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

Abstract

Provided are: a regeneration method for an acid-gas adsorption device, the method enabling smooth recovery of acid-gas recovery performance and reduced running costs; and a manufacturing method for an acid-gas adsorption device, the method enabling the manufacture of an acid-gas adsorption device having a 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 in which a gas including an acid gas is supplied to the acid-gas adsorption device so as to contact an acid-gas adsorption layer, causing an acid gas adsorbent to adsorb the acid gas; a step in which the acid gas is desorbed from the acid gas adsorbent; a step in which, after undergoing the step of adsorbing the acid gas and the step of desorbing the acid gas, the acid-gas adsorption layer of the acid-gas adsorption device is removed from the surface of a base material; and a step in which an acid-gas adsorption layer, which includes a porous carrier and the acid gas adsorbent, is formed on the surface of the base material from which the acid-gas adsorption layer has been removed.

Description

[Technical field]

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

[0002] In recent years, efforts have been made to separate and capture acidic gases contained in the atmosphere in order to reduce the environmental load. Such acidic gases include mainly carbon dioxide (hereinafter sometimes referred to as CO2), which is a 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 separating and capturing such carbon dioxide, a CO2 capture absorbent structure has been proposed that includes a honeycomb substrate having a plurality of partition walls, thereby forming a plurality of flow channels, and functional structural unit groups disposed in and on the partition walls (see, for example, Patent Document 1). In such a CO2 capture absorbent structure, CO2 can be captured from a gas fluid flowing through the absorbent structure, and the captured CO2 can be desorbed under predetermined conditions. However, when the adsorption and desorption of CO2 contained in the atmosphere is repeated using the CO2 capture absorbent structure described in Patent Document 1, the CO2 capture rate may gradually decrease due to impurities contained in the atmosphere and repeated heating treatment. In this case, the entire CO2 capture absorptive structure must be replaced, which increases the running costs. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2013 / 119929 Summary of the Invention [Problem to be solved by the invention]

[0004] The main object of the present invention is to provide a method for regenerating an acid gas adsorption apparatus that can smoothly recover acid gas recovery performance and reduce running costs, and 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 acidic gas adsorption device according to an embodiment of the present invention includes the steps of: supplying a gas containing an acidic gas to an acidic gas adsorption device having a substrate and an acidic gas adsorption layer disposed on the surface of the substrate, the acidic gas adsorption layer including a porous carrier and an acidic gas adsorbent, so as to contact the acidic gas adsorption layer, thereby allowing the acidic gas to be adsorbed by the acidic gas adsorbent; desorbing the acidic gas from the acidic gas adsorbent; removing the acidic gas adsorption layer of the acidic gas adsorption device after the steps of adsorbing the acidic gas and desorbing the acidic gas have been performed from the surface of the substrate; and forming an acidic gas adsorption layer including a porous carrier and an acidic gas adsorbent on the surface of the substrate from which the acidic gas adsorption layer has been removed. [2] One embodiment is the method for regenerating an acidic gas adsorption apparatus according to the above item [1], wherein the acidic gas is carbon dioxide. [3] One embodiment is the method for regenerating an acidic gas adsorption device described in item [1] or [2] above, in which the substrate is a honeycomb substrate having partition walls defining a plurality of cells, and the acidic gas adsorption layer is formed on a surface of the partition walls. [4] One embodiment is the method for regenerating an acidic gas adsorption apparatus according to any one of the above items [1] to [3], wherein the material constituting the substrate comprises at least one selected from the group consisting of cordierite, alumina, mullite, silicon carbide, a silicon-silicon carbide composite material, and silicon nitride, the porous carrier comprises a metal-organic framework and / or activated carbon, and in the step of removing the acidic gas adsorption layer from the surface of the substrate, the acidic gas adsorption apparatus is heated to burn off the acidic gas adsorption layer. [5] One embodiment is the method for regenerating an acid gas adsorption apparatus according to item [4] above, in which the acid gas adsorption apparatus is heated to 400°C or higher in the step of removing the acid gas adsorption layer from the surface of the substrate. [6] One embodiment is a method for regenerating an acidic gas adsorption device according to any one of items [1] to [3] above, wherein the material constituting the substrate comprises at least one selected from the group consisting of alumina, silicon carbide, and silicon-silicon carbide composite materials, the porous support comprises mesoporous silica and / or zeolite, and in the step of removing the acidic gas adsorption layer from the surface of the substrate, the acidic gas adsorption layer is brought into contact with an acidic solution to dissolve the acidic gas adsorption layer. [7] One embodiment is the method for regenerating an acidic gas adsorption apparatus according to the above item [6], wherein the acidic solution contains at least one selected from hydrofluoric acid, sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid. [8] One embodiment is a method for regenerating an acidic gas adsorption device according to any one of items [1] to [3] above, wherein the material constituting the substrate comprises silicon carbide and / or a silicon-silicon carbide composite material, the porous support comprises mesoporous alumina, and in the step of removing the acidic gas adsorption layer from the surface of the substrate, the acidic gas adsorption layer is brought into contact with an alkaline solution to dissolve the acidic gas adsorption layer. [9] One embodiment is the method for regenerating an acidic gas adsorption apparatus according to the above item [8], wherein the alkaline solution contains at least one selected from the group consisting of sodium hydroxide and potassium hydroxide.

[10] One embodiment is a method for regenerating an acidic gas adsorption apparatus according to any one of items [1] to [3] above, wherein the acidic gas adsorption layer includes particles including the porous carrier and the acidic gas adsorbent, and an organic binder capable of binding the particles, the organic binder being soluble in an aprotic polar solvent and substantially insoluble in a protic polar solvent, and in the step of removing the acidic gas adsorption layer from the surface of the substrate, the acidic gas adsorption layer is brought into contact with an aprotic polar solvent to dissolve the organic binder.

[11] One embodiment is the method for regenerating an acid gas adsorption apparatus according to any one of items [1] to

[10] above, wherein in the step of adsorbing an acid gas onto the acid gas adsorbent, the gas containing the acid gas supplied to the acid gas adsorption apparatus is air.

[12] A method for producing an acidic gas adsorption device according to another aspect of the present invention includes the steps of: supplying a gas containing an acidic gas to an acidic gas adsorption device having a substrate and an acidic gas adsorption layer disposed on the surface of the substrate, the acidic gas adsorption layer including a porous carrier and an acidic gas adsorbent, so as to contact the acidic gas adsorption layer, thereby allowing the acidic gas to be adsorbed by the acidic gas adsorbent; desorbing the acidic gas from the acidic gas adsorbent; removing the acidic gas adsorption layer of the acidic gas adsorption device after the steps of adsorbing the acidic gas and desorbing the acidic gas have been performed from the surface of the substrate; and forming an acidic gas adsorption layer including a porous carrier and an acidic gas adsorbent on the surface of the substrate from which the acidic gas adsorption layer has been removed.

[13] One embodiment is the method for producing an acidic gas adsorption apparatus according to item

[12] above, wherein the acidic gas is carbon dioxide. Effect of the Invention

[0006] According to an embodiment of the present invention, it is possible to realize a method for regenerating an acid gas adsorption apparatus that can smoothly recover acid gas recovery performance and reduce running costs, and a method for manufacturing an acid gas adsorption apparatus that can manufacture an acid gas adsorption apparatus with excellent acid gas recovery performance. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic perspective view of a carbon dioxide adsorption device according to one embodiment of the present invention. [Diagram 2] FIG. 2 is a schematic cross-sectional view of the carbon dioxide adsorption apparatus of FIG. [Diagram 3] FIG. 3 is a schematic perspective view of the carbon dioxide adsorbing device of FIG. 1 with the carbon dioxide adsorbing layer removed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0009] A. Overview of the regeneration method for acid gas adsorption equipment FIG. 1 is a schematic perspective view of a carbon dioxide adsorption device according to one embodiment of the present invention; FIG. 2 is a schematic cross-sectional view of the carbon dioxide adsorption device of FIG. 1; and FIG. 3 is a schematic perspective view of the carbon dioxide adsorption device of FIG. 1 with the carbon dioxide adsorption layer removed. A method for regenerating an acidic gas adsorption device according to one embodiment of the present invention includes the steps of: supplying a gas containing an acidic gas to an acidic gas adsorption device 100, which includes a substrate 1 and an acidic gas adsorption layer 15 disposed on the surface of the substrate 1, the acidic gas adsorption layer 15 including a porous carrier and an acidic gas adsorbent, so as to contact the acidic gas adsorption layer 15, thereby adsorbing the acidic gas to the acidic gas adsorbent (adsorption step); desorbing the acidic gas from the acidic gas adsorbent (desorption step); removing the acidic gas adsorption layer 15 of the acidic gas adsorption device 100, after the adsorption and desorption steps have been performed, from the surface of the substrate 1 (removal step); and forming an acidic gas adsorption layer 15 including a porous carrier and an acidic gas adsorbent on the surface of the substrate 1 from which the acidic gas adsorption layer 15 has been removed (reformation step). The inventors have found that the life of the substrate is longer than the life of the acid gas adsorbent, and have completed the present invention. More specifically, after removing the acid gas adsorption layer of the acid gas adsorption device in which the adsorption process and the desorption process have been carried out from the surface of the substrate, a new acid gas adsorption layer is formed on the surface of the substrate. This regenerates the acid gas adsorption device. Therefore, the substrate can be reused while smoothly recovering the excellent acid gas recovery performance. As a result, the running cost can be reduced.

[0010] Examples of acid 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. The carbon dioxide adsorption device 100 as one embodiment of the acid gas adsorption device will be described in detail below.

[0011] B. Carbon dioxide adsorption device As described above, the carbon dioxide adsorption device 100 includes the substrate 1 and the carbon dioxide adsorption layer 15. The structure of the substrate 1 is not particularly limited, and examples thereof include a filter structure such as a honeycomb shape or 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 cells 14 extend from the first end face 1a (inlet end face) to the second end face 1b (outlet end face) of the honeycomb substrate 10 in the length direction (axial direction) of the honeycomb substrate 10 (see FIG. 2). The cells 14 have any appropriate shape in a cross section perpendicular to the length direction of the honeycomb substrate 10. Examples of the cross-sectional shape of the cells include a triangle, a rectangle, a pentagon, a polygon having hexagons or more, a circle, and an ellipse. The cross-sectional shapes and sizes of the cells may all be the same, or may be at least partially different. Among such cross-sectional shapes of the cells, a hexagon or a quadrangle is preferable, and a square, a rectangle, or a hexagon is more preferable.

[0013] The cell density (i.e., the number of cells 14 per unit area) in a cross section perpendicular to the longitudinal direction of the honeycomb substrate can be appropriately set depending on the purpose. The cell density is, for example, 4 cells / cm 2 ~320 cells / cm 2 If the cell density is in this range, the strength and effective GSA (geometric surface area) of the honeycomb substrate can be sufficiently ensured.

[0014] The honeycomb substrate 10 has any appropriate shape (overall shape). Examples of the shape of the honeycomb substrate include a cylindrical shape with a circular bottom, an elliptical cylindrical shape with an elliptical bottom, a rectangular prism with a polygonal bottom, and a cylindrical shape with an irregular bottom. The honeycomb substrate 10 in the illustrated example has a cylindrical shape. The outer diameter and length of the honeycomb substrate can be appropriately set depending on the purpose. Although not illustrated, the honeycomb substrate may have a hollow region in the center in a cross section perpendicular 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 bodies.

[0016] The outer peripheral wall 11 has a cylindrical shape. The thickness of the outer peripheral wall 11 can be set arbitrarily and appropriately. The thickness of the outer peripheral wall 11 can be, 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 perpendicular 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 rectangular except for the portions where the first partition wall 13a and the second partition wall 13b contact the outer peripheral wall 11. The configuration of the partition walls is not limited to the above-described partition wall 13. The partition walls may have a first partition wall extending in the radial direction and a second partition wall extending in the circumferential direction, which define a plurality of cells.

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

[0019] The porosity of the partition walls 13 can be appropriately set depending on the purpose. The porosity of the partition walls 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 by, for example, mercury intrusion porosimetry. The density of the partition walls 13 can be appropriately set depending on the purpose. For example, the density is 1.7 g / cm 3 More than 1.8 g / cm, preferably 1.8 g / cm 3 or more, for example 2.8 g / cm 3 Less than 2.6 g / cm, preferably 2.6 g / cm 3 The density can be measured by, for example, mercury intrusion porosimetry.

[0020] Representative examples of the material constituting the partition wall 13 include ceramics. Examples of the 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 alone or in combination. Among the materials constituting the partition wall, preferred examples include cordierite, alumina, mullite, silicon carbide, silicon-silicon carbide composite materials, and silicon nitride, and more preferred examples include silicon carbide and silicon-silicon carbide composite materials.

[0021] Such a honeycomb-shaped substrate 10 can be typically produced by the following method. First, a binder and water or an organic solvent are added to the material powder containing the above-mentioned ceramic powder as necessary, and the resulting mixture is kneaded to form a clay. The clay is molded into a desired shape (typically by extrusion molding), and then dried and fired as necessary to produce the honeycomb-shaped substrate 10. When firing, the mixture is fired at, for example, 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, a gas flow path 16 is formed in a portion (typically a central portion) in the cross section of the cell 14 where the carbon dioxide adsorption layer 15 is not formed. The carbon dioxide adsorption layer 15 may be formed on the entire inner surface of the partition wall 13 (i.e., so as to surround the gas flow path 16) as in the illustrated example, or may be formed on a part of the surface of the partition wall. When the carbon dioxide adsorption layer 15 is formed on the entire inner surface of the partition wall 13, the efficiency of removing CO2 can be improved.

[0023] The gas flow passages 16 extend from the first end face 1a (inlet end face) to the second end face 1b (outlet end face) in the same manner as the cells 14. The cross-sectional shape of the gas flow passages 16 may be the same as that of the cells 14, preferably a hexagon or a quadrangle, and more preferably a square, a rectangle, or a hexagon. The cross-sectional shapes and sizes of the gas flow passages 16 may all be the same, or at least some of them may be different.

[0024] The carbon dioxide adsorption layer 15 includes a porous carrier and a carbon dioxide adsorbent. In the carbon dioxide adsorption layer 15, the porous carrier forms mesopores. 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; zeolites; and carbon nanotubes. Of these, metal-organic frameworks (MOFs), mesoporous silica, and mesoporous alumina are preferred.

[0025] The BET specific surface area of ​​the porous support is, for example, 50 m 2 / g or more, preferably 500m 2 If the surface area of ​​the porous carrier is equal to or greater than the lower limit, the carbon dioxide adsorbent can be sufficiently supported, and the CO2 absorption rate can be improved. The upper limit of the BET specific surface area of ​​the porous carrier is typically 2000 m 2 / g or less.

[0026] The content of the porous carrier in the carbon dioxide adsorption layer 15 is, for example, 0.1 mass % or more, preferably 10 mass % or more, and for example, 70 mass % or less, preferably 50 mass % or less.

[0027] 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 is, for example, 1000 μm or less, preferably 500 μm or less.

[0028] The carbon dioxide adsorbent is typically supported on a porous carrier and faces the gas flow passage 16 . As the carbon dioxide adsorbent, any suitable compound capable of adsorbing and desorbing CO2 may be used. Examples of the carbon dioxide adsorbent include nitrogen-containing compounds described below; alkaline compounds such as sodium hydroxide and potassium hydroxide; carbonates such as calcium carbonate and potassium carbonate; bicarbonates such as calcium bicarbonate and potassium bicarbonate; metal-organic frameworks (MOFs) such as MOF-74, MOF-200, and MOF-210; zeolites; activated carbon; and nitrogen-doped carbon. The carbon dioxide adsorbent is preferably made of a material different from the porous carrier.

[0029] Among the carbon dioxide adsorbents, nitrogen-containing compounds are more preferred. More specifically, the 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 amino groups to tertiary amino groups such as polyamidoamine, polyethyleneimine, and polystyrene to which amino groups have been added; organic monomers having primary amino groups to tertiary amino groups such as ethyleneimine and styrene to which amino groups have been added; and organic / inorganic compounds to which amino groups have been added as substituents. The carbon dioxide adsorbents can be used alone or in combination.

[0030] The carbon dioxide adsorbent content in the carbon dioxide adsorption layer 15 is, for example, 0.1 mass% or more, preferably 0.5 mass% or more. When the carbon dioxide adsorbent content is equal to or more than the lower limit, an excellent CO2 absorption rate can be stably ensured. The upper limit of the carbon dioxide adsorbent content is typically 30 mass% or less.

[0031] Such a carbon dioxide adsorption layer 15 can be typically produced by the following method. First, a dispersion of the porous carrier is prepared by dispersing the above-mentioned porous carrier in a dispersion medium, and a carbon dioxide adsorbent is added to the dispersion. Next, the dispersion containing the porous carrier and the carbon dioxide adsorbent is applied to the substrate 1 (specifically, the partition walls 13), and the coating is dried and sintered as necessary to form the carbon dioxide adsorption layer 15. The method of forming the carbon dioxide adsorption layer will be described in detail in the explanation of the re-forming step in Section E.

[0032] The method for producing the carbon dioxide adsorption layer 15 is not limited to the above. For example, a dispersion of the porous carrier is prepared by dispersing the porous carrier in a dispersion medium, and the dispersion is applied onto the substrate 1 (specifically, the partition wall 13), and the coating is dried and sintered to form a carrier-containing film. Then, a liquid carbon dioxide adsorbent or a solution of the carbon dioxide adsorbent is applied to the carrier-containing film at room temperature and normal pressure. As a result, the carbon dioxide adsorbent is absorbed into the porous carrier of the carrier-containing film and supported thereon. Thus, the carbon dioxide adsorption layer 15 is formed.

[0033] In another embodiment, the carbon dioxide adsorption layer 15 includes particles having the above-mentioned carbon dioxide adsorbent and the above-mentioned porous carrier, and an organic binder. The above-mentioned carbon dioxide adsorbent and the above-mentioned particles having the porous carrier have carbon dioxide adsorption ability, and are hereinafter referred to as carbon dioxide adsorption particles. The organic binder can bind the carbon dioxide adsorption particles, and is typically fixed to the substrate 1. The organic binder is soluble in aprotic polar solvents and is substantially insoluble in protic polar solvents. That is, the organic binder has resistance (water resistance) to water, which is a protic polar solvent. Since the organic binder is substantially insoluble in protic polar solvents and has water resistance, it is possible to suppress the organic binder from swelling due to water vapor in the atmosphere, for example. Therefore, it is possible to suppress the volume expansion and / or decrease in strength of the organic binder, and thus to suppress changes in the structure in which the organic binder binds and holds the carbon dioxide adsorption particles. As a result, it is possible to maintain excellent carbon dioxide adsorption ability regardless of the usage environment.

[0034] The surface of the carbon dioxide adsorption layer 15 opposite the partition wall 13 preferably has a three-dimensional mesh structure or a porous lamellar structure. Therefore, acidic gases such as carbon dioxide can be efficiently diffused from the surface to the inside of the carbon dioxide adsorption layer. In particular, since the organic binder has water resistance, such a fine structure can be stably maintained on the surface that can come into contact with acidic gases regardless of the usage environment.

[0035] The carbon dioxide adsorbing particles are typically in a solid state at room temperature and normal pressure (23°C, 0.1 MPa). The carbon dioxide adsorbing layer 15 contains a plurality of carbon dioxide adsorbing particles. The carbon dioxide adsorbing particles contained in the carbon dioxide adsorbing layer 15 may be primary particles or secondary particles formed by agglomeration of a plurality of primary particles.

[0036] Among the carbon dioxide adsorbents contained in the carbon dioxide adsorbing particles, the above-mentioned nitrogen-containing compounds are preferred, and the above-mentioned organic monomers having a primary amino group to a tertiary amino group and the above-mentioned organic polymers having a primary amino group to a tertiary amino group are more preferred. The weight-average molecular weight M w (polystyrene equivalent) is, for example, 1,000 or more, preferably 50,000 or more, and for example, 1 million or less, preferably 300,000 or less.

[0037] In one embodiment, the carbon dioxide adsorbent material contained in the carbon dioxide adsorbing 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 equal to or less than 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 an aprotic polar solvent is, for example, 1 g / 100 g-aprotic polar solvent or less, preferably 0.5 g / 100 g-aprotic polar solvent or less. If the solubility of the carbon dioxide adsorbent in an aprotic polar solvent is equal to or less than the above upper limit, the carbon dioxide adsorbent can be prevented from dissolving in the aprotic polar solvent in the manufacture of the acidic gas adsorption device. The lower limit of the solubility of the carbon dioxide adsorbent in an aprotic polar solvent is typically equal to or more than 0.01 g / 100 g-aprotic polar solvent.

[0038] The solubility parameter of the carbon dioxide adsorbent is, for example, 7 or more, preferably 8 or more, and is, for example, 20 or less, preferably 15 or less. The solubility parameter can be calculated, for example, by the Hildebrand method.

[0039] The organic binder may be any suitable organic compound capable of binding carbon dioxide adsorption particles. The organic binder is soluble in aprotic polar solvents and substantially insoluble in protic polar solvents. Examples of the organic binder include fluoropolymers such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylenepropene copolymer (FEP), and ethylenetetrafluoroethylene copolymer (ETFE); and amorphous plastics such as polyethersulfone (PES). The organic binder may be used alone or in combination. Among organic binders, preferably, an organic binder having at least water as a poor solvent (an organic binder substantially insoluble in water) is used, more preferably, a fluoropolymer is used, and further preferably, polyvinylidene fluoride is used. When the organic binder contains a fluoropolymer (polyvinylidene fluoride), it is possible to impart excellent heat resistance and water resistance to the carbon dioxide adsorption device.

[0040] The solubility of the organic binder in a protic polar solvent (typically water) is, for example, 0.1 g / 100 g of protic polar solvent or less, preferably 0.05 g / 100 g of protic polar solvent or less. If the solubility of the organic binder in a protic polar solvent (typically water) is equal to or less than 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 of protic polar solvent or less. Protic polar solvents That's all.

[0041] The solubility parameter of the organic binder is, for example, 9 or more, preferably 10 or more, and is, for example, 15 or less, preferably 13 or less.

[0042] The carbon dioxide adsorption layer 15 may contain any suitable additive in addition to the carbon dioxide adsorbent particles and the organic binder. The total content of the carbon dioxide adsorbent particles and the organic binder in the carbon dioxide adsorption layer 15 is, for example, 30 volume % or more, preferably 50 volume % or more, and for example, 100 volume % or less, preferably 99 volume % or less. The volume % can be measured, for example, by microstructural observation or elemental analysis.

[0043] The content of the carbon dioxide adsorbing particles in the carbon dioxide adsorption layer 15 is, for example, 5% by volume or more, and preferably 30% by volume or more. When the content of the carbon dioxide adsorbing particles is equal to or more than the lower limit, the carbon dioxide adsorption performance of the carbon dioxide adsorption device can be sufficiently ensured. The upper limit of the content of the carbon dioxide adsorbing particles is typically 85% by volume or less.

[0044] The content of the organic binder in the carbon dioxide adsorption layer 15 is, for example, 5% by volume or more, and preferably 15% by volume or more. When the content of the organic binder is equal to or more than the lower limit, the carbon dioxide adsorbent particles can be prevented from falling off from the carbon dioxide adsorption layer in the adsorption step and / or desorption step described below. The upper limit of the content of the organic binder is typically 70% by volume or less.

[0045] The carbon dioxide adsorption layer 15 typically has interconnected pores. The porosity of the carbon dioxide adsorption layer 15 is, for example, 10% or more and 90% or less, preferably 10% or more and 60% or less, and more preferably 15% or more and 40% or less.

[0046] The carbon dioxide adsorption layer 15 containing the carbon dioxide adsorbing particles and the organic binder can be typically produced by the following method. First, the organic binder is dissolved in an aprotic polar solvent to prepare a binder solution, the carbon dioxide adsorbing particles are dispersed in the binder solution, and then the binder solution is applied to the surface of the substrate 1 (specifically, the partition walls 13) to form a precursor film. beforeThe aprotic polar solvent contained in the precursor film is replaced with a poor solvent for the organic binder to form the carbon dioxide adsorption layer 15. The method for forming the carbon dioxide adsorption layer will be described in detail in the explanation of the re-forming step in Section E.

[0047] The method for producing the carbon dioxide adsorption layer 15 containing the carbon dioxide adsorbing particles and the organic binder is not limited to the above. For example, the porous carrier described above may be dispersed in the binder solution described above, the binder solution is applied to the surface of the substrate 1 (specifically, the partition wall 13) to form a precursor film, and then the aprotic polar solvent contained in the precursor film is replaced with a poor solvent for the organic binder to form a carrier-containing film containing the porous carrier and the organic binder, and then the carbon dioxide adsorbent is supported on the porous carrier contained in the carrier-containing film to form the carbon dioxide adsorbent, thereby forming the carbon dioxide adsorption layer 15.

[0048] C. Adsorption and Desorption Steps As described above, the regeneration method of the carbon dioxide adsorption device according to one embodiment includes an adsorption process of adsorbing CO2 into the carbon dioxide adsorbent provided in the carbon dioxide adsorption device 100, and a desorption process of desorbing CO2 from the carbon dioxide adsorbent.

[0049] In the adsorption step, typically, a gas containing CO2 (CO2-containing gas) is passed through the gas flow passage 16 of the honeycomb substrate to contact 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 vol. % or less. The CO2-containing gas typically contains nitrogen in addition to CO2. The temperature of the CO2-containing gas in the adsorption step is, for example, 0° C. or more and 40° C. or less. The pressure of the CO2-containing gas in the adsorption step is, for example, 0.3×10 5 Pa or more 2.0×10 5 P a The relative humidity RH of the CO2-containing gas in the adsorption process is, for example, 10% RH or more and 60% RH or less. The duration of the adsorption process is, for example, 15 minutes or more and 3 hours or less. The flow rate of the CO2-containing gas in the adsorption process is, for example, 0.5 m / sec or more and 5 m / sec or less.

[0050] As a result, the carbon dioxide adsorbent facing the gas flow passage 16 adsorbs CO2. The CO2 recovery rate in the adsorption process (=100-(CO2 concentration in gas that has passed through the gas flow passage / CO2 concentration in gas before flowing into the gas flow passage×100)) is, for example, 80% or more, preferably 85% or more, more preferably 90% or more, and is, for example, 100% or less.

[0051] The desorption process (sometimes called the desorption process) is carried out after the adsorption process. In the desorption process, the carbon dioxide adsorption device is typically heated and the desorbed CO2 is sucked in and collected using a pump or the like, or the collected CO2 is fed back into the carbon dioxide adsorption device and heated to collect the desorbed CO2. The temperature in the desorption step is, for example, more than 40° C., preferably 70° C. or higher, and for example, 200° C. or lower, preferably 110° C. or lower. The duration of the desorption step is, for example, 1 minute or longer and 1 hour or shorter. This causes the CO2 held in the carbon dioxide adsorbent to be desorbed (released, desorbed) from the carbon dioxide adsorbent, allowing the CO2 to be captured and used for various purposes (e.g., methanation).

[0052] These adsorption and desorption steps can preferably be carried out repeatedly. In one embodiment, the cycle of the adsorption and desorption steps can be carried out, 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.

[0053] D. Removal process In one embodiment, after the adsorption and desorption steps are performed (preferably after cycles of the adsorption and desorption steps are performed in the above ranges), a removal step is performed. In the removal step, the carbon dioxide adsorption layer 15 of the carbon dioxide adsorption device after the adsorption step and desorption step have been carried out is removed from the surface of the substrate 1 (representatively, the partition wall 13).

[0054] Any suitable method may be adopted as the method for removing the carbon dioxide adsorption layer depending on the material of the substrate and the type of the porous carrier. Examples of the removal method include a method of heating the carbon dioxide adsorption device to burn off the carbon dioxide adsorption layer (burning method); a method of contacting the carbon dioxide adsorption layer with an acidic solution to dissolve the carbon dioxide adsorption layer (acid dissolution method); and a method of contacting the carbon dioxide adsorption layer with an alkaline solution to dissolve the carbon dioxide adsorption layer (alkali dissolution method). In the removal step, a method of contacting the carbon dioxide adsorption layer with an organic solvent to dissolve only the carbon dioxide adsorbent in the organic solvent and removing it is also considered. However, such a method may not be able to sufficiently remove the carbon dioxide adsorbent from the carbon dioxide adsorption layer, and deteriorated carbon dioxide adsorbent may remain. Therefore, if a re-forming step is performed after the removal step to form the carbon dioxide adsorption layer again, the deteriorated carbon dioxide adsorbent may adversely affect the newly formed carbon dioxide adsorption layer. In addition, if the porous carrier is fixed to the substrate by drying and / or sintering, the porous carrier cannot be removed with an organic solvent, so that if a re-forming step is performed after the removal step, a carbon dioxide adsorption layer may be formed on the remaining porous carrier, narrowing the gas flow path. Therefore, a removal process using an organic solvent is not suitable for a carbon dioxide adsorption device in which a carbon dioxide adsorption layer, which includes a porous carrier and a carbon dioxide adsorbent and is fixed to the substrate, is disposed on the substrate. On the other hand, when the carbon dioxide adsorption layer includes carbon dioxide adsorbent particles and an organic binder and the organic binder is fixed to the substrate, it is possible to remove the carbon dioxide adsorption layer by contacting the carbon dioxide adsorption layer with an aprotic polar solvent (aprotic polar solvent dissolution method).

[0055] D-1. Burning method When the material constituting the substrate 1 (honeycomb substrate 10) contains at least one selected from the group consisting of cordierite, alumina, mullite, silicon carbide, a silicon-silicon carbide composite material, and silicon nitride, and the porous carrier contains an organic metal structure and / or activated carbon, the removal step is preferably performed by a burning-out method. In the burnout method, the carbon dioxide adsorption device in which the adsorption step and the desorption step have been carried out is heated to burn out the carbon dioxide adsorption layer (porous carrier and carbon dioxide adsorbent). The heating temperature is, for example, 400° C. or higher, preferably 500° C. or higher, and, for example, 700° C. or lower, preferably 650° C. or lower. The heating time is not particularly limited as long as the carbon dioxide adsorption layer can be removed, and is, for example, 1 hour or longer and 48 hours or shorter.

[0056] D-2. Acid dissolution method When the material constituting the substrate 1 (honeycomb substrate 10) contains at least one selected from the group consisting of alumina, silicon carbide, or silicon-silicon carbide composite materials, and the porous support contains mesoporous silica and / or zeolite, the removal step is preferably performed using an acid dissolution method. In the acid dissolution method, an acidic solution is passed through the gas flow path 16 of the carbon dioxide adsorption device 100 in which the adsorption step and the desorption step have been carried out, and the acidic solution is brought into contact with the carbon dioxide adsorption layer 15. As a result, the carbon dioxide adsorption layer (the porous carrier and the carbon dioxide adsorbent) is dissolved in the acidic solution and removed. The acidic solution is typically an aqueous solution of an acid component. The acid dissociation constant pKa of the acid component in water is, for example, -4.0 or more, preferably -3.7 or more, and for example, 3 or less, preferably 2.7 or less. Specific examples of the acid component include hydrofluoric acid, sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid. The concentration of the acid component in the acidic solution is, for example, 30% by mass or more, preferably 70% by mass or more, and for example, 100% by mass or less, preferably 90% by mass or less.

[0057] D-3. Alkaline dissolution method When the material constituting the substrate 1 (honeycomb substrate 10) contains silicon carbide and / or a silicon-silicon carbide composite material and the porous carrier contains mesoporous aluminum, the removal step is preferably performed using an alkali dissolution method. alkaliIn the dissolution method, an alkaline solution is passed through the gas flow path 16 of the carbon dioxide adsorption device 100 in which the adsorption step and the desorption step have been carried out, and the alkaline solution is brought into contact with the carbon dioxide adsorption layer 15. As a result, the carbon dioxide adsorption layer (the porous carrier and the carbon dioxide adsorbent) is dissolved in the alkaline solution and removed. The alkaline solution is typically an aqueous solution of an alkaline component. The base dissociation constant pKb of the alkaline component in water is, for example, 0 or more, preferably 1 or more, and for example, 3 or less, preferably 2.5 or less. Specific examples of the alkaline component include sodium hydroxide and potassium hydroxide. The concentration of the alkaline component in the alkaline solution is, for example, 10% by mass or more, preferably 20% by mass or more, and for example, 100% by mass or less, preferably 90% by mass or less.

[0058] D-4. Aprotic polar solvent dissolution method When the carbon dioxide adsorption layer includes carbon dioxide adsorbent particles and an organic binder, the removal step preferably involves the selection of an aprotic polar solvent dissolution method. In the aprotic polar solvent dissolution method, an aprotic polar solvent is circulated through the gas flow path 16 of the carbon dioxide adsorption device 100 in which the adsorption step and the desorption step have been carried out, and the aprotic polar solvent is brought into contact with the carbon dioxide adsorption layer 15. As a result, the organic binder contained in the carbon dioxide adsorption layer is dissolved in the aprotic polar solvent, and the carbon dioxide adsorbing particles are separated from the substrate. As a result, the carbon dioxide adsorption layer is removed. The aprotic polar solvent from which the carbon dioxide adsorption layer has been removed contains carbon dioxide adsorbent particles and an organic binder. Therefore, after removing the carbon dioxide adsorbent particles from the aprotic polar solvent containing the carbon dioxide adsorbent particles and the organic binder by filtration or the like, a protic polar solvent can be added to the aprotic polar solvent containing the organic binder to precipitate only the organic binder, which can then be reused.

[0059] The aprotic polar solvent may be any suitable organic solvent.The aprotic polar solvent may be, for example, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMA), dimethylsulfoxide (DMSO), or tetrahydrofuran (THF).The aprotic polar solvent may be used alone or in combination. Among the aprotic polar solvents, N-methyl-2-pyrrolidone (NMP) is preferable. When the aprotic polar solvent contains NMP, the organic binder (particularly PVDF) can be dissolved more smoothly, and the carbon dioxide adsorption layer can be removed smoothly with low energy.

[0060] As a result of the above, the carbon dioxide adsorption layer (the porous carrier and the carbon dioxide adsorbent) is removed from the surface of the substrate 1 (representatively, the partition walls 13) as shown in Fig. 3. The surface of the substrate 1 (representatively, the partition walls 13) is washed as necessary.

[0061] E. Reshaping process In one embodiment, a reforming step is carried out after the removing step. In the reforming step, a new carbon dioxide adsorption layer 15 is formed on the surface of the substrate 1 (typically the partition wall 13) from which the carbon dioxide adsorption layer 15 has been removed.

[0062] In the re-forming step, for example, the above-mentioned porous carrier is first dispersed in a dispersion medium to prepare a dispersion slurry of the porous carrier. Examples of the dispersion medium include water, alcohols, and diols. The dispersion medium can be used alone or in combination. Among the dispersion media, preferred are aqueous solvents (water and mixed solvents containing water). The concentration of the porous carrier in the dispersion slurry is, for example, 10% by mass or more, preferably 15% by mass or more, and, for example, 50% by mass or less, preferably 30% by mass or less. By adjusting the concentration of the porous carrier within the above range, the carbon dioxide adsorption layer can be stably formed on the substrate.

[0063] Next, a carbon dioxide adsorbent is added to the dispersion slurry. The concentration of the carbon dioxide adsorbent in the dispersion slurry is, for example, 5% by mass or more, preferably 10% by mass or more, and for example, 30% by mass or less, preferably 20% by mass or less.

[0064] Next, the dispersion slurry containing the porous carrier and the carbon dioxide adsorbent is applied onto the substrate 1 (specifically, the partition walls 13) by any appropriate method. In one embodiment, the dispersion is caused to flow through the cells 14 of the honeycomb substrate 10. This allows the dispersion to be smoothly applied onto the surfaces of the partition walls. The number of times the dispersion slurry is applied is appropriately changed depending on the thickness of the carbon dioxide adsorption layer.

[0065] Next, the honeycomb substrate coated with the dispersion slurry is heated, for example, to 50°C to 200°C to dry the coating film, and sintered as necessary. The drying time is, for example, 0.5 hours or more and 24 hours or less. When sintering, the sintering is performed, for example, at 80°C to 300°C. The sintering time is, for example, 1 hour or more and 100 hours or less. As a result, a carbon dioxide adsorption layer containing the porous carrier and the carbon dioxide adsorbent is formed again on the substrate 1 (specifically, the partition walls 13).

[0066] In another embodiment, for example, first, the above-mentioned dispersion slurry liquid is applied onto the substrate 1 (specifically, the partition wall 13) in the same manner as described above. Next, the coating film on the substrate to which the dispersion slurry liquid has been applied is dried, and then sintered by heating, for example, at 400°C or more and 800°C or less. The sintering time is, for example, 1 hour or more and 100 hours or less. In this way, a carrier-containing film is formed. Next, a liquid carbon dioxide adsorbent or a solution of the carbon dioxide adsorbent is applied to the carrier-containing film at room temperature and normal pressure in the same manner as described above. As a result, the carbon dioxide adsorbent is impregnated into the porous carrier of the carrier-containing film and supported thereon. This also allows a carbon dioxide adsorption layer including a porous carrier and a carbon dioxide adsorbent to be formed again on the substrate 1 (specifically, the partition wall 13).

[0067] In yet another embodiment, the binder solution is prepared by dissolving the organic binder in the aprotic polar solvent, which is capable of dissolving the organic binder and is insoluble in the carbon dioxide adsorbent particles (more specifically, the carbon dioxide adsorbent).

[0068] 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 the above upper limit or less, 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 equal to or more than the lower limit, the carbon dioxide adsorbent can be prevented from dissolving in the aprotic polar solvent. The upper limit of the solubility parameter distance between the carbon dioxide adsorbent and the aprotic polar solvent is typically 10 or less.

[0069] Next, the above-mentioned carbon dioxide adsorbing particles are added to and dispersed in the binder solution.

[0070] 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 1 by any appropriate method in the same manner as described above. As a result, the particle-dispersed binder solution is applied to the surface of the base material 1 (typically, the surface of the partition wall 13) to form a precursor film. The precursor film contains the above-mentioned carbon dioxide adsorbent particles, the above-mentioned organic binder, and the above-mentioned aprotic polar solvent.

[0071] Next, the aprotic polar solvent contained in the precursor film is replaced with a poor solvent for the organic binder. The poor solvent dissolves the organic binder less easily than the aprotic polar solvent (good solvent), and the organic binder is substantially insoluble in the poor solvent. The solubility parameter distance between the organic binder and the poor solvent is typically larger 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.

[0072] Examples of poor solvents include protic polar solvents such as alcohols such as water, ethanol, butanol, and isopropyl alcohol (IPA); and fluorocarbons such as hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), and hydrofluoroolefins (HFOs). The poor solvents can be used alone or in combination. Among the poor solvents, water is preferred.

[0073] Substitution of aprotic polar solvents results in membranes that are stable in protic solvents.

[0074] This allows the carbon dioxide adsorption layer 15 containing the carbon dioxide adsorbing particles and the organic binder to be formed again on the surface of the base material 1 (typically the surface of the partition wall 13). Thereafter, the carbon dioxide adsorption layer 15 is dried as necessary.

[0075] The process of reforming the carbon dioxide adsorption layer containing the carbon dioxide adsorbent particles and the organic binder is not limited to the above embodiment. For example, first, a binder solution is prepared in the same manner as above. Next, the porous carrier described above is added to the binder solution and dispersed therein.

[0076] As a result, the porous carrier is dispersed in the binder solution, and a binder solution in which the porous carrier is dispersed (carrier-dispersed binder solution) is prepared.

[0077] Next, the carrier-dispersed binder solution is applied to the surface of the substrate 1 by the above-mentioned application method. As a result, the carrier dispersion binder solution is applied to the surface of the base material 1 (typically the surface of the partition wall 13) to form a precursor film. The precursor film contains the above-mentioned porous carrier, the above-mentioned organic binder, and the above-mentioned aprotic polar solvent.

[0078] Next, the aprotic polar solvent contained in the precursor film is replaced with the poor solvent described above. As a result, a carrier-containing film is formed on the surface of the substrate 1 (typically, the surface of the partition wall 13). Thereafter, the carrier-containing film is dried as necessary. The carrier-containing film contains the porous carrier and the organic binder described above.

[0079] Next, the carbon dioxide adsorbent 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 normal pressure. More specifically, the carbon dioxide adsorbent in liquid form at room temperature and normal pressure is applied to the carrier-containing membrane by the above-mentioned application method. As a result, the carbon dioxide adsorbent is absorbed into the porous carrier of the carrier-containing membrane and supported thereon, forming carbon dioxide adsorbent particles composed of the acid gas adsorption compound and the porous carrier. That is, the carbon dioxide adsorption layer 15 is composed of carbon dioxide adsorbent particles and an organic binder. In this manner, the carbon dioxide adsorption layer 15 containing the carbon dioxide adsorbing particles and the organic binder can be formed again.

[0080] In this manner, the carbon dioxide adsorption device 100 is regenerated. In other words, this method of regenerating a carbon dioxide adsorption device (acid gas adsorption device) is a method of manufacturing a carbon dioxide adsorption device (acid gas adsorption device) equipped with a new carbon dioxide adsorption layer (acid gas adsorption layer). The method of manufacturing a carbon dioxide adsorption device (acid gas adsorption device) includes the above-mentioned adsorption step, the above-mentioned desorption step, the above-mentioned removal step, and the above-mentioned re-formation step. With this method of manufacturing a carbon dioxide adsorption device, a carbon dioxide adsorption device having excellent CO2 recovery performance can be manufactured. [Industrial Applicability]

[0081] The method for regenerating an acid gas adsorption device according to an embodiment of the present invention is used to regenerate an acid gas adsorption device used for separating and recovering acid gas, and can be particularly suitably used to regenerate a carbon dioxide adsorption device used in a carbon dioxide capture, utilization and storage (CCUS) cycle. [Explanation of symbols]

[0082] 10 Honeycomb substrate 13 Bulkhead 14 Cells 15 Carbon dioxide adsorption layer 100 Carbon dioxide adsorption device

Claims

1. a step of supplying a gas containing an acidic gas to an acidic gas adsorption apparatus including a substrate and an acidic gas adsorption layer disposed on a surface of the substrate, the acidic gas adsorption layer including a porous carrier and a nitrogen-containing compound, so as to contact the acidic gas adsorption layer, thereby allowing the acidic gas to be adsorbed by the nitrogen-containing compound; desorbing acid gases from the nitrogen-containing compounds; a step of removing the acidic gas adsorption layer from the surface of the base material of the acidic gas adsorption apparatus in which the step of adsorbing the acidic gas and the step of desorbing the acidic gas have been performed; and forming an acidic gas adsorption layer comprising a porous carrier and a nitrogen-containing compound on the surface of the substrate from which the acidic gas adsorption layer has been removed.

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

3. The substrate is a honeycomb substrate having partition walls defining a plurality of cells, The method for regenerating an acidic gas adsorption apparatus according to claim 1 or 2, wherein the acidic gas adsorption layer is formed on a surface of the partition wall.

4. the material constituting the substrate includes at least one selected from the group consisting of cordierite, alumina, mullite, silicon carbide, a silicon-silicon carbide composite material, and silicon nitride; the porous support comprises a metal-organic framework and / or activated carbon; 3. The method for regenerating an acidic gas adsorption device according to claim 1, wherein in the step of removing the acidic gas adsorption layer from the surface of the base material, the acidic gas adsorption device is heated to burn off the acidic gas adsorption layer.

5. 5. The method for regenerating an acidic gas adsorption device according to claim 4, wherein the acidic gas adsorption device is heated to 400° C. or higher in the step of removing the acidic gas adsorption layer from the surface of the base material.

6. the material constituting the substrate includes at least one selected from the group consisting of cordierite, alumina, mullite, silicon carbide, a silicon-silicon carbide composite material, and silicon nitride; the porous support comprises a metal-organic framework and / or activated carbon; 4. The method for regenerating an acidic gas adsorption device according to claim 3, wherein in the step of removing the acidic gas adsorption layer from the surface of the base material, the acidic gas adsorption device is heated to burn off the acidic gas adsorption layer.

7. 3. The method for regenerating an acidic gas adsorption apparatus according to claim 1, wherein in the step of causing the nitrogen-containing compound to adsorb the acidic gas, the gas containing the acidic gas supplied to the acidic gas adsorption apparatus is air.

8. 4. The method for regenerating an acidic gas adsorption apparatus according to claim 3, wherein in the step of causing the nitrogen-containing compound to adsorb the acidic gas, the gas containing the acidic gas supplied to the acidic gas adsorption apparatus is air.

9. A step of supplying a gas containing an acidic gas to an acidic gas adsorption apparatus including a substrate and an acidic gas adsorption layer disposed on a surface of the substrate, the acidic gas adsorption layer including a porous carrier and a nitrogen-containing compound, so as to contact the acidic gas adsorption layer, thereby allowing the acidic gas to be adsorbed by the nitrogen-containing compound; desorbing an acid gas from the nitrogen-containing compound; a step of removing the acidic gas adsorption layer from the surface of the base material of the acidic gas adsorption apparatus in which the step of adsorbing the acidic gas and the step of desorbing the acidic gas have been performed; and forming an acidic gas adsorption layer comprising a porous carrier and a nitrogen-containing compound on the surface of the substrate from which the acidic gas adsorption layer has been removed.

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