as an adsorbent or catalyst. For example, a porous material with a relatively large specific surface area is preferred. For example, oxides of semimetallic elements and metallic elements or solid solutions thereof can be preferably used as the porous particles 30. Specific examples include silica particles, alumina particles, ceria particles, zirconia particles, and titania particles. Any one or more of these can be used without any particular limitation. Among these, it is preferable that the porous particles 30 include silica particles.

[0034] The porous particle 30 has a plurality of pores 32. The porous particle 30 may be, for example, a mesoporous material having mesopores. "Mesopores" refers to pores having a pore diameter in the range of 2 nm or more and less than 50 nm, based on the IUPAC classification. The average pore diameter B of the porous particle 30 is, for example, preferably 2 nm or more, more preferably 10 nm or more, and even more preferably 12 nm or more. This allows the active substance to be favorably introduced into the pores 32 when it is supported. The average pore diameter B of the porous particle 30 is, for example, preferably 100 nm or less, more preferably 70 nm or less, and even more preferably 50 nm or less, and is preferably less than 50 nm, for example, 40 nm or less, and particularly preferably 30 nm or less. This allows the specific surface area of ​​the porous particle 30 to be favorably increased, thereby further improving the water absorption of the carrier structure 10. The "average pore size of the porous particles" can be measured by measuring the pore size distribution of the carrier structure by a gas adsorption method based on the BJH method using a commercially available pore size distribution measuring device.

[0035] The average particle size of the porous particles 30 is not particularly limited. If the average particle size of the porous particles 30 is too small, they tend to be difficult to disperse in the support structure 10. From this perspective, the average particle size of the porous particles 30 is, for example, 100 nm or more, and may be 1 μm or more, 3 μm or more, or 5 μm or more. On the other hand, as described above, the porous particles 30 contain many voids (pores 32). Therefore, if the average particle size is too large, the porous particles 30 may be easily broken due to collisions between the porous particles. From this perspective, the average particle size of the porous particles 30 is, for example, 100 μm or less, 50 μm or less, or 15 μm or less. In this specification, the "average particle size of the porous particles" refers to the arithmetic mean value of the circle-equivalent diameter measured based on observation with an optical microscope. Here, the circle-equivalent diameter refers to the diameter of a circle having the same area as the area of ​​an ellipse formed by the major axis, which is the longest diameter of a porous particle observed in a microscope image, and the minor axis, which is the longest diameter of a line intersecting the major axis at a right angle. In this specification, the average particle size of porous particles refers to the arithmetic mean value of the circle-equivalent diameters of 200 randomly selected porous particles.

[0036] From the viewpoint of increasing the contact area between the active substance and the harmful component, it is preferable that the specific surface area of ​​the porous particles 30 is large. Although not particularly limited, the specific surface area of ​​the porous particles 30 measured by the BET method (BET specific surface area) is, for example, 190 m ２ / g or more 650m ２ / g or less, and ２ / g or more 450m ２ In this specification, the "BET specific surface area of ​​the porous particles" can be measured by a nitrogen adsorption method using a commercially available specific surface area measuring device.

[0037] Furthermore, from the viewpoint of increasing the amount of active substance supported, it is preferable that the oil absorption of the porous particles 30 is high. Although not particularly limited, the oil absorption of the porous particles 30 is preferably, for example, 100 ml / 100 g or more and 400 ml / 100 g or less, and more preferably 130 ml / 100 g or more and 380 ml / 100 g or less. The "oil absorption of the porous particles" can be measured using a general absorption measurement device and DBP (dibutyl phthalate) as the reagent liquid in accordance with JIS K6217-4 (2008).

[0038] The content of the porous particles 30 is not particularly limited, but is preferably 20% by mass or more and 70% by mass or less, more preferably 30% by mass or more and 65% by mass or less, even more preferably 40% by mass or more and 60% by mass or less, and may be 50% by mass or more and 60% by mass or less, when the total mass of the support structure 10 is taken as 100% by mass. This makes it possible to suitably improve the water absorption of the support structure 10. Furthermore, from the viewpoint of further suitably improving the water absorption rate of the support structure 10, it is preferable that the content ratio of the porous particles 30 is higher than that of the resin component. From this viewpoint, the content of the porous particles 30 may be more than 50% by mass, for example, 52% by mass or more and 60% by mass or less.

[0039] Although not particularly limited, in the support structure 10, the ratio (A / B) of the average pore diameter A of the resin matrix 20 to the average pore diameter B of the porous particles 30 is preferably 20 or more and 200 or less, more preferably 24 or more and 165 or less, and may be 50 or more and 120 or less. In other words, the support structure 10 preferably has a structure having both relatively small pores (e.g., mesopores of less than 50 nm) derived from the porous particles 30 and relatively large pores (e.g., pores of 0.5 μm or more) derived from the pores 22 of the resin matrix 20. This can suitably improve the water absorption of the support structure 10.

[0040] Although not particularly limited, in the carrier structure 10, the mass ratio of the porous particles 30 to the resin constituting the resin matrix 20 is preferably, for example, 20:80 to 70:30, more preferably 30:70 to 65:35, and even more preferably 40:60 to 65:35. This allows the balance between the average pore diameter A derived from the resin matrix 20 and the average pore diameter B derived from the porous particles 30 to be suitably adjusted, thereby improving the water absorption rate of the carrier structure 10.

[0041] <Method for manufacturing carrier structure> Next, an example of a method for manufacturing the carrier structure 10 disclosed herein will be described. The carrier structure 10 disclosed herein can include a preparation step of preparing a carrier structure forming slurry, a molding step of producing a molded body from the carrier structure forming slurry, an immersion step of immersing the molded body in an aqueous solvent, and a drying step of drying the molded body after the immersion step. Note that the carrier structure 10 disclosed herein is not limited to those manufactured by the following manufacturing method.

[0042] In the preparation step, a slurry-like composition (slurry for forming a support structure) containing at least the porous particles 30, a resin, and an organic solvent is prepared. As an example, in the preparation step, the porous particles 30 are introduced into the organic solvent and stirred. As a result, the porous particles 30 are dispersed in the organic solvent. Next, the resin is introduced into the organic solvent in which the porous particles 30 are dispersed and stirred. As a result, the resin is dissolved in the organic solvent. Although not particularly limited, in the preparation step, the porous particles 30 and the resin are introduced into the organic solvent and stirred while heated to 40°C to 60°C.

[0043] The porous particles 30 may preferably be those described above. Of these, silica particles are preferably used. As the resin, a resin that dissolves in an organic solvent and precipitates in a network structure during the immersion step described below may preferably be used. Of these, PEI, PES, and PVDF are preferably used. The mass ratio of the porous particles 30 to the resin is preferably 20:80 to 70:30, more preferably 30:70 to 65:35, and even more preferably 55:45 to 65:35.

[0044] The organic solvent is not particularly limited as long as it can dissolve the resin. Examples of organic solvents include amides such as diethylformamide, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, and dimethylimidazolidinone; alkyl ketones such as dimethyl sulfoxide, acetone, and methyl ethyl ketone; ethers such as tetrahydrofuran, dioxane, and diglyme; and glycol ethers such as ethylene glycol and diethylene glycol. These may be used alone or in combination of two or more. The mass ratio of the organic solvent contained in the support structure-forming slurry is not particularly limited. The content of the organic solvent in the support structure-forming slurry is preferably, for example, 30% by mass to 80% by mass. This allows for the production of a molded body in the molding process.

[0045] In addition, conventionally known additives may be added to the support structure forming slurry as long as they do not significantly impair the effects of the technology disclosed herein. Examples of such additives include dispersants, plasticizers, antifoaming agents, thickeners, etc. For example, hydrophilic polymers such as polyethylene glycol (PEG) can be preferably used as additives. The content of the additive in the support structure forming slurry is preferably, for example, 30% by mass or less, and may be 20% by mass or less, or may be 10% by mass or less.

[0046] In the molding step, a molded body is molded using the above-prepared slurry for forming the carrier structure. For example, a sheet-like molded body can be produced by supplying the slurry for forming the carrier structure to a predetermined thickness on a glass substrate using a doctor blade. Alternatively, a molded body of a desired shape can be produced by extruding the slurry for forming the carrier structure into a predetermined shape, printing it on a metal plate or metal mesh, or dip-coating it onto a core material.

[0047] In the immersion step, the molded body prepared in the molding step is immersed in an aqueous solvent (e.g., water). As a result, the organic solvent contained in the molded body is replaced with the aqueous solvent, and the resin is precipitated. The areas where the organic solvent contained in the molded body has been replaced with the aqueous solvent become pores 22, and when the resin precipitates, the resin matrix 20 as described above is suitably formed. Because the porous particles 30 are dispersed in the organic solvent, the resin matrix 20 is formed so as to envelop the porous particles 30, and the porous particles 30 are arranged in the pores 22 of the resin matrix 20.

[0048] The aqueous solvent used in the immersion step is not particularly limited. The aqueous solvent may be, for example, water, a mixed solution of water and alcohol, or water to which a surfactant may be added. Preferred aqueous solvents include ion-exchanged water (deionized water), pure water, ultrapure water, and distilled water.

[0049] In the drying step, the compact after the immersion step is dried to remove the aqueous solvent from the compact. This allows the carrier structure 10 having the structure described above to be suitably produced. The drying means used in the drying step are not particularly limited, and for example, a hot air dryer, a low-humidity air dryer, a vacuum dryer, various infrared dryers, an electromagnetic induction dryer, a microwave dryer, dry air, etc., or drying promotion means such as air blowing, reduced pressure, and heating can be used alone or in combination. The drying temperature (such as the set temperature of the dryer) in the drying step can be appropriately selected depending on the type and amount of solvent in the mixture, and can be set, for example, to 60°C to 150°C, preferably 80°C to 120°C. The drying time can also be appropriately selected depending on the type and amount of aqueous solvent, and is not particularly limited.

[0050] In this manner, a carrier structure 10 having good water absorption properties can be suitably produced. Such a carrier structure 10 is suitable for carrying an active substance, particularly a carrier for carrying CO ２ The carrier can be suitably used for carrying an amine liquid that absorbs the amine.

[0051] <Test Examples> Test examples relating to the technology disclosed herein will be described below, but it is not intended that the technology disclosed herein be limited to such test examples.

[0052] <Preparation of Support Structure> (Example 1) First, porous silica particles (SiO ２ 135 g of cellulose acylate (cellulose acetate, average particle diameter: 9 μm), 80 g of polyetherimide (PEI) as a resin, 500 g of dimethyl sulfoxide (DMSO) as an organic solvent, and 28 g of polyethylene glycol (PEG) as an additive were prepared. Thus, a slurry for forming a carrier structure of Example 1 was prepared. Next, the slurry for forming a carrier structure of Example 1 was applied to a glass substrate using a doctor blade to a thickness of 2 mm, thereby obtaining a sheet-like molded product. The sheet-like molded product was immersed in water for 24 hours. The molded product after immersion in water was then dried at 80°C for 5 hours, thereby obtaining a sheet-like carrier structure (carrier sheet) of Example 1.

[0053] (Example 2) In Example 2, SiO 2 having an average particle size of 6 μm was used as the porous particles. ２ Then, each material was mixed in a mass ratio of SiO ２ The components were mixed in a ratio of 18:11:67:4, to prepare a slurry for forming a carrier structure of Example 2. The slurry was formed into a sheet in the same manner as in Example 1, and then the sheet was immersed for 24 hours in a solution prepared by mixing water and ethanol in a ratio of 5:95. Except for these, the same procedure as in Example 1 was carried out to obtain a carrier structure of Example 2 formed into a sheet.

[0054] (Example 3) In Example 3, N-methylpyrrolidone (NMP) was used as the solvent. Each material was mixed in a mass ratio of SiO ２The components were mixed in a ratio of 18:11:67:4, so as to prepare a slurry for forming a carrier structure of Example 3. Except for this, the same procedure as in Example 1 was carried out to obtain a carrier structure of Example 3 formed into a sheet shape.

[0055] (Example 4) In Example 4, SiO 2 having an average particle size of 6 μm was used as the porous particles. ２ Then, each material was mixed in a mass ratio of SiO ２ The components were mixed in a ratio of 14:8:51:27, to prepare a slurry for forming a carrier structure of Example 4. Except for this, the same procedure as in Example 1 was carried out to obtain a carrier structure of Example 4 formed into a sheet shape.

[0056] (Example 5) In Example 5, SiO 2 having an average particle size of 6 μm was used as the porous particles. ２ Polyethersulfone (PES) was used as the resin. Each material was mixed in a mass ratio of SiO ２ The components were mixed in a ratio of 18:11:67:4, and a slurry for forming a carrier structure of Example 5 was prepared. Except for this, the same procedure as in Example 1 was repeated to obtain a carrier structure of Example 5 formed into a sheet shape.

[0057] (Example 6) In Example 6, NMP was used as the solvent. Each material was mixed in a mass ratio of SiO ２ The components were mixed in a ratio of 16:20:60:4 to prepare a slurry for forming a carrier structure of Example 6. Except for this, the same procedure as in Example 1 was carried out to obtain a carrier structure of Example 6 formed into a sheet shape.

[0058] (Example 7) In Example 7, PES was used as the resin. N-methylpyrrolidone (NMP) was used as the solvent. Each material was mixed in a mass ratio of SiO ２ The components were mixed in a ratio of 24:13.5:56:6.5 to prepare a slurry for forming a carrier structure of Example 7. Except for this, the same procedure as in Example 1 was repeated to obtain a carrier structure of Example 7 formed into a sheet shape.

[0059] (Example 8) In Example 8, PEI and polymethyl methacrylate (PMMA) were used as the resin. N-methylpyrrolidone (NMP) was used as the solvent. SiO２ The components were mixed in a ratio of 16:10:10:60:4 to prepare a slurry for forming a carrier structure of Example 7. Except for this, the same procedure as in Example 1 was repeated to obtain a carrier structure of Example 8 formed into a sheet shape.

[0060] (Example 9) In Example 9, PEI and ethyl cellulose (EC) were used as the resin. N-methylpyrrolidone (NMP) was used as the solvent. SiO ２ The components were mixed in a ratio of 16:10:10:60:4 to prepare a slurry for forming a carrier structure of Example 9. Except for this, the same procedure as in Example 1 was repeated to obtain a carrier structure of Example 9 formed into a sheet shape.

[0061] (Example 10) In Example 10, porous silica particles (SiO ２ 10 g of porous silica particles (average particle diameter: 6 μm) were prepared. Using a mold and a press, the porous silica particles were press-molded to a diameter of 15 mm and a thickness of 2 mm to obtain a molded body. The molded body was dried at 800° C. for 2 hours to obtain a support structure of Example 10.

[0062] (Example 11) In Example 11, PES was used as the resin. NMP was used as the solvent. SiO ２ The components were mixed in a ratio of 18:10.8:67:4.2 to prepare a slurry for forming a carrier structure of Example 11. Except for this, the same procedure as in Example 1 was repeated to obtain a carrier structure of Example 11 formed into a sheet shape.

[0063] <Measurement of Average Pore Diameter of Resin Matrix> The average pore diameter of the resin matrix contained in the support structure of each example was measured using mercury intrusion porosimetry. Specifically, first, the support structure of each example was cut into a size of approximately 5 mm x 5 mm and pretreated by heating to 120 ° C. for 3 hours. Next, mercury was introduced into the support structure in a range of 0.10 to 60,000 psia using a mercury porosimeter (Micromeritics, Auto Pore IV 9500) to obtain the pore distribution of each example. The average pore diameter A (μm) of the resin matrix contained in the support structure of each example was calculated from the peak position of the obtained pore distribution. The results are shown in Table 1. Note that Example 10 did not contain a resin, but the pore diameter calculated in the same manner as above was used as the average pore diameter A, and the results are shown in Table 1.

[0064] <Measurement of Average Pore Diameter of Porous Particles> The average pore diameter of the porous particles contained in the support structure of each example was measured using a nitrogen gas adsorption method. Specifically, first, the support structure of each example was cut into a size of about 5 mm x 5 mm, and pretreated by holding it under vacuum at 120°C for 3 hours. Next, using a pore size distribution measuring device (Microtrac-Bell, BELSORP MINI), nitrogen gas was introduced at 77 K to determine the adsorption isotherm of each example. The obtained adsorption isotherm was converted into a pore distribution by the BJH method, and the pore volume V (cm / g) and specific surface area S (m ２ The average pore diameter B (nm) of the porous particles contained in the carrier structure of each example was calculated using the following formula: average pore diameter B (nm) = 4V / S. The results are shown in Table 1.

[0065] <Measurement of Water Absorption and Porosity> The water absorption and porosity of each carrier structure were measured based on the Archimedes method. Specifically, first, the dry weight W Ａｉｒ Next, the carrier structure of each example was immersed in distilled water, and then placed in a desiccator equipped with a vacuum pump, and vacuum was applied for 45 minutes, and the weight in water W Ａｑ and water weight W ａ＋ｗ The water absorption (Aw) was calculated based on the following formula (3). The porosity (P) was calculated based on the following formula (4). The results are shown in Table 1. Aw (%) = (W ａ＋ｗ-W Ａｉｒ ) / W Ａｉｒ ×100 (3) P (%) = (W ａ＋ｗ -W Ａｉｒ ) / (W ａ＋ｗ -W Ａｑ ) x 100 (4)

[0066] <Observation of Support Structure> A scanning electron microscope (SEM) was used to observe the cross section of the support structure of Example 3. Fig. 2 shows an SEM photograph of Example 3 (magnification: 1000 times), and Fig. 3 shows an SEM photograph of Example 3 (magnification: 2000 times).

[0067]

[0068] As shown in Table 1, it can be seen that the water absorption rate is 147% or more in Examples 1 to 9 and Example 11. This is presumably because, in Examples 1 to 9 and Example 11, the resin matrix has a three-dimensional network structure containing pores, and the porous particles are arranged in the pores of the resin matrix, thereby exhibiting favorable water absorption. On the other hand, it can be seen that the carrier structure of Example 10, which does not contain resin and is composed of porous particles, has a higher porosity than Examples 6, 8, and 9, but a lower water absorption rate than Examples 6, 8, and 9. This is presumably because, although Example 10 has many mesopores derived from the porous particles, there are no relatively large pores exceeding 0.5 μm derived from the resin matrix, and therefore the water absorption rate is not favorably improved.

[0069] While specific examples of the technology disclosed herein have been described in detail above, these are merely examples and do not limit the scope of the claims. The technology described in the claims includes various modifications and alterations of the specific examples exemplified above.

[0070] The technology disclosed herein includes the following items 1 to 8. The following items 1 to 8 are not limited to the above-described embodiment.

[0071] Item 1 relates to a carrier structure for supporting an active substance. The carrier structure in item 1 includes a resin matrix and porous particles having mesopores, the resin matrix having a three-dimensional network structure including pores, and the porous particles are disposed in the pores of the resin matrix.

[0072] Item 2 is the carrier structure according to item 1, wherein the average pore diameter A of the resin matrix is ​​0.5 μm or more and 10 μm or less. Alternatively, the average pore diameter B of the porous particles is 10 nm or more and 50 nm or less. Alternatively, the average pore diameter A of the resin matrix is ​​0.5 μm or more and 5 μm or less, and the average pore diameter B of the porous particles is 10 nm or more and 40 nm or less.

[0073] Item 3 is the carrier structure according to item 1 or 2, wherein the ratio (A / B) of the average pore diameter A of the resin matrix to the average pore diameter B of the porous particles is 20 or more and 200 or less.

[0074] Item 4 is the support structure according to any one of items 1 to 3, wherein the porosity based on Archimedes' method is 75% or more and 90% or less.

[0075] Item 5 is the carrier structure according to any one of items 1 to 4, wherein the water absorption rate based on Archimedes' method is 145% or more and 350% or less.

[0076] Item 6 is the carrier structure according to any one of items 1 to 5, wherein the carrier structure has hot water resistance of 120° C. or higher and 250° C. or lower.

[0077] Item 7 is the carrier structure according to any one of items 1 to 6, wherein the resin matrix contains a resin having a glass transition temperature of 70° C. or higher and 250° C. or lower.

[0078] Item 8 is the support structure according to any one of items 1 to 7, wherein the porous particles include at least one selected from the group consisting of silica particles, alumina particles, ceria particles, zirconia particles, and titania particles.

[0079] According to the present invention, a carrier structure having excellent water absorption properties can be provided.

[0080] 10 Support structure 20 Resin matrix 22 Pore 30 Porous particle 32 Pore

Claims

1. A carrier structure for carrying an active substance, comprising: a resin matrix; and porous particles having a plurality of mesopores, wherein the resin matrix has a three-dimensional network structure including pores, and the porous particles are disposed in the pores of the resin matrix.

2. The support structure according to claim 1, wherein the average pore size A of the resin matrix is ​​0.5 μm or more and 10 μm or less.

3. The carrier structure according to claim 1, wherein the average pore diameter B of the porous particles is 10 nm or more and 50 nm or less.

4. The support structure according to claim 1, wherein the average pore diameter A of the resin matrix is ​​0.5 μm or more and 5 μm or less, and the average pore diameter B of the porous particles is 10 nm or more and 40 nm or less.

5. The support structure according to any one of claims 1 to 4, wherein the ratio (A / B) of the average pore diameter A of the resin matrix to the average pore diameter B of the porous particles is 20 or more and 200 or less.

6. The support structure according to any one of claims 1 to 4, having a porosity based on Archimedes' method of 75% or more and 90% or less.

7. The carrier structure according to any one of claims 1 to 4, which has a water absorption rate based on Archimedes' method of 145% or more and 350% or less.

8. The carrier structure according to any one of claims 1 to 4, which has hot water resistance of 120°C or higher and 250°C or lower.

9. The carrier structure according to any one of claims 1 to 4, wherein the resin matrix contains a resin having a glass transition temperature of 70°C or higher and 250°C or lower.

10. The support structure according to any one of claims 1 to 4, wherein the porous particles include at least one type selected from the group consisting of silica particles, alumina particles, ceria particles, zirconia particles, and titania particles.

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