Method for regenerating an acid gas adsorption device, method for manufacturing an acid gas adsorption device, and method for operating an acid gas adsorption device

Abstract

Provided are: a regeneration method for an acid-gas adsorption device and an operating method for an acid-gas adsorption device, the methods being capable of smoothly recovering the acid-gas recovery performance and reducing running costs; and a manufacturing method for an acid-gas adsorption device, the method being capable of manufacturing an acid-gas adsorption device achieving superior acid-gas recovery performance. A regeneration method for an acid-gas adsorption device according to an embodiment of the present invention includes: a step for causing an acid gas to be adsorbed by an acid-gas adsorbent by supplying the acid gas to an acid-gas adsorption device so as to come into contact with an acid-gas adsorbing layer; a step for causing the acid gas to be desorbed from the acid-gas adsorbent; and a step for supplying the acid-gas adsorbent to the acid-gas adsorbing layer of the acid-gas adsorption device, which has been subjected to the step for causing the acid gas to be adsorbed and the step for causing the acid gas to be desorbed, so that the acid-gas adsorbent is attached to the acid-gas adsorbing layer.

Description

[Technical Field]

[0001] The present invention relates to a method for regenerating an acid gas adsorption apparatus, a method for manufacturing an acid gas adsorption apparatus, and a method for operating an acid gas adsorption apparatus. [Background technology]

[0002] In recent years, efforts have been made to separate and recover acidic gases contained in the atmosphere in order to reduce environmental impact. One example of such acidic gas is carbon dioxide (hereinafter sometimes referred to as CO2), which is a major cause of global warming. A representative example of such efforts is the Carbon dioxide Capture, Utilization and Storage (CCUS) cycle. As a carbon dioxide adsorption device used for such carbon dioxide separation and recovery, a CO2 capture absorption structure has been proposed, comprising a honeycomb substrate having multiple partition walls that form multiple flow channels, and functional structural units arranged in and on the partition walls (see, for example, Patent Document 1). Such a CO2 capture absorption structure can capture CO2 from the gaseous fluid flowing through the absorption structure, and the captured CO2 can be desorbed under predetermined conditions. However, when the CO2 capture absorption structure described in Patent Document 1 is repeatedly used to adsorb and desorb CO2 contained in the atmosphere, the CO2 recovery rate may gradually decrease due to impurities in the atmosphere and repeated heat treatment. In this case, the entire CO2 capture absorption structure needs to be replaced, which leads to increased running costs. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2013 / 119929 [Overview of the project] [Problems that the invention aims to solve]

[0004] The main object of the present invention is to provide a method for regenerating an acid gas adsorption apparatus and a method for operating an acid gas adsorption apparatus that can smoothly restore the acid gas recovery performance and reduce running costs, as well as a method for manufacturing an acid gas adsorption apparatus that can produce an acid gas adsorption apparatus having excellent acid gas recovery performance. [Means for solving the problem]

[0005] [1] A method for regenerating an acid gas adsorption apparatus according to an embodiment of the present invention includes: a step of supplying an acid gas to an acid gas adsorption apparatus comprising a substrate and an acid gas adsorption layer disposed on the surface of the substrate, which includes an acid gas adsorption material, so as to bring the acid gas into contact with the acid gas adsorption layer, thereby adsorbing the acid gas onto the acid gas adsorption material; a step of desorbing the acid gas from the acid gas adsorption material; and a step of supplying an acid gas adsorption material to the acid gas adsorption layer of the acid gas adsorption apparatus in which the steps of adsorbing the acid gas and desorbing the acid gas have been carried out, thereby adhering the acid gas to it. [2] In the regeneration method for the acid gas adsorption apparatus described in [1] above, the acid gas may be carbon dioxide. [3] In the regeneration method for the acid gas adsorption apparatus described in [1] or [2] above, the substrate may be a honeycomb substrate having partitions defining a plurality of cells, and the acid gas adsorption layer may be formed on the surface of the partitions. [4] In the regeneration method for an acid gas adsorption apparatus described in any of [1] to [3] above, the material constituting the substrate is selected from cordierite, alumina, mullite, silicon carbide, silicon-silicon carbide composite material, silicon nitride, or a combination thereof. [5] In the method for regenerating an acid gas adsorption apparatus described in any of [1] to [4] above, the acid gas adsorbent is selected from nitrogen-containing compounds, organometallic structures, activated carbon, nitrogen-doped carbon, alkali compounds, carbonates, bicarbonates, zeolites, ionic liquids, or combinations thereof. [6] In the method for regenerating an acid gas adsorption apparatus described in any of [1] to [5] above, the acid gas adsorption layer may further include a porous carrier. [7] In the method for regenerating an acid gas adsorption apparatus described in any of [1] to [6] above, the acid gas adsorption layer may include particles containing at least the acid gas adsorbent and an organic binder capable of binding the particles. The organic binder may be soluble in a non-protic polar solvent and substantially insoluble in a protic polar solvent. In the step of supplying and adhering the acid gas adsorbent to the acid gas adsorption layer, particles containing at least the acid gas adsorbent may be supplied to the acid gas adsorption layer. [8] A method for manufacturing an acid gas adsorption apparatus according to another aspect of the present invention includes the steps of: supplying an acid gas to an acid gas adsorption apparatus comprising a substrate and an acid gas adsorption layer disposed on the surface of the substrate, which includes an acid gas adsorption material, so as to bring the acid gas into contact with the acid gas adsorption layer, thereby adsorbing the acid gas onto the acid gas adsorption material; desorbing the acid gas from the acid gas adsorption material; and supplying an acid gas adsorption material to the acid gas adsorption layer of the acid gas adsorption apparatus in which the steps of adsorbing the acid gas and desorbing the acid gas have been carried out, thereby adhering the acid gas to it. [9] A method for operating an acid gas adsorption apparatus according to yet another aspect of the present invention comprises an acid gas adsorption apparatus comprising a substrate and an acid gas adsorption layer disposed on the surface of the substrate, the acid gas adsorption layer including an acid gas adsorbent, comprising the steps of: supplying an acid gas to the acid gas adsorption layer so as to bring it into contact with the acid gas adsorption layer, thereby adsorbing the acid gas onto the acid gas adsorbent; and desorbing the acid gas from the acid gas adsorbent, wherein in the step of adsorbing the acid gas onto the acid gas adsorbent, the acid gas adsorbent is supplied to and adheres to the acid gas adsorption layer together with the acid gas. [Effects of the Invention]

[0006] According to embodiments of the present invention, it is possible to realize a method for regenerating an acid gas adsorption apparatus and an operating method for an acid gas adsorption apparatus that can smoothly restore the acid gas recovery performance and reduce running costs, as well as a method for manufacturing an acid gas adsorption apparatus that can produce an acid gas adsorption apparatus having excellent acid gas recovery performance. [Brief explanation of the drawing]

[0007] [Figure 1] Figure 1 is a schematic perspective view of a carbon dioxide adsorption device according to one embodiment of the present invention. [Figure 2] Figure 2 is a schematic cross-sectional view of the carbon dioxide adsorption apparatus shown in Figure 1. [Modes for carrying out the invention]

[0008] Embodiments of the present invention will be described below with reference to the drawings, but the present invention is not limited to these embodiments.

[0009] A. Outline of the regeneration method for acid gas adsorption devices Figure 1 is a schematic perspective view of a carbon dioxide adsorption apparatus according to one embodiment of the present invention; Figure 2 is a schematic cross-sectional view of the carbon dioxide adsorption apparatus of Figure 1. A method for regenerating an acid gas adsorption device according to one embodiment of the present invention includes: a step of supplying an acid gas to an acid gas adsorption device 100 comprising a base material 1 and an acid gas adsorption layer 15 disposed on the surface of the base material 1, which contains an acid gas adsorbent, so that the acid gas comes into contact with the acid gas adsorption layer 15 and the acid gas is adsorbed by the acid gas adsorbent (adsorption step); a step of desorbing the acid gas from the acid gas adsorbent (desorption step); and a step of supplying an acid gas adsorbent to the acid gas adsorption layer 15 of the acid gas adsorption device 100 after the adsorption step and desorption step have been carried out and adhering it (adhesion step). The inventors of this invention have discovered that the lifespan of the substrate is longer than that of the acid gas adsorbent, and have completed this invention. More specifically, an acid gas adsorbent is newly supplied and attached to the acid gas adsorption layer of an acid gas adsorption apparatus in which an adsorption process and a desorption process have been carried out. As a result, even if the acid gas recovery performance of the acid gas adsorption layer deteriorates during the adsorption and desorption processes, the attachment process can smoothly restore the acid gas recovery performance of the acid gas adsorption layer. Consequently, the substrate can be reused, and running costs can be reduced.

[0010] Examples of acidic gases include carbon dioxide (CO2), hydrogen sulfide, sulfur dioxide, nitrogen dioxide, and hydrogen chloride. In one embodiment, the acid gas is carbon dioxide (CO2). In this embodiment, the acid gas adsorption device 100 is a carbon dioxide adsorption device 100, the acid gas adsorption layer 15 is a carbon dioxide adsorption layer 15, and the acid gas adsorbent is a carbon dioxide adsorbent. Hereinafter, the carbon dioxide adsorption device 100 as an embodiment of the acid gas adsorption device will be described in detail.

[0011] B. Carbon Dioxide Adsorption Device As described above, the carbon dioxide adsorption device 100 includes a substrate 1 and a carbon dioxide adsorption layer 15. The structure of the substrate 1 is not particularly limited, and examples include a honeycomb structure, a filter structure such as a filter cloth; a pellet structure, etc. The carbon dioxide adsorption layer 15 is not particularly limited as long as it is disposed on the surface of the substrate 1.

[0012] B-1. Substrate (Honeycomb Substrate) In one embodiment, the substrate 1 is a honeycomb substrate 10 having a plurality of cells 14. The cell 14 extends from the first end face 1a (inflow end face) to the second end face 1b (outflow end face) of the honeycomb substrate 10 in the length direction (axial direction) of the honeycomb substrate 10 (see FIG. 2). The cell 14 has an arbitrary appropriate shape in a cross section in a direction orthogonal to the length direction of the honeycomb substrate 10. Examples of the cross-sectional shape of the cell include a triangle, a quadrilateral, a pentagon, a polygon with six or more sides, a circle, and an ellipse. The cross-sectional shapes and sizes of the cells may all be the same, or at least some may be different. Among such cross-sectional shapes of the cells, hexagons and quadrilaterals are preferably mentioned, and squares, rectangles or hexagons are more preferably mentioned.

[0013] The cell density (that is, the number of cells 14 per unit area) in a cross section in a direction orthogonal to the length direction of the honeycomb substrate can be appropriately set according to the purpose. The cell density is, for example, 4 cells / cm 2 ~320 cells / cm 2 and can be. If the cell density is within such a range, the strength and effective GSA (geometric surface area) of the honeycomb substrate can be sufficiently ensured.

[0014] The honeycomb-shaped substrate 10 has an arbitrary appropriate shape (overall shape). Examples of the shape of the honeycomb-shaped substrate include a cylindrical shape with a circular bottom surface, an elliptical columnar shape with an elliptical bottom surface, a prismatic shape with a polygonal bottom surface, and a columnar shape with an irregular bottom surface. The honeycomb-shaped substrate 10 in the illustrated example has a cylindrical shape. The outer diameter and length of the honeycomb-shaped substrate can be appropriately set according to the purpose. Although not shown, the honeycomb-shaped substrate may have a hollow region in its central portion in a cross section in a direction orthogonal to the length direction.

[0015] The honeycomb-shaped substrate 10 typically includes an outer peripheral wall 11 and partition walls 13 located inside the outer peripheral wall 11. In the illustrated example, the outer peripheral wall 11 and the partition walls 13 are integrally formed. The outer peripheral wall 11 and the partition walls 13 may be separate.

[0016] The outer peripheral wall 11 has a cylindrical shape. The thickness of the outer peripheral wall 11 can be arbitrarily and appropriately set. The thickness of the outer peripheral wall 11 is, for example, 0.1 mm to 10 mm.

[0017] The partition walls 13 define a plurality of cells 14. More specifically, the partition walls 13 have a first partition wall 13a and a second partition wall 13b that are orthogonal to each other, and the first partition wall 13a and the second partition wall 13b define a plurality of cells 14. The cross-sectional shape of the cells 14 is square except for the portions where the first partition wall 13a and the second partition wall 13b contact the outer peripheral wall 11. Note that the configuration of the partition walls is not limited to the partition walls 13 described above. The partition walls may have a first partition wall extending in the radial direction and a second partition wall extending in the circumferential direction, and they may define a plurality of cells.

[0018] The thickness of the partition wall 13 can be appropriately set depending on the application of the honeycomb substrate. Typically, the thickness of the partition wall 13 is thinner than the thickness of the outer peripheral wall 11. For example, the thickness of the partition wall 13 is 0.03 mm to 0.6 mm. The thickness of the partition wall is measured, for example, by cross-sectional observation using an SEM (scanning electron microscope). If the thickness of the partition wall is within this range, the mechanical strength of the honeycomb substrate can be made sufficient, and the opening area (total area of ​​cells in the cross-section) can be made sufficient.

[0019] The porosity of the partition wall 13 can be appropriately set depending on the purpose. The porosity of the partition wall 13 is, for example, 15% or more, preferably 20% or more, and for example, 70% or less, preferably 45% or less. The porosity can be measured, for example, by the mercury intrusion method. The density of the partition walls 13 can be appropriately set depending on the purpose. For example, their density could be 1.7 g / cm³. 3 Preferably 1.8 g / cm³ 3 That's all; for example, 2.8 g / cm³ 3 Preferably, 2.6 g / cm³ 3 The following applies. Note that density can be measured, for example, by the mercury intrusion method.

[0020] Typical materials for the partition wall 13 include ceramics. Examples of ceramics include silicon carbide, silicon-silicon carbide composite materials, cordierite, mullite, alumina, silicon nitride, spinel, silicon carbide-cordierite composite materials, lithium aluminum silicate, and aluminum titanate. The materials constituting the partition wall can be used individually or in combination. Among the materials constituting the partition wall, cordierite, alumina, mullite, silicon carbide, silicon-silicon carbide composite materials, and silicon nitride are preferred, and silicon carbide and silicon-silicon carbide composite materials are preferred.

[0021] Such a honeycomb-shaped substrate 10 is typically manufactured by the following method. First, a binder and water or an organic solvent are added as needed to the material powder containing the ceramic powder described above, and the resulting mixture is kneaded to form a clay. The clay is then molded into a desired shape (typically by extrusion molding), dried, and fired as needed to produce the honeycomb-shaped substrate 10. When firing, for example, it is fired at 1200°C to 1500°C. The firing time is, for example, 1 hour or more and 20 hours or less.

[0022] B-2. Carbon dioxide adsorption layer In one embodiment, the carbon dioxide adsorption layer 15 is formed on the surface of the partition wall 13. In the honeycomb substrate 10, the gas channel 16 is formed in the portion of the cross-section of the cell 14 where the carbon dioxide adsorption layer 15 is not formed (typically the central portion). The carbon dioxide adsorption layer 15 may be formed over the entire inner surface of the partition wall 13 (i.e., surrounding the gas channel 16), as shown in the illustrated example, or it may be formed on a part of the surface of the partition wall. If the carbon dioxide adsorption layer 15 is formed over the entire inner surface of the partition wall 13, the CO2 removal efficiency can be improved.

[0023] The gas flow path 16 extends from the first end face 1a (inlet end face) to the second end face 1b (outlet end face), similar to the cell 14. The cross-sectional shape of the gas flow path 16 can be the same as that of the cell 14 described above, preferably a hexagon or quadrilateral, and more preferably a square, rectangle, or hexagon. The cross-sectional shape and size of the gas flow path 16 may all be the same, or at least some may differ.

[0024] The thickness of the carbon dioxide adsorption layer 15 is not particularly limited, but is, for example, 10 μm or more, preferably 50 μm or more, and for example, 1000 μm or less, preferably 500 μm or less.

[0025] B-2-1. Carbon dioxide adsorption layer made of carbon dioxide adsorbent material The carbon dioxide adsorption layer 15 contains a carbon dioxide adsorbent as an example of an acidic gas adsorbent. In one embodiment, the carbon dioxide adsorption layer consists of a carbon dioxide adsorbent and is directly supported on the partition wall and facing the gas flow path.

[0026] As the carbon dioxide adsorbent, any suitable compound capable of adsorbing and desorbing CO2 can be used. Examples of carbon dioxide adsorbents include nitrogen-containing compounds (described later); alkali compounds such as sodium hydroxide and potassium hydroxide; carbonates such as calcium carbonate and potassium carbonate; bicarbonates such as calcium bicarbonate and potassium bicarbonate; organometallic structures (MOFs) such as MOF-74, MOF-200, and MOF-210; zeolites; activated carbon; nitrogen-doped carbon; and ionic liquids.

[0027] Among carbon dioxide adsorbents, nitrogen-containing compounds are more preferably used. More specifically, nitrogen-containing compounds include amine compounds such as monoethanolamine, diethanolamine, triethanolamine, N-(3-aminopropyl)diethanolamine, aminopropyltrimethoxysilane, polyvinylamine, methyldiethylamine, and tetraethylenepentamine; piperazine compounds such as 1-(2-hydroxyethyl)piperazine; aminosilane coupling agents such as polyethyleneimine-trimethoxysilane, aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-(2-aminoethyl)-3-aminopropyl-trimethoxysilane; organic polymers having primary to tertiary amino groups such as polyethyleneimine, polyamidoamine, and polystyrene with amino groups; organic monomers having primary to tertiary amino groups such as ethyleneimine and styrene with amino groups; and organic / inorganic compounds with amino groups as substituents. Carbon dioxide adsorbents can be used alone or in combination.

[0028] In this embodiment, the carbon dioxide adsorption layer substantially contains no components other than the carbon dioxide adsorbent. When the carbon dioxide adsorption layer consists of a carbon dioxide adsorbent, the content ratio of the carbon dioxide adsorbent in the carbon dioxide adsorption layer is typically 95.0% by mass or more and 100% by mass or less. When the content ratio of the carbon dioxide adsorbent is within the above range, an excellent CO2 recovery rate can be stably ensured.

[0029] A carbon dioxide adsorption layer made of a carbon dioxide adsorbent is typically prepared by the following method. First, a carbon dioxide adsorption solution is prepared by dissolving the carbon dioxide adsorbent described above in a solvent. Examples of solvents include water, alcohols, and diols. The solvent can be used alone or in combination. Among the solvents, aqueous solvents (water and mixed solvents containing water) are preferred. Next, the carbon dioxide adsorption solution is applied to a substrate (specifically, a partition wall), the coating is dried, and if necessary, sintered to form a carbon dioxide adsorption layer made of the carbon dioxide adsorbent.

[0030] B-2-2. Carbon dioxide adsorption layer containing an ionic liquid and a carbon dioxide adsorbent other than an ionic liquid. The carbon dioxide adsorption layer may contain an ionic liquid. In this case, the carbon dioxide adsorption layer preferably contains an ionic liquid and a carbon dioxide adsorbent other than the ionic liquid (hereinafter referred to as "other carbon dioxide adsorbent"). The ionic liquid is typically a coating of the other carbon dioxide adsorbent (for example, a nitrogen-containing compound). Including an ionic liquid in the carbon dioxide adsorption layer can improve the performance and extend the lifespan of the carbon dioxide adsorbent.

[0031] Ionic liquids are liquid "salts" composed solely of ions (anions and cations), and are in a liquid state at room temperature and pressure (23°C, 0.1 MPa). Examples of cations in ionic liquids include ammonium-based ions such as imidazolium salts and pyridinium salts, phosphonium ions, sulfonium salts, and inorganic ions. Examples of anions in ionic liquids include halogen-based ions such as bromide ions and triflate; boron-based ions such as tetraphenylborate; phosphorus-based ions such as hexafluorophosphate; and sulfur-based ions such as alkyl sulfonates. Such ionic liquids can be used individually or in combination. Among ionic liquids, a combination of imidazolium salts as cations and triflate as anion is preferred.

[0032] When the carbon dioxide adsorption layer contains both an ionic liquid and other carbon dioxide adsorbents, the total content ratio of the ionic liquid and other carbon dioxide adsorbents (i.e., the total amount of carbon dioxide adsorbents) in the carbon dioxide adsorption layer is, for example, 30% by mass or more, preferably 50% by mass or more, and for example, 100% by mass or less, preferably 99% by mass or less. In this embodiment, the content of the ionic liquid is, for example, 0.000001 parts by mass or more, preferably 0.00001 parts by mass or more, and for example, 0.1 parts by mass or less, preferably 0.05 parts by mass or less, per 1 part by mass of the other carbon dioxide adsorbent. When the content of the ionic liquid is within the above range, the performance of the carbon dioxide adsorbent and its lifespan can be stably improved and extended.

[0033] B-2-3. Carbon dioxide adsorption layer containing carbon dioxide adsorbent and porous material In one embodiment, the carbon dioxide adsorption layer further includes a porous carrier in addition to the carbon dioxide adsorbent described above. In this case, the carbon dioxide adsorbent is typically supported on the porous carrier and faces the gas flow path. When the carbon dioxide adsorption layer includes a porous carrier, new carbon dioxide adsorbent can be stably attached to the carbon dioxide adsorption layer (specifically the porous carrier) during the adhesion process.

[0034] The porous support can form mesopores in the carbon dioxide adsorption layer. Examples of the porous support include metal-organic frameworks (MOFs) such as MOF-74, MOF-200, and MOF-210; activated carbon; nitrogen-doped carbon; mesoporous silica; mesoporous alumina; zeolite; and carbon nanotubes. Preferably, metal-organic frameworks (MOFs), activated carbon, zeolite, mesoporous silica, and mesoporous alumina are included. The porous support can be used alone or in combination. Preferably, a material different from the carbon dioxide adsorbent is employed as the porous support.

[0035] The BET specific surface area of the porous support is, for example, 50 m 2 / g or more, preferably 500 m 2 / g or more. If the surface area of the porous support is at least the above lower limit, the carbon dioxide adsorbent can be stably supported, and the CO2 recovery rate can be improved. The upper limit of the BET specific surface area of the porous support is typically 2000 m 2 / g or less.

[0036] When the carbon dioxide adsorption layer contains a carbon dioxide adsorbent and a porous support, the total content ratio of the carbon dioxide adsorbent and the porous support in the carbon dioxide adsorption layer is, for example, 30% by mass or more, preferably 50% by mass or more, and for example, 100% by mass or less, preferably 99% by mass or less. In the present embodiment, the content ratio of the porous support in the carbon dioxide adsorption layer is, for example, 0.1% by mass or more, preferably 10% by mass or more, and for example, 70% by mass or less, preferably 50% by mass or less. Also, the content ratio of the porous support is, for example, 0.01 part by mass or more, preferably 0.3 part by mass or more, and for example, 0.7 part by mass or less, preferably 0.5 part by mass or less, relative to 1 part by mass of the carbon dioxide adsorbent. When the content ratio of the porous support is within the above range, the carbon dioxide adsorbent can be more stably adhered in the adhesion step."

[0037] A carbon dioxide adsorption layer containing a carbon dioxide adsorbent and a porous carrier is typically prepared by the following method. First, a dispersion of the porous carrier is prepared by dispersing the porous carrier in a dispersion medium as needed, and the carbon dioxide adsorbent is added to the dispersion. The dispersion medium is, for example, the same as the solvent described in section B-2-1 above. Next, the dispersion containing the carbon dioxide adsorbent and the porous carrier is applied to a substrate (specifically, a partition wall), and the coating is dried and, if necessary, sintered to form a carbon dioxide adsorption layer. Alternatively, a dispersion containing a carbon dioxide adsorbent other than an ionic liquid and a porous carrier is applied to the substrate, the coating is dried, and if necessary, sintered, and then only the ionic liquid is applied to the substrate to form a carbon dioxide adsorption layer.

[0038] The method for producing a carbon dioxide adsorption layer containing a carbon dioxide adsorbent and a porous carrier is not limited to the above. For example, a dispersion of the porous carrier can be prepared by dispersing the porous carrier in a dispersion medium, and the dispersion can be applied to a substrate. After drying the coating, the film can be heated to, for example, 400°C to 800°C to sinter it, thereby forming a carrier-containing film. Subsequently, a liquid carbon dioxide adsorbent or a solution of the carbon dioxide adsorbent can be applied to the carrier-containing film at room temperature and atmospheric pressure. This allows the carbon dioxide adsorbent to permeate and be supported by the porous carrier of the carrier-containing film, thereby forming a carbon dioxide adsorption layer.

[0039] B-2-4. Carbon dioxide adsorption layer containing carbon dioxide adsorption particles and organic binder In another embodiment, the carbon dioxide adsorption layer includes particles containing at least the carbon dioxide adsorbent described above, and an organic binder. The particles containing the carbon dioxide adsorbent have carbon dioxide adsorption capacity and will be referred to as carbon dioxide adsorption particles below. The organic binder can bind the carbon dioxide adsorption particles and typically adheres to the substrate. The organic binder is soluble in aprotic polar solvents and substantially insoluble in protic polar solvents. That is, the organic binder is resistant to water, which is a protic polar solvent. Because the organic binder is substantially insoluble in protic polar solvents and is water resistant, swelling of the organic binder due to, for example, water vapor in the atmosphere can be suppressed. Therefore, volume expansion and / or decrease in strength of the organic binder can be suppressed, and consequently, changes in the structure by which the organic binder binds and holds the carbon dioxide adsorption particles can be suppressed. As a result, excellent carbon dioxide adsorption capacity can be maintained regardless of the usage environment.

[0040] The surface of the carbon dioxide adsorption layer opposite the substrate preferably has a three-dimensional network structure or a porous lamellar structure. This allows for efficient diffusion of acidic gases such as carbon dioxide from the surface to the interior of the carbon dioxide adsorption layer. In particular, since the organic binder is water-resistant, such a fine structure can be stably maintained on surfaces that come into contact with acidic gases, regardless of the usage environment.

[0041] The carbon dioxide adsorption particles are typically in a solid state at room temperature and pressure (23°C, 0.1 MPa). The carbon dioxide adsorption layer contains multiple carbon dioxide adsorption particles. The carbon dioxide adsorption particles, when contained in the carbon dioxide adsorption layer, may be primary particles or secondary particles formed by the aggregation of multiple primary particles.

[0042] In one embodiment, carbon dioxide adsorbent particles include the carbon dioxide adsorbent described above and a carrier supporting the carbon dioxide adsorbent. However, carbon dioxide adsorbent particles may consist only of the carbon dioxide adsorbent and may not include a carrier. In other words, acidic gas adsorbent particles can also consist only of a solid carbon dioxide adsorbent at room temperature and pressure.

[0043] Among the carbon dioxide adsorbents contained in the carbon dioxide adsorption particles, preferably, the nitrogen-containing compounds described above are included, and more preferably, the organic monomers having primary to tertiary amino groups described above, and the organic polymers having primary to tertiary amino groups described above. The weight-average molecular weight M of the organic polymer w (In terms of polystyrene equivalent) is, for example, 1,000 or more, preferably 50,000 or more, and for example, 1,000,000 or less, preferably 300,000 or less.

[0044] In one embodiment, the carbon dioxide adsorbent contained in the carbon dioxide adsorbent particles is substantially insoluble in protic polar solvents (typically water) and aprotic polar solvents. The solubility of the carbon dioxide adsorbent in water is, for example, 0.1 g / 100 g-H2O or less, preferably 0.05 g / 100 g-H2O or less. If the solubility of the carbon dioxide adsorbent in water is below the above upper limit, excellent water resistance can be stably imparted to the carbon dioxide adsorption device. The lower limit of the solubility of the carbon dioxide adsorbent in water is typically 0.01 g / 100 g-H2O or more. The solubility of the carbon dioxide adsorbent in aprotic polar solvent is, for example, 1 g / 100 g of aprotic polar solvent or less, preferably 0.5 g / 100 g of aprotic polar solvent or less. If the solubility of the carbon dioxide adsorbent in aprotic polar solvent is below the above upper limit, the dissolution of the carbon dioxide adsorbent in aprotic polar solvent can be suppressed during the manufacture of the carbon dioxide adsorption device. The lower limit of the solubility of the carbon dioxide adsorbent in aprotic polar solvent is typically 0.01 g / 100 g of aprotic polar solvent or more.

[0045] The solubility parameter of the carbon dioxide adsorbent is, for example, 7 or higher, preferably 8 or higher, and for example, 20 or lower, preferably 15 or lower. The solubility parameter can be calculated, for example, by the Hildebrandt method.

[0046] Any suitable carrier capable of supporting the carbon dioxide adsorbent can be used. Preferably, the carrier is the porous carrier described above. Metallic materials may also be used from the viewpoint of thermal conductivity. Examples include ferrous materials such as carbon steel and alloy steel; and non-ferrous metals and their alloys such as copper, aluminum, and nickel. In the case of metallic materials, the porous shape is not limited.

[0047] Any suitable organic compound capable of binding carbon dioxide adsorbent particles can be used as the organic binder. The organic binder is soluble in aprotic polar solvents and substantially insoluble in protic polar solvents. Examples of organic binders include fluoropolymers such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), perfluoroalkoxyalkanes (PFA), perfluoroethylene propene copolymer (FEP), and ethylene tetrafluoroethylene copolymer (ETFE); and amorphous plastics such as polyethersulfone (PES). The organic binder can be used alone or in combination. Among the organic binders, preferably, are organic binders that use water as a poor solvent (organic binders that are substantially insoluble in water), more preferably, are fluorine polymers, and even more preferably, are polyvinylidene fluoride. When the organic binder contains a fluorine polymer (polyvinylidene fluoride), excellent heat resistance and water resistance can be imparted to the carbon dioxide adsorption device.

[0048] The solubility of the organic binder in a protic polar solvent (typically water) is, for example, 0.1 g / 100 g-protic polar solvent or less, preferably 0.05 g / 100 g-protic polar solvent or less. If the solubility of the organic binder in a protic polar solvent (typically water) is below the above upper limit, excellent water resistance can be stably imparted to the acid gas adsorption device. The lower limit of the solubility of the organic binder in a protic polar solvent (typically water) is typically 0.01 g / 100 g- Protic polar solvent That's all.

[0049] The solubility parameter of the organic binder is, for example, 9 or higher, preferably 10 or higher, and for example, 15 or lower, preferably 13 or lower.

[0050] The carbon dioxide adsorption layer may contain carbon dioxide adsorption particles and an organic binder, as well as any suitable additives. The total content of carbon dioxide adsorbent particles and organic binder in the carbon dioxide adsorption layer is, for example, 30% by volume or more, preferably 50% by volume or more, and for example, 100% by volume or less, preferably 99% by volume or less. The volume percentage can be measured, for example, by microstructural observation or elemental analysis.

[0051] The content of carbon dioxide adsorbent particles in the carbon dioxide adsorption layer is, for example, 5% by volume or more, preferably 30% by volume or more. If the content of carbon dioxide adsorbent particles is above the lower limit mentioned above, the carbon dioxide adsorption performance of the carbon dioxide adsorption device can be sufficiently ensured. The upper limit of the content of carbon dioxide adsorbent particles is typically 85% by volume or less.

[0052] The organic binder content in the carbon dioxide adsorption layer is, for example, 5% by volume or more, preferably 15% by volume or more. If the organic binder content is above the lower limit mentioned above, it is possible to suppress the detachment of carbon dioxide adsorption particles from the carbon dioxide adsorption layer during the adsorption and / or desorption processes described later. The upper limit of the organic binder content is typically 70% by volume or less.

[0053] The carbon dioxide adsorption layer typically has interconnected pores. The porosity of the carbon dioxide adsorption layer 15 is, for example, 10% to 90%, preferably 10% to 60%, and more preferably 15% to 40%.

[0054] A carbon dioxide adsorption layer containing carbon dioxide adsorption particles and an organic binder can typically be prepared by the following method. First, the organic binder is dissolved in an aprotic polar solvent to prepare a binder solution.

[0055] A non-protic polar solvent can dissolve the above-mentioned organic binder, and the above-mentioned carbon dioxide adsorbent particles (more specifically, carbon dioxide adsorbent) are insoluble. Any suitable organic solvent can be used as the aprotic polar solvent. Examples of aprotic polar solvents include N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF). Aprotic polar solvents can be used alone or in combination. Among aprotic polar solvents, N-methyl-2-pyrrolidone (NMP) is preferred. When the aprotic polar solvent contains NMP, the organic binder (especially PVDF) can be dissolved more smoothly, and the dissolution of the carbon dioxide adsorbent can be stably suppressed.

[0056] The solubility parameter distance between the organic binder and the aprotic polar solvent is, for example, 3 or less, preferably 2 or less. If the solubility parameter distance between the organic binder and the aprotic polar solvent is below the above upper limit, the organic binder can be smoothly dissolved in the aprotic polar solvent. The lower limit of the solubility parameter distance between the organic binder and the aprotic polar solvent is typically 0 or more. The solubility parameter distance between the carbon dioxide adsorbent and the aprotic polar solvent is, for example, 2 or more, preferably 3 or more, and more preferably 4 or more. If the solubility parameter distance between the carbon dioxide adsorbent and the aprotic polar solvent is above the lower limit mentioned above, the dissolution of the carbon dioxide adsorbent in the aprotic polar solvent can be suppressed. The upper limit of the solubility parameter distance between the carbon dioxide adsorbent and the aprotic polar solvent is typically 10 or less.

[0057] Next, the carbon dioxide adsorbent particles described above are added to the binder solution and dispersed.

[0058] A solution of an organic binder in an aprotic polar solvent, in which carbon dioxide adsorbing particles are dispersed (particle-dispersed binder solution), is applied to the surface of the substrate by any suitable method, as described above. This process coats the surface of the substrate (typically the surface of the partition wall) with the particle-dispersed binder solution, forming a precursor film. The precursor film contains the carbon dioxide-adsorbing particles described above, the organic binder described above, and the aprotic polar solvent described above.

[0059] Next, the aprotic polar solvent contained in the precursor film is replaced with a poor solvent for the organic binder. Poor solvents dissolve organic binders less readily than the aprotic polar solvents (good solvents) described above, and in effect, organic binders are insoluble in poor solvents. The solubility parameter distance between the organic binder and the poor solvent is typically greater than the solubility parameter distance between the organic binder and the aprotic polar solvent (good solvent). The solubility parameter distance between the organic binder and the poor solvent is, for example, 2 or more, preferably 3 or more, and more preferably 4 or more.

[0060] Examples of poor solvents include protic polar solvents such as water, ethanol, butanol, and alcohols such as isopropyl alcohol (IPA); and chlorofluorocarbons such as hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), and hydrofluoroolefins (HFOs). Poor solvents can be used alone or in combination. Among poor solvents, water is preferred.

[0061] By substituting an aprotic polar solvent, a film stable in protic solvents can be obtained.

[0062] This allows for the formation of a carbon dioxide adsorption layer containing carbon dioxide adsorption particles and an organic binder on the surface of the substrate (typically the surface of the partition wall). Subsequently, the carbon dioxide adsorption layer is dried as needed.

[0063] Furthermore, the method for forming a carbon dioxide adsorption layer containing carbon dioxide adsorption particles and an organic binder is not limited to the embodiments described above. For example, first, a binder solution is prepared in the same manner as described above. Then, the porous carrier described above is added to the binder solution and dispersed.

[0064] This disperses the porous support in the binder solution, preparing a binder solution containing dispersed porous support (support-dispersed binder solution).

[0065] Next, the carrier-dispersed binder solution is applied to the surface of the substrate using the application method described above. This coats the surface of the substrate (typically the surface of the partition wall) with the carrier-dispersed binder solution, forming a precursor film. The precursor film contains the porous carrier described above, the organic binder described above, and the aprotic polar solvent described above.

[0066] Next, the aprotic polar solvent contained in the precursor film is replaced with the poor solvent described above. This forms a carrier-containing film on the surface of the substrate (typically the surface of the partition wall). Subsequently, the carrier-containing film is dried as needed. The carrier-containing film contains the porous carrier described above and the organic binder described above.

[0067] Next, the carbon dioxide adsorbent described above is supported on the porous carrier contained in the carrier-containing membrane. The carbon dioxide adsorbent used in this embodiment is preferably liquid at room temperature and atmospheric pressure. More specifically, the liquid carbon dioxide adsorbent is applied to the carrier-containing membrane at room temperature and atmospheric pressure using the coating method described above. As a result, the carbon dioxide adsorbent permeates and is supported on the porous carrier of the carrier-containing membrane, forming carbon dioxide adsorbent particles composed of an acidic gas adsorbent compound and a porous carrier. That is, the carbon dioxide adsorption layer is composed of carbon dioxide adsorbent particles and an organic binder. By the above method, a carbon dioxide adsorption layer containing carbon dioxide adsorption particles and an organic binder can be formed.

[0068] Such a carbon dioxide adsorption device 100 may be provided in a carbon dioxide adsorption facility, although it is not shown. In one embodiment, the carbon dioxide adsorption facility includes: a plurality of carbon dioxide adsorption devices; a fan for supplying a gas containing CO2 (CO2-containing gas) to a carbon dioxide adsorption layer; and a pump for sucking up the CO2 released from the carbon dioxide adsorption layer.

[0069] C. Adsorption and Desorption Processes As described above, a method for regenerating a carbon dioxide adsorption device according to one embodiment includes an adsorption step of adsorbing CO2 onto the carbon dioxide adsorbent material provided in the carbon dioxide adsorption device 100; and a desorption step of desorbing CO2 from the carbon dioxide adsorbent material.

[0070] In the adsorption process, a CO2-containing gas is typically circulated through the gas channel 16 to bring the CO2 into contact with the carbon dioxide adsorption layer 15. In one embodiment, the CO2-containing gas is air (atmosphere). The CO2 concentration in the CO2-containing gas is, for example, 100 ppm or more and 2 volume percent or less. In addition to CO2, the CO2-containing gas typically contains nitrogen. The temperature of the CO2-containing gas in the adsorption process is, for example, 0°C or more and 40°C or less. The pressure of the CO2-containing gas in the adsorption process is, for example, 0.3 × 10⁻⁶ 5 Pa or more 2.0×10 5 The pressure is below Pa. The relative humidity (RH) of the CO2-containing gas in the adsorption process is, for example, between 10%RH and 60%RH. The duration of the adsorption process is, for example, between 15 minutes and 3 hours. The flow rate of the CO2-containing gas in the adsorption process is, for example, between 0.5 m / sec and 5 m / sec.

[0071] As a result, the carbon dioxide adsorbent facing the gas channel 16 adsorbs CO2. The CO2 recovery rate in the adsorption process (= 100 - (CO2 concentration in the gas that has passed through the gas channel / CO2 concentration in the gas before it enters the gas channel × 100)) is, for example, 80% or more, preferably 85% or more, more preferably 90% or more, and for example, 100% or less.

[0072] The desorption process (sometimes called the desorption process) is carried out after the adsorption process. Typically, in the desorption process, the carbon dioxide adsorption device is heated and the detached CO2 is collected by sucking it up with a pump, or the collected CO2 is injected back into the carbon dioxide adsorption device, heated, and the detached CO2 is collected again. The temperature during the desorption process is, for example, above 40°C, preferably above 70°C, and for example below 200°C, preferably below 110°C. The duration of the desorption process is, for example, between 1 minute and 1 hour. As a result, the CO2 held by the carbon dioxide adsorbent is detached (released, desorbed) from the adsorbent. Therefore, the CO2 can be recovered and used for various applications (e.g., methanation).

[0073] These adsorption and desorption steps are preferably performed repeatedly. In one embodiment, the cycle of the adsorption and desorption steps is performed, for example, 10 or more times, preferably 30 or more times, more preferably 50 or more times, and even more preferably 100 or more times.

[0074] D. Adhesion process In one embodiment, the adhesion step is performed after the adsorption and desorption steps have been carried out (preferably after the adsorption and desorption cycles have been performed within the above range). Alternatively, the adhesion step may be performed after the CO2 recovery rate in the adsorption step falls below the above lower limit.

[0075] A pretreatment step may be performed after the adsorption and desorption steps, and before the adhesion step, to remove impurities adhering to the carbon dioxide adsorption device. When a pretreatment step is performed, impurities contained in the carbon dioxide adsorption device (for example, dirt and dust adhering to the surface of the carbon dioxide adsorption layer) are removed before the adhesion step, so that a new carbon dioxide adsorbent can be uniformly applied to the carbon dioxide adsorption layer in the subsequent adhesion step. Examples of pretreatment methods include passing a larger amount of air than the CO2-containing gas used in the adsorption process through the gas channel, or passing water vapor through the gas channel.

[0076] In the adhesion process, new carbon dioxide adsorbent material is supplied to and attached (supported) to the carbon dioxide adsorption layer 15 of the carbon dioxide adsorption apparatus 100, which has undergone the adsorption and desorption processes. The carbon dioxide adsorbent material supplied in the adhesion process may be the same as or different from the carbon dioxide adsorbent material contained in the carbon dioxide adsorption layer 15. Preferably, the carbon dioxide adsorbent material supplied in the adhesion process is the same as the carbon dioxide adsorbent material contained in the carbon dioxide adsorption layer 15.

[0077] Depending on the material of the substrate and the type of carbon dioxide adsorbent, any suitable method can be used for supplying the carbon dioxide adsorbent. Examples of supply methods include spray coating the carbon dioxide adsorbent solution onto the carbon dioxide adsorption layer (spray coating method); immersing the carbon dioxide adsorption device in the carbon dioxide adsorption solution (wash coating method); flowing the carbon dioxide adsorbent solution into the gas flow path of the carbon dioxide adsorption device (flow method); and electrostatically coating the carbon dioxide adsorbent onto the carbon dioxide adsorption layer (electrostatic coating method). Preferably, the carbon dioxide adsorption device is positioned such that one end (inlet) of the gas flow path is located above the other end (outlet) of the gas flow path. This allows the supplied carbon dioxide adsorption device to fall actively due to gravity, enabling uniform application to the carbon dioxide adsorption layer and improving the carbon dioxide adsorption performance of the regenerated carbon dioxide adsorption device.

[0078] D-1. Spray application method When the adhesion process is carried out by a spray coating method, the carbon dioxide recovery performance of the carbon dioxide adsorption device can be restored on-site without removing the carbon dioxide adsorption device from the carbon dioxide adsorption equipment (not shown). Therefore, replacement of the carbon dioxide adsorption device becomes unnecessary, and maintenance costs for the carbon dioxide adsorption equipment can be reduced. When the thickness of the carbon dioxide adsorption layer is 1 mm or less, the spray coating method is preferably selected for the adhesion process.

[0079] In the spray application method, first, the carbon dioxide adsorbent solution is atomized (misted) and applied to the carbon dioxide adsorption layer. This coats the surface of the carbon dioxide adsorption layer with the carbon dioxide adsorbent solution. Then, if necessary, the coating is dried at, for example, between 20°C and 200°C.

[0080] A carbon dioxide adsorbent solution is typically prepared by dissolving the carbon dioxide adsorbent described above in a solvent. Examples of solvents include water, alcohols, and diols, and preferably aqueous solvents (water and mixed solvents containing water). The solvent can be used alone or in combination. The concentration of the carbon dioxide adsorbent in the carbon dioxide adsorbent solution is, for example, 0.1% by mass or more, preferably 5.0% by mass or more, and for example, 50% by mass or less, preferably 30% by mass or less. Examples of spraying methods include air spraying and ultrasonic spraying, with air spraying being preferred. The amount of carbon dioxide adsorbent solution applied is typically such that the thickness of the carbon dioxide adsorbent applied by the spraying method is 1 mm or less, preferably 0.1 mm or less.

[0081] D-2. Wash Coat Method When the adhesion process is carried out by the wash-coat method, the carbon dioxide recovery performance can be smoothly restored despite being a simple method. When the thickness of the carbon dioxide adsorption layer is 0.1 mm or more, and a uniform thickness is required in the longitudinal direction of the adsorption device, the wash-coat method is preferably selected for the adhesion process.

[0082] In the wash-coat method, the carbon dioxide adsorption device is first immersed in a carbon dioxide adsorption solution. This causes the carbon dioxide adsorption solution to adhere to the surface of the carbon dioxide adsorption layer. After that, the carbon dioxide adsorption device is removed from the carbon dioxide adsorption solution and dried as needed, for example, at a temperature between 20°C and 200°C.

[0083] The carbon dioxide adsorbent solution is, for example, the same as the carbon dioxide adsorbent solution described in item D-1 above. The immersion time is typically 10 minutes to 24 hours, and is such that the thickness of the carbon dioxide adsorbent applied by the wash-coat method is 0.01 mm or more, preferably 0.1 mm or more.

[0084] D-3. Distribution law When the adhesion process is carried out by the distribution method, the carbon dioxide recovery performance of the carbon dioxide adsorption device can be restored on-site, similar to the spray coating method described above, and the maintenance costs of the carbon dioxide adsorption equipment can be reduced. When the thickness of the carbon dioxide adsorption layer is 0.1 mm or more, the flow method is preferably selected for the adhesion process.

[0085] In the distribution method, first, the carbon dioxide adsorbent solution is poured into the gas flow path of the carbon dioxide adsorption device. This coats the surface of the carbon dioxide adsorption layer with the carbon dioxide adsorbent solution. Then, if necessary, the coating is dried at, for example, between 20°C and 200°C.

[0086] The carbon dioxide adsorbent solution is, for example, the same as the carbon dioxide adsorbent solution described in section D-1 above. The flow rate of the carbon dioxide adsorbent solution is typically such that the thickness of the carbon dioxide adsorbent applied by the flow method is 0.01 mm or more, preferably 0.1 mm or more.

[0087] D-4. Electrostatic coating method When the adhesion process is carried out by electrostatic coating, the yield of the applied carbon dioxide adsorbent solution is high, thus reducing the cost of the coating material. When the thickness of the carbon dioxide adsorption layer is 1 mm or less and a uniform thickness is required, electrostatic coating is preferably selected for the adhesion process. The amount of carbon dioxide adsorbent solution applied is typically such that the thickness of the carbon dioxide adsorbent applied by electrostatic coating is 1 mm or less, preferably 0.1 mm or less.

[0088] D-5.Particle supply method Carbon dioxide adsorption particles may be supplied to the carbon dioxide adsorption layer using an organic binder (particle supply method). This also allows for the recovery of carbon dioxide from the carbon dioxide adsorption equipment on-site and reduces the maintenance costs of the carbon dioxide adsorption equipment.

[0089] In the particle supply method, first, a dispersion of carbon dioxide adsorbent particles is introduced into the gas channel of the carbon dioxide adsorption apparatus. Next, a protic polar solvent (typically water) is introduced into the gas channel. This supplies carbon dioxide adsorbent particles to the surface of the carbon dioxide adsorption layer, causing them to adhere to the organic binder facing the gas channel. After that, the carbon dioxide adsorption layer is dried as needed.

[0090] As a result, the carbon dioxide adsorption device 100 is regenerated. This method for regenerating a carbon dioxide adsorption device (acid gas adsorption device) is, in other words, a method for manufacturing a carbon dioxide adsorption device (acid gas adsorption device) that has a carbon dioxide adsorption layer (acid gas adsorption layer) with restored performance. The method for manufacturing a carbon dioxide adsorption device (acid gas adsorption device) includes the adsorption step described above; the desorption step described above; and the adhesion step described above. This method for manufacturing a carbon dioxide adsorption device (acid gas adsorption device) makes it possible to manufacture a carbon dioxide adsorption device with excellent CO2 recovery performance (acid gas recovery performance).

[0091] E. Operation method of carbon dioxide adsorption device In the above embodiment, the adhesion process is performed after the adsorption and desorption processes have been carried out, but the adhesion process can also be carried out simultaneously with the adsorption process. Thus, the operation method of the carbon dioxide adsorption device (acid gas adsorption device) includes the above-described adsorption process and the above-described desorption process, and in the adsorption process, the carbon dioxide adsorbent (acid gas adsorbent) is supplied to the carbon dioxide adsorption layer (acid gas adsorption layer) together with CO2 (acid gas) and adheres to it. When the adhesion process and the adsorption process are carried out simultaneously, the excellent performance of the carbon dioxide adsorption device (acid gas adsorption device) can be maintained without performing separate maintenance on the carbon dioxide adsorption device (acid gas adsorption device).

[0092] More specifically, in the adsorption process, a carbon dioxide adsorbent solution is sprayed onto the CO2-containing gas flowing into the gas channel, causing droplets of the carbon dioxide adsorbent solution to be entrained in the CO2-containing gas. As a result, when the CO2-containing gas passes through the gas channel, droplets of the carbon dioxide adsorbent solution adhere to the surface of the carbon dioxide adsorption layer, supplying new carbon dioxide adsorbent material to the carbon dioxide adsorption layer. Therefore, the decrease in CO2 recovery performance that occurs with repeated adsorption and desorption processes can be suppressed.

[0093] The carbon dioxide adsorbent solution is, for example, the same as the carbon dioxide adsorbent solution described in Section D-1 above. The method for spraying the carbon dioxide adsorbent solution is, for example, the same as the spray method described in Section D-1 above.

[0094] Furthermore, in the adsorption process, the CO2-containing gas introduced into the gas channel may be accompanied by powdered carbon dioxide adsorbent particles, or a dispersion in which carbon dioxide adsorbent particles are dispersed in an aprotic solvent. In this case, as the CO2-containing gas passes through the gas channel, the carbon dioxide adsorbent particles will adhere to the organic binder on the surface of the carbon dioxide adsorption layer. Therefore, new carbon dioxide adsorbent particles can be supplied to the carbon dioxide adsorption layer. [Industrial applicability]

[0095] The method for regenerating an acidic gas adsorption device according to an embodiment of the present invention can be used for regenerating an acidic gas adsorption device used for the separation and recovery of acidic gases, and is particularly suitable for regenerating a carbon dioxide adsorption device used in the carbon dioxide capture, utilization, and storage (CCUS) cycle. [Explanation of symbols]

[0096] 10 Honeycomb-shaped substrate 13 Bulkhead 14 cells 15 Carbon dioxide adsorption layer 100 Carbon Dioxide Adsorption Device

Claims

1. An acid gas adsorption apparatus comprising a substrate and an acid gas adsorption layer disposed on the surface of the substrate, the acid gas adsorption layer containing an acid gas adsorbent, is supplied with an acid gas so as to come into contact with the acid gas adsorption layer, thereby causing the acid gas to be adsorbed by the acid gas adsorbent; A step of desorbing the acidic gas from the acidic gas adsorbent; The steps include: supplying an acid gas adsorbent to the acid gas adsorption layer of an acid gas adsorption apparatus that has undergone the steps of adsorbing the acid gas and desorbing the acid gas, and adhering the acid gas adsorbent to it; A method for regenerating an acid gas adsorption apparatus, wherein the acid gas adsorption layer further comprises a porous carrier.

2. The method for regenerating an acid gas adsorption apparatus according to claim 1, wherein the acid gas is carbon dioxide.

3. The substrate is a honeycomb-shaped substrate having partitions that define a plurality of cells, The method for regenerating an acid gas adsorption apparatus according to claim 1, wherein the acid gas adsorption layer is formed on the surface of the partition wall.

4. The method for regenerating an acidic gas adsorption apparatus according to claim 1, wherein the material constituting the substrate is selected from cordierite, alumina, mullite, silicon carbide, silicon-silicon carbide composite material, silicon nitride, or a combination thereof.

5. The method for regenerating an acidic gas adsorption apparatus according to claim 1, wherein the acidic gas adsorbent is selected from nitrogen-containing compounds, organometallic structures, activated carbon, nitrogen-doped carbon, alkali compounds, carbonates, bicarbonates, zeolites, ionic liquids, or combinations thereof.

6. The acidic gas adsorption layer comprises particles containing at least the acidic gas adsorbent, and an organic binder capable of binding the particles. The organic binder is soluble in a non-protic polar solvent and substantially insoluble in protic polar solvents. A method for regenerating an acid gas adsorption apparatus according to claim 1, wherein in the step of supplying an acid gas adsorbent to the acid gas adsorption layer and allowing it to adhere, particles containing at least the acid gas adsorbent are supplied to the acid gas adsorption layer.

7. An acid gas adsorption apparatus comprising a substrate and an acid gas adsorption layer disposed on the surface of the substrate, the acid gas adsorption layer containing an acid gas adsorbent, is supplied with an acid gas so as to come into contact with the acid gas adsorption layer, thereby causing the acid gas to be adsorbed by the acid gas adsorbent; The process includes: a step of desorbing the acidic gas from the acidic gas adsorbent; The acidic gas adsorption layer further comprises a porous carrier, A method for operating an acid gas adsorption apparatus, wherein, in the step of adsorbing an acid gas onto the acid gas adsorbent, the acid gas adsorbent is supplied to and adheres to the acid gas adsorption layer together with the acid gas.

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