Carrier structure

Abstract

The carrier structure (10) disclosed herein is a carrier structure (10) for supporting an active material, and includes a resin matrix (20) and porous particles (30) having a plurality of mesopores (32). The resin matrix (20) has a three-dimensional network structure including pores (22), and the porous particles (30) are disposed in the pores (22) of the resin matrix (20).

Description

Technical Field

[0001] This invention relates to support structures for loading active substances such as adsorbents and catalysts. It should be noted that this international application claims priority to Japanese Patent Application No. 2023-140985, filed August 31, 2023, the entire contents of which are incorporated herein by reference. Background Technology

[0002] The exhaust gases emitted from thermal power plants, factories, automobiles, etc., contain various harmful components, necessitating the development of materials and technologies for their selective separation and recovery. For example, carbon dioxide (CO2), a greenhouse gas contributing to global warming, urgently requires significant reductions in its emissions. To efficiently separate and recover such components, materials including active substances such as adsorbents and catalysts, and carriers supporting these active substances, are used. Patent documents 1 and 2 are cited as examples of related technologies.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Publication No. 2014-533195

[0006] Patent Document 2: Japanese Patent Publication No. 2018-505071 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] Examples of carriers for loading active substances such as adsorbents and catalysts include honeycomb structures and carriers using non-woven fabrics as substrates. However, these carriers, because they are only disposed on the surface of the substrate, suffer from the problem of low loading capacity of active substances per unit volume.

[0009] Furthermore, other examples of supports for loading active substances such as adsorbents and catalysts include structures composed of support particles. To increase the loading capacity, support particles with high specific surface area and pore volume can be used. Structures composed of such support particles are formed by sintering or densifying the support particles through pressing. Therefore, even when using support particles with high specific surface area and pore volume, the specific surface area and pore volume decrease during the structure formation process. Moreover, this results in a reduction in the loading capacity of the active substance. According to the results of the inventors' research, it has been found that as long as the support structure has excellent water absorption, the loading capacity of the introduced active substances such as adsorbents and catalysts can be increased.

[0010] The present invention was made in view of the above-mentioned actual situation, and its main purpose is to provide a carrier structure with excellent water absorption.

[0011] Methods for solving problems

[0012] The carrier structure disclosed herein is a carrier structure for loading active substances, comprising a resin matrix and porous particles having multiple mesopores. The resin matrix has a three-dimensional network structure containing fine pores, and the porous particles are disposed in the fine pores of the resin matrix.

[0013] According to this structure, since the mesopores of the porous particles are not crushed or buried by the resin, the water absorption of the carrier structure is appropriately improved. Furthermore, the water absorption of the carrier structure is also appropriately improved by utilizing the fine pores of the resin matrix. Thus, a carrier structure capable of increasing the loading capacity of active substances can be realized.

[0014] In a preferred embodiment of the carrier structure disclosed herein, the average pore size A of the resin matrix is ​​0.5 μm or more and 10 μm or less. Furthermore, in another preferred embodiment, the average pore size B of the porous particles is 10 nm or more and 50 nm or less.

[0015] In a particularly preferred embodiment, the average pore size A of the resin matrix is ​​0.5 μm or more and 5 μm or less, and the average pore size B of the porous particles is 10 nm or more and 40 nm or less.

[0016] Based on the above composition, the water absorption of the carrier structure can be improved more appropriately.

[0017] In a preferred embodiment of the carrier structure disclosed herein, the ratio (A / B) of the average pore size A of the resin matrix to the average pore size B of the porous particles is 20 or more and 200 or less.

[0018] Based on this composition, a carrier structure with excellent water absorption can be more appropriately achieved.

[0019] In a preferred embodiment of the carrier structure disclosed herein, the porosity based on the Archimedes method is 75% or more and 90% or less.

[0020] Based on this composition, a carrier structure with suitable water absorption can be provided.

[0021] In a preferred embodiment of the carrier structure disclosed herein, the water absorption rate based on the Archimedes method is 145% or more and 350% or less.

[0022] Based on this composition, a carrier structure is realized that can improve the recovery rate and separation performance of harmful components.

[0023] In a preferred embodiment of the carrier structure disclosed herein, the hot water resistance is above 120°C and below 250°C.

[0024] Based on this composition, a carrier structure with excellent hot water resistance can be provided.

[0025] In a preferred embodiment of the carrier structure disclosed herein, the resin matrix comprises a resin having a glass transition temperature of 70°C or higher and 250°C or lower.

[0026] Based on this configuration, the heat resistance of the carrier structure can be appropriately improved.

[0027] In a preferred embodiment of the carrier structure disclosed herein, the porous particles comprise at least one selected from silica particles, alumina particles, cerium dioxide particles, zirconium oxide particles, and titanium dioxide particles.

[0028] Based on this composition, it is possible to more appropriately load active substances such as adsorbents and catalysts. Attached Figure Description

[0029] Figure 1 This diagram schematically illustrates the structure of a carrier structure according to one embodiment.

[0030] Figure 2 A cross-sectional FE-SEM image (1000x magnification) showing the cross-section of the carrier slice in Example 3.

[0031] Figure 3 A cross-sectional FE-SEM image (2000x magnification) showing the cross-section of the carrier slice in Example 3. Detailed Implementation

[0032] The preferred embodiments of the technology disclosed herein will now be described. It should be noted that matters other than those specifically mentioned in this specification, i.e., matters necessary for implementation, can be understood based on the technical content taught in this specification and general technical knowledge of those skilled in the art. The content of the technology disclosed herein can be implemented based on the content disclosed in this specification and general technical knowledge in the art. It should be noted that the expression "A to B" indicating a range in this specification means A or more and B or less.

[0033] <Carrier Structure>

[0034] Figure 1 A diagram schematically illustrating the structure of the carrier structure disclosed herein. For example... Figure 1As shown, the carrier structure 10 disclosed herein comprises a resin matrix 20 and porous particles 30. The carrier structure 10 disclosed herein is a carrier structure capable of loading various active substances such as adsorbents and catalysts. As the active substance, a CO2 adsorbent that chemically adsorbs carbon dioxide (CO2) is preferably preferred. Specifically, examples of CO2 adsorbents include amine compounds having primary to tertiary amino groups, such as amino organosilanes, aliphatic amines, and aliphatic polyamines. The carrier structure 10 disclosed herein, for example, can be suitably used as a CO2 adsorption material by loading CO2 adsorbents such as amine compounds capable of absorbing CO2.

[0035] The carrier structure 10 can be formed into a sheet, cuboid, cube, prism, cylinder, sphere, etc. There are no particular limitations, but it is preferred that the carrier structure 10 is formed into a sheet. When the carrier structure 10 is sheet-shaped, it is preferred that the thickness is, for example, 0.3 mm or more and 5 mm or less.

[0036] The resin matrix 20 contained in the carrier structure 10 disclosed herein is as follows: Figure 1 As shown, the structure has a three-dimensional mesh structure containing pores 22. The resin matrix 20 may function as a framework in the carrier structure 10. The resin matrix 20 may be formed, for example, by bonding resin grains. The pores 22 may be interconnected pores. A plurality of porous particles 30 are disposed within the pores 22. The porous particles 30 have a plurality of pores 32. The porous particles 30 preferably exist in the pores 22 in a state where they are mostly separated from the resin matrix 20. The presence of the resin matrix 20 and the porous particles 30 in the carrier structure 10 can be confirmed, for example, by observing the surface or cross-section of the carrier structure 10 using a scanning electron microscope (SEM).

[0037] Regarding the carrier structure 10 disclosed herein, by distributing porous particles 30 in the pores 22 of the resin matrix 20, the water absorption is appropriately improved. This allows for the loading of more active material than previously possible, increasing the loading per unit volume and improving the recovery and separation performance of harmful components. This is not intended to limit the technology disclosed herein; the reasons for achieving this effect are presumably as follows. In the carrier structure 10, by distributing porous particles 30 in the pores 22 of the resin matrix 20, the porous particles 30 can exist in a state where the pores 32 of the porous particles 30 are not crushed or buried by the resin. Furthermore, the resin matrix 20 also has suitable pores 22, so active material can also be loaded into these pores 22. Therefore, high water absorption can be achieved in the carrier structure 10 disclosed herein.

[0038] As described above, the carrier structure 10 has a high water absorption rate. Without particular limitation, the water absorption rate of the carrier structure 10 disclosed herein, based on the Archimedes method, is preferably 140% or more, more preferably 145% or more, even more preferably 147% or more, and can be 190% or more, or 200% or more. Because the carrier structure 10 has a high water absorption rate, the loading of active material per unit volume increases, thereby improving the separation and recovery performance of harmful components. From this viewpoint, a high water absorption rate is preferred, but there is no particular limitation on the upper limit. For example, the water absorption rate of the carrier structure 10 based on the Archimedes method can be 400% or less, 370% or less, or 350% or less. It should be noted that the "water absorption rate of the carrier structure" can be calculated based on the Archimedes method. More specifically, the dry weight W of the carrier structure is measured. Air , weight in water W Aq Water content W a+w Based on the following formula (1), the water absorption rate (Aw) can be calculated.

[0039] Aw (%) = (W a+w -W Air ) / W Air ×100 (1)

[0040] Without particular limitation, 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 for suitable contact between the component to be recovered (e.g., CO2) and the active substance (e.g., amine compound). The porosity of the carrier structure 10 based on the Archimedes method is preferably, for example, 90% or less, and may be 86% or less. It should be noted that the "porosity of the carrier structure" can be calculated based on the Archimedes method. More specifically, the dry weight W of the carrier structure is measured. Air , weight in water W Aq Water content W a+w Based on the following formula (2), the porosity (P) can be calculated.

[0041] P(%) = (W) a+w -W Air ) / (W a+w -W Aq )×100 (2)

[0042] Furthermore, while not particularly limited, the carrier structure 10 preferably 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 can be 150°C or higher, or 160°C or higher. Therefore, the carrier structure 10 disclosed herein can be suitably used in environments exceeding 100°C and in relatively humid environments. The hot water resistance of the carrier structure 10 is preferably, for example, 250°C or lower, and can be 200°C or lower. It should be noted that the "hot water resistance of the carrier structure" can be evaluated by drying the carrier structure immersed in hot water in an autoclave and measuring its strength using conventionally known tensile tests.

[0043] The resin matrix 20 has a three-dimensional network structure comprising a plurality of micropores 22. The average pore size 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 can be 1 μm or more. This appropriately improves the water absorption of the carrier structure 10. If the average pore size A of the resin matrix 20 is too large, the porous particles 30 may detach from the resin matrix 20. From this viewpoint, the average pore size A of the resin matrix 20 is preferably, for example, 10 μm or less, more preferably 7 μm or less, even more preferably 5 μm or less, and even more preferably 3 μm or less. It should be noted that the "average pore size of the resin matrix" can be determined using the mercury indentation method with a commercially available mercury porosimeter.

[0044] The resin matrix 20 contains resin and can be formed by bonding the grains of the resin. While not particularly limited, it is preferable that the resin matrix 20 contains a resin with 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, but can be 100°C or higher, or 120°C or higher. For example, the glass transition temperature of the resin contained in the resin matrix 20 can be 260°C or lower, or 250°C or lower. It should be noted that the "glass transition temperature of the resin" can be determined using conventionally known methods such as differential scanning calorimetry (DSC) and dynamic viscoelasticity determination (DMA).

[0045] Furthermore, without particular limitation, it is preferable that the resin matrix 20 contains a resin with high hot water resistance. This improves 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 can be 150°C or higher, or 160°C or higher. The hot water resistance of the resin contained in the resin matrix 20 is preferably, for example, 300°C or lower, and can be 250°C or lower, or 200°C or lower. It should be noted that "hot water resistance of the resin" can be the nominal value (catalog value) according to the respective manufacturers, etc.

[0046] There is no particular limitation on the resin content. When the total mass of the carrier structure 10 is set to 100% by mass, it 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 can be 40% by mass or more and 50% by mass or less. This allows for a suitable increase in the water absorption of the carrier structure 10. Furthermore, from the viewpoint of more suitablely increasing the water absorption rate of the carrier structure 10, it is preferable that the proportion of porous particles 30 is higher than that of the resin constituting the resin matrix 20. From this viewpoint, the resin content can be less than 50% by mass, for example, it can be 40% by mass or more and 48% by mass or less.

[0047] There are no particular limitations on the resin components included in the resin matrix 20, such as acrylic resins, cellulose resins, and resins classified as superplastics (super engineering plastics). The resin matrix 20 may contain any one of the above-mentioned resins individually, or may contain two or more in combination.

[0048] As an acrylic resin, it includes all polymers and their derivatives containing alkyl methacrylates as constituent monomers. It should be noted that in this specification, the terms "(meth)acrylate" and the like are used generally to refer to acrylates and / or methacrylates. Examples of acrylic resins include polymers containing alkyl methacrylates as main monomers (comprising 50% or more of the total monomer mass), and copolymers containing the main monomer and copolymerizable by the main monomer. Specifically, examples include poly(meth)acrylic acid, poly(meth)acrylamide, and polymethyl methacrylate (PMMA). Preferably, the resin matrix 20 contains methacrylic acid or PMMA.

[0049] Cellulose-based resins comprise compounds (cellulose derivatives) entirely derived from cellulose. Specifically, examples include ethyl cellulose (EC), hydroxyethyl cellulose (HEC), ethyl methyl cellulose (EMC), hydroxyethyl methyl cellulose (HEMC), nitrocellulose, and diacetyl cellulose. Preferably, the resin matrix 20 comprises ethyl cellulose.

[0050] Superplastics are thermoplastic resins with extremely high heat resistance and mechanical strength. Specifically, examples of superplastics include fluorinated resins such as polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluorovinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), trifluoroethylene chloropolymer (PCTFE), tetrafluoroethylene-ethylene copolymer (ETFE), trifluoroethylene-ethylene chloropolymer (ECTFE), and vinylidene fluoride homopolymer (PVDF); thermoplastic polyimides such as polybenzimidazole (PBI), polyimide (PI), polyetherimide (PEI), and polyamide-imide (PAI); and polyethersulfone (PES), polyetheretherketone (PEEK), polyether sulfide, and polyphenylene sulfide. Preferably, the resin matrix 20 includes PEI, PES, and PVDF.

[0051] The porous particles 30 can be any inorganic porous material capable of supporting active substances such as adsorbents and catalysts. For example, porous materials with a large specific surface area are preferred. As porous particles 30, oxides of half-metallic elements and metallic elements, or their solid solutions, are preferred. Specifically, examples include silica particles, alumina particles, cerium dioxide particles, zirconium oxide particles, and titanium dioxide particles. Any one or more of these can be used without particular limitation. Among them, the porous particles 30 preferably include silica particles.

[0052] The porous particles 30 have a plurality of pores 32. The porous particles 30 may be, for example, mesoporous materials with mesopores. The term "mesoporous" refers to pores with a pore size of 2 nm or more but less than 50 nm, based on IUPAC classification. The average pore size B of the porous particles 30 is preferably 2 nm or more, more preferably 10 nm or more, and even more preferably 12 nm or more. Thus, when loading active substances, they can be suitably introduced into the pores 32. The average pore size B of the porous particles 30 is preferably 100 nm or less, more preferably 70 nm or less, even more preferably 50 nm or less, even more preferably less than 50 nm, for example 40 nm or less, and particularly preferably 30 nm or less. Thus, the specific surface area of ​​the porous particles 30 can be suitably increased, and the water absorption of the carrier structure 10 can be further improved. It should be noted that the "average pore size of the porous particles" can be measured for the carrier structure using a commercially available pore size distribution measuring device or by using a gas adsorption method based on the BJH method.

[0053] There is no particular limitation on the average particle size of the porous particles 30. If the average particle size of the porous particles 30 is too small, they tend to become difficult to disperse in the carrier structure 10. From this perspective, the average particle size of the porous particles 30 can be, for example, 100 nm or more, 1 μm or more, 3 μm or more, or 5 μm or more. On the other hand, as mentioned above, the porous particles 30 contain multiple voids (pores 32), so if the average particle size is too large, they may easily crack due to collisions between the porous particles. From this perspective, the average particle size of the porous particles 30 can be, for example, 100 μm or less, 50 μm or less, or 15 μm or less. Furthermore, in this specification, the term "average particle size of the porous particles" refers to the arithmetic mean of the equivalent diameter of a circle as measured by optical microscopy. The so-called circular equivalent diameter refers to the diameter of a circle whose area is the same as the area of ​​the ellipse formed by the longest diameter (major axis) of the porous particle observed under a microscope and the longest diameter (minor axis) of the line that intersects the major axis at a right angle. In this specification, the average particle size of the porous particles refers to the arithmetic mean of the circular equivalent diameters of 200 randomly selected porous particles.

[0054] From the viewpoint of increasing the contact area between the active substance and harmful components, a large specific surface area of ​​the porous particles 30 is preferred. There are no particular limitations, but the specific surface area of ​​the porous particles 30, as measured by the BET method (BET specific surface area), is preferably, for example, 190 m². 2 / g or more and 650m 2 / g or less, more preferably 200m 2 / g or more and 450m 2 / g or less. It should be noted that the "BET specific surface area of ​​porous particles" in this specification can be determined using a commercially available specific surface area measuring device and the nitrogen adsorption method.

[0055] Furthermore, from the viewpoint of increasing the loading of active substances, it is preferable that the porous particles 30 have a high oil absorption capacity. There are no particular limitations, but the oil absorption capacity of the porous particles 30 is preferably 100 ml / 100g or more and 400 ml / 100g or less, more preferably 130 ml / 100g or more and 380 ml / 100g or less. It should be noted that the "oil absorption capacity of the porous particles" can be determined using a general absorbance measuring device, using DBP (dibutyl phthalate) as the reagent liquid, and according to JIS K6217-4 (2008).

[0056] The content of porous particles 30 is not particularly limited. When the total mass of the carrier structure 10 is set to 100% by mass, it 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 can be 50% by mass or more and 60% by mass or less. This allows for a suitable increase in the water absorption of the carrier structure 10. Furthermore, from the viewpoint of more suitablely increasing the water absorption rate of the carrier structure 10, it is preferable that the content of porous particles 30 is higher than that of the resin component. From this viewpoint, the content of porous particles 30 can exceed 50% by mass, for example, it can be 52% by mass or more and 60% by mass or less.

[0057] While not particularly limited, in the carrier structure 10, the ratio (A / B) of the average pore size A of the resin matrix 20 to the average pore size 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. That is, the carrier structure 10 preferably has both relatively small pores (e.g., mesopores less than 50 nm) from the porous particles 30 and relatively large pores (e.g., pores of 0.5 μm or more) from the pores 22 of the resin matrix 20. This allows for a suitable improvement in the water absorption of the carrier structure 10.

[0058] While not particularly limited, in the carrier structure 10, the mass ratio of 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. Thus, by appropriately adjusting the balance between the average pore size A from the resin matrix 20 and the average pore size B from the porous particles 30, the water absorption rate of the carrier structure 10 can be improved.

[0059] <Manufacturing Method of Carrier Structure>

[0060] Secondly, an example of a method for manufacturing the carrier structure 10 disclosed herein will be described. The carrier structure 10 disclosed herein may include: a preparation step of preparing a carrier structure forming slurry; a molding step of making a molded body from the carrier structure forming slurry; an impregnation step of immersing the molded body in an aqueous solvent; and a drying step of drying the molded body after the impregnation step. Furthermore, the carrier structure 10 disclosed herein is not limited to being manufactured by the following manufacturing method.

[0061] In the preparation step, a slurry-like composition (slurry for carrier structure formation) comprising at least porous particles 30, resin, and an organic solvent is prepared. As an example, in the preparation step, porous particles 30 are added to an organic solvent and stirred. This disperses the porous particles 30 in the organic solvent. Next, resin is added to the organic solvent in which the porous particles 30 are dispersed and stirred. This dissolves the resin in the organic solvent. Without particular limitation, it is preferable that the porous particles 30 and resin are added to the organic solvent in the preparation step and stirred while heating to 40°C to 60°C.

[0062] The porous particles 30 described above are preferably used. Silica particles are preferred. As the resin, a resin that dissolves in an organic solvent and precipitates in a network structure during the impregnation process described later is preferred. PEI, PES, and PVDF are preferred. Regarding the mass ratio of porous particles 30 to resin, a mixture of, for example, 20:80 to 70:30 is preferred, a mixture of, more preferably, 30:70 to 65:35 is preferred, and a mixture of, even more preferably, 55:45 to 65:35 is preferred.

[0063] There are no particular limitations on the type of organic solvent, as long as it can dissolve the resin. Examples of organic solvents include amides such as diethylformamide, dimethylacetamide, N-methylpyrrolidone, and dimethylimidazolinone; alkyl ketones such as dimethyl sulfoxide, acetone, and methyl ethyl ketone; ethers such as tetrahydrofuran, dioxane, and diethylene glycol dimethyl ether; and glycol ethers such as ethylene glycol and diethylene glycol. One of these can be used alone, or two or more can be used in combination. There are no particular limitations on the mass ratio of organic solvents in the slurry used to form the carrier structure. The content of organic solvents in the slurry used to form the carrier structure is preferably, for example, 30% to 80% by mass. This allows for the suitable fabrication of molded articles during the molding process.

[0064] Furthermore, regarding the slurry for forming the carrier structure, conventionally known additives may be added as long as they do not significantly impair the effects of the technology disclosed herein. Examples of such additives include dispersants, plasticizers, defoamers, and thickeners. For example, hydrophilic polymers such as polyethylene glycol (PEG) are preferably used as additives. The content of additives in the slurry for forming the carrier structure is preferably, for example, 30% by mass or less, possibly 20% by mass or less, or possibly 10% by mass or less.

[0065] In the molding process, the carrier structure forming slurry prepared above is used to form a molded body. For example, by using a doctor blade, the carrier structure forming slurry is supplied to a glass substrate at a predetermined thickness, thereby producing a sheet-like molded body. Alternatively, by extruding the carrier structure forming slurry in a predetermined mold, printing it on a metal plate or metal screen, or impregnating it with a core material, a molded body of the desired shape can be produced.

[0066] In the impregnation process, the molded body prepared in the molding process is impregnated with an aqueous solvent (e.g., water). This replaces the organic solvent in the molded body with an aqueous solvent, causing resin to precipitate. The portions of the molded body where the organic solvent is replaced with an aqueous solvent become pores 22, and the resin matrix 20 is suitably formed during resin precipitation. Since the porous particles 30 are dispersed in the organic solvent, the resin matrix 20 is formed in a manner that incorporates the porous particles 30, with the porous particles 30 disposed within the pores 22 of the resin matrix 20.

[0067] There are no particular limitations on the aqueous solvent used in the impregnation process. The aqueous solvent may be water, a mixture of water and alcohol, or water with added surfactants. Preferably, ion-exchanged water, pure water, ultrapure water, or distilled water can be used as the aqueous solvent.

[0068] In the drying process, the molded body after the impregnation process is dried, and the aqueous solvent is removed from the molded body. This allows for the suitable fabrication of a carrier structure 10 having the aforementioned structure. There are no particular limitations on the drying method used in the drying process; for example, hot air drying devices, low-humidity air drying devices, vacuum drying devices, various infrared drying devices, electromagnetic induction drying devices, microwave drying devices, and drying-promoting methods such as air supply, pressure reduction, and heating can be used individually or in combination. The drying temperature (such as the set temperature of the drying device) can be appropriately selected based on the type and amount of solvent in the mixture; for example, it can be set to 60°C to 150°C, preferably 80°C to 120°C. Furthermore, the drying time is also only required to be selected based on the type and amount of the aqueous solvent and is not particularly limited.

[0069] As described above, a carrier structure 10 with good water absorption can be suitably manufactured. This carrier structure 10 is preferably used as a carrier for loading active substances, especially as a carrier for loading amine solutions that absorb CO2.

[0070] <Experimental Example>

[0071] The following describes test examples related to the technology disclosed herein, but it is not intended to limit the technology disclosed herein to these test examples.

[0072] <Fabrication of the Carrier Structure>

[0073] (Example 1)

[0074] First, 135g of porous silica particles (SiO2, average particle size 9μm) as porous particles, 80g of polyetherimide (PEI) as resin, 500g of dimethyl sulfoxide (DMSO) as organic solvent, and 28g of polyethylene glycol (PEG) as additive were prepared. This prepared the slurry for forming the carrier structure of Example 1. Next, using a doctor blade, the slurry for forming the carrier structure of Example 1 was coated onto a glass substrate to a thickness of 2mm, thereby obtaining a sheet-like molded body. This sheet-like molded body was immersed in water for 24 hours. Then, by drying the molded body after immersion in water at 80°C for 5 hours, the carrier structure of Example 1 (carrier sheet) was obtained in sheet form.

[0075] (Example 2)

[0076] In Example 2, SiO2 with an average particle size of 6 μm was used as the porous particles. Furthermore, the materials were mixed in a mass ratio of SiO2:PEI:DMSO:PEG = 18:11:67:4 to prepare a slurry for forming the carrier structure of Example 2. This slurry was then formed into a sheet, similar to Example 1, and the sheet was immersed in a solution of water and ethanol in a 5:95 ratio for 24 hours. Apart from these steps, the carrier structure of Example 2, formed into a sheet, was obtained in the same manner as in Example 1.

[0077] (Example 3)

[0078] In Example 3, N-methylpyrrolidone (NMP) was used as the solvent. Furthermore, the materials were mixed in a mass ratio of SiO2:PEI:NMP:PEG = 18:11:67:4 to prepare the slurry for forming the carrier structure of Example 3. Otherwise, the carrier structure of Example 3, formed in a sheet-like manner, was obtained in the same manner as in Example 1.

[0079] (Example 4)

[0080] In Example 4, SiO2 with an average particle size of 6 μm was used as the porous particles. Furthermore, the materials were mixed in a mass ratio of SiO2:PEI:DMSO:PEG = 14:8:51:27 to prepare the slurry for forming the support structure of Example 4. Otherwise, similar to Example 1, the support structure of Example 4, formed in a sheet-like shape, was obtained.

[0081] (Example 5)

[0082] In Example 5, SiO2 with an average particle size of 6 μm was used as the porous particles. Polyethersulfone (PES) was used as the resin. Furthermore, the materials were mixed in a mass ratio of SiO2:PES:NMP:PEG = 18:11:67:4 to prepare the slurry for forming the carrier structure of Example 5. Otherwise, similar to Example 1, the carrier structure of Example 5 was formed in a sheet-like shape.

[0083] (Example 6)

[0084] In Example 6, NMP was used as the solvent. Furthermore, the materials were mixed in a mass ratio of SiO2:PEI:NMP:PEG = 16:20:60:4 to prepare the slurry for forming the carrier structure of Example 6. Otherwise, similar to Example 1, the carrier structure of Example 6 was formed in a sheet-like shape.

[0085] (Example 7)

[0086] In Example 7, PES was used as the resin. N-methylpyrrolidone (NMP) was used as the solvent. The materials were mixed in a mass ratio of SiO2:PES:NMP:PEG = 24:13.5:56:6.5 to prepare the slurry for forming the carrier structure of Example 7. Otherwise, similar to Example 1, the carrier structure of Example 7 was formed in a sheet-like shape.

[0087] (Example 8)

[0088] In Example 8, PEI and polymethyl methacrylate (PMMA) were used as the resin. N-methylpyrrolidone (NMP) was used as the solvent. The slurry for forming the carrier structure of Example 7 was prepared by mixing the PEI, PMMA, NMP, and PEG in a mass ratio of 16:10:10:60:4. Otherwise, similarly to Example 1, the carrier structure of Example 8, formed in a sheet-like shape, was obtained.

[0089] (Example 9)

[0090] In Example 9, PEI and ethyl cellulose (EC) were used as resins. N-methylpyrrolidone (NMP) was used as a solvent. The slurry for forming the carrier structure of Example 9 was prepared by mixing the PEI, EC, NMP, and PEG in a mass ratio of 16:10:10:60:4. Otherwise, similar to Example 1, the carrier structure of Example 9 was formed in a sheet-like shape.

[0091] (Example 10)

[0092] In Example 10, 10g of porous silica particles (SiO2, average particle size 6μm) were prepared as porous particles. The porous silica particles were pressed into shape using a mold and a press to form... A molded body with a diameter of 15 mm and a thickness of 2 mm was obtained. The molded body was then dried at 800°C for 2 hours to obtain the carrier structure of Example 10.

[0093] (Example 11)

[0094] In Example 11, PES was used as the resin. NMP was used as the solvent. Furthermore, the slurry for forming the carrier structure of Example 11 was prepared by mixing the PES, NMP, and PEG in a mass ratio of 18:10.8:67:4.2. Otherwise, similar to Example 1, the carrier structure of Example 11 was formed in a sheet-like shape.

[0095] <Determination of the average pore size of the resin matrix>

[0096] The average pore size of the resin matrix contained in the carrier structure of each example was determined using mercury infiltration. Specifically, firstly, the carrier structure of each example was cut into pieces approximately 5 mm × 5 mm in size and pretreated by heating to 120°C for 3 hours. Secondly, mercury was introduced into the carrier structure within the range of 0.10 to 60000 psia using a mercury porosimeter (Micrometrititics, Auto Pore IV 9500) to obtain the pore distribution of each example. The average pore size A (μm) of the resin matrix contained in the carrier structure of each example was calculated from the peak positions of the obtained pore distribution. The results are shown in Table 1. Furthermore, Example 10 did not contain resin, and the pore size calculated using the same method as above was used as the average pore size A, and the results are shown in Table 1.

[0097] <Determination of the average pore size of porous particles>

[0098] The average pore size of the porous particles contained in the support structures of each example was determined using nitrogen adsorption. Specifically, firstly, each support structure was cut into pieces approximately 5 mm × 5 mm in size and pretreated under vacuum at 120°C for 3 hours. Secondly, using a pore size distribution measuring device (MicrotracBEL, BELSORPMINI), nitrogen was introduced at 77 K to obtain the adsorption isotherms for each example. The obtained adsorption isotherms were converted into pore size distribution using the BJH method, and the pore volume V (cm² / g) and specific surface area S (m² / g) were calculated. 2 / g). Then, the average pore size B (nm) of the porous particles contained in the carrier structure of each example was calculated using the following formula: average pore size B (nm) = 4V / S. The results are shown in Table 1.

[0099] <Determination of water absorption and porosity>

[0100] For each example of the carrier structure, the water absorption and porosity were determined based on the Archimedes method. Specifically, firstly, the dry weight W of each example of the carrier structure was measured. Air Next, the carrier structures of each example were immersed in distilled water and then placed in a desiccator equipped with a vacuum pump for 45 minutes under vacuum. The weight W in the water was then measured. Aq and water content weight W a+w Then, based on the following equation (3), the water absorption rate (Aw) is calculated. In addition, based on the following equation (4), the porosity (P) is calculated. The results are shown in Table 1.

[0101] Aw (%) = (W a+w -W Air ) / W Air ×100 (3)

[0102] P(%) = (W) a+w -W Air ) / (W a+w -W Aq )×100 (4)

[0103] <Observation of the carrier structure>

[0104] The cross-section of the carrier structure in Example 3 was observed using a scanning electron microscope (SEM). Figure 2 The image shown in Example 3 is an SEM image (magnification: 1000x). Figure 3 The image shown is an SEM image of Example 3 (magnification: 2000x).

[0105] [Table 1]

[0106]

[0107] As shown in Table 1, the water absorption rate in Examples 1-9 and Example 11 is over 147%. This is presumably because the resin matrix in Examples 1-9 and Example 11 has a three-dimensional network structure containing fine pores, with porous particles disposed within these pores, thus exhibiting suitable water absorption. On the other hand, in the carrier structure of Example 10, which is resin-free and composed of porous particles, although the porosity ratios of Examples 6, 8, and 9 are high, the water absorption ratios of Examples 6, 8, and 9 are low. This is presumably because although Example 10 has many mesopores from the porous particles, it lacks relatively large pores exceeding 0.5 μm from the resin matrix, therefore the water absorption is not adequately improved.

[0108] The above description provides detailed examples of the technology disclosed herein, but these are merely illustrative and do not limit the scope of the claims. The technology described in the claims includes embodiments that incorporate various modifications and alterations to the specific examples described above.

[0109] It should be noted that the technology disclosed herein includes the following items 1 to 8. Items 1 to 8 are not limited to the embodiments described above.

[0110] Project 1 relates to a carrier structure for loading active substances. The carrier structure in Project 1 includes a resin matrix and porous particles having mesoporous structures, the resin matrix having a three-dimensional network structure containing fine pores, and the porous particles being disposed in the fine pores of the resin matrix.

[0111] Project 2 is the carrier structure described in Project 1, wherein the average pore size A of the resin matrix is ​​0.5 μm or more and 10 μm or less. Alternatively, the average pore size B of the porous particles is 10 nm or more and 50 nm or less. Alternatively, the average pore size A of the resin matrix is ​​0.5 μm or more and 5 μm or less, and the average pore size B of the porous particles is 10 nm or more and 40 nm or less.

[0112] Item 3 is the carrier structure described in Item 1 or Item 2, wherein the ratio (A / B) of the average pore size A of the resin matrix to the average pore size B of the porous particles is 20 or more and 200 or less.

[0113] Project 4 is any of the carrier structures described in Projects 1 to 3, wherein the porosity based on the Archimedes method is 75% or more and 90% or less.

[0114] Project 5 is any of the carrier structures described in Projects 1 to 4, wherein the water absorption rate based on the Archimedes method is above 145% and below 350%.

[0115] Item 6 is any of the carrier structures described in Items 1 to 5, wherein the hot water resistance is above 120℃ and below 250℃.

[0116] Item 7 is the carrier structure described in any one of Items 1 to 6, wherein the resin matrix comprises a resin with a glass transition temperature of 70°C or higher and 250°C or lower.

[0117] Item 8 is the carrier structure described in any one of Items 1 to 7, wherein the porous particles include at least one selected from silica particles, alumina particles, cerium dioxide particles, zirconium oxide particles, and titanium dioxide particles.

[0118] Industrial availability

[0119] According to the present invention, a carrier structure with excellent water absorption can be provided.

[0120] Explanation of reference numerals in the attached figures

[0121] 10. Carrier Structure

[0122] 20 Resin matrix

[0123] 22 fine pores

[0124] 30 porous particles

[0125] 32 fine pores

Claims

1. A carrier structure for loading active substances, comprising a resin matrix and porous particles having multiple mesopores, wherein the resin matrix has a three-dimensional network structure containing fine pores, and the porous particles are disposed in the fine pores of the resin matrix.

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

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

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

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

6. The carrier structure according to any one of claims 1 to 4, wherein, The porosity based on the Archimedes method is above 75% and below 90%.

7. The carrier structure according to any one of claims 1 to 4, wherein, The water absorption rate based on the Archimedes method is above 145% and below 350%.

8. The carrier structure according to any one of claims 1 to 4, wherein, It is resistant to hot water temperatures above 120℃ and below 250℃.

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

10. The carrier structure according to any one of claims 1 to 4, wherein, The porous particles include at least one selected from silica particles, alumina particles, cerium dioxide particles, zirconium oxide particles, and titanium dioxide particles.

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