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

Abstract

The invention provides a regeneration method of an acid gas adsorption device and an operation method of the acid gas adsorption device, which can smoothly recover acid gas recovery performance and reduce operation cost. And a method for producing an acid gas adsorption device, which is capable of producing an acid gas adsorption device having excellent acid gas recovery performance. A method for regenerating an acid gas adsorption device according to an embodiment of the present invention comprises the steps of: supplying an acid gas to an acid gas adsorption device so as to be in contact with an acid gas adsorption layer, and adsorbing the acid gas on an acid gas adsorption material; the acid gas is separated from the acid gas adsorption material; and supplying and adhering an acid gas adsorption material to an acid gas adsorption layer of the acid gas adsorption device subjected to the step of adsorbing the acid gas and the step of desorbing the acid gas.

Description

Technical Field

[0001] The present invention relates to a regeneration method of an acid gas adsorption device, a manufacturing method of an acid gas adsorption device, and an operation method of an acid gas adsorption device. Background Art

[0002] In recent years, efforts have been made to separate and recover acid gases contained in the atmosphere in order to reduce the environmental load. As such acid gases, carbon dioxide (hereinafter sometimes referred to as CO2) that causes global warming can be mainly cited. As a representative example of this effort, the carbon dioxide capture, utilization and storage (CCUS) cycle is known. As a carbon dioxide adsorption device for separating and recovering carbon dioxide, a CO2 capture absorbent structure has been proposed, which includes: a honeycomb substrate having a plurality of partitions, thereby forming a plurality of flow channels; and a functional structural unit, which is arranged in and on the partitions (for example, see Patent Document 1). In the CO2 capture absorbent structure, CO2 can be captured from a gas fluid flowing in the absorbent structure, and the captured CO2 can be released under specified conditions. However, if the CO2 capture absorbent structure described in Patent Document 1 is used to repeatedly adsorb and release CO2 contained in the atmosphere, the CO2 recovery rate may gradually decrease due to impurities contained in the atmosphere and repeated heating treatment. In this case, the entire CO 2 capturing absorbent structure needs to be replaced, which causes a problem of increased running costs.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: International Publication No. 2013 / 119929 Summary of the invention

[0006] The main object of the present invention is to provide a regeneration method of an acid gas adsorption device and an operation method of an acid gas adsorption device, which can smoothly restore the acid gas recovery performance and reduce the operating cost, and a manufacturing method of an acid gas adsorption device that can manufacture an acid gas adsorption device with excellent acid gas recovery performance.

[0007] [1] A method for regenerating an acid gas adsorption device according to an embodiment of the present invention comprises the following steps: supplying acid gas to the acid gas adsorption device in a manner that the acid gas adsorption layer of the acid gas adsorption device having a substrate and an acid gas adsorption layer is in contact with the acid gas adsorption layer, thereby causing the acid gas to be adsorbed on an acid gas adsorption material contained in the acid gas adsorption layer, wherein the acid gas adsorption layer is arranged on the surface of the substrate; causing the acid gas to be desorbed from the acid gas adsorption material; and supplying the acid gas adsorption material to the acid gas adsorption layer of the acid gas adsorption device on which the steps of adsorbing the acid gas and desorbing the acid gas have been performed, thereby causing the acid gas to adhere.

[0008] [2] In the method for regenerating an acid gas adsorption device described in [1] above, the acid gas may be carbon dioxide.

[0009] [3] In the method for regenerating an acid gas adsorption device 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 surfaces of the partitions.

[0010] [4] In the method for regenerating an acidic gas adsorption device described in any one of [1] to [3] above, the material constituting the above-mentioned substrate is selected from cordierite, alumina, mullite, silicon carbide, silicon-silicon carbide composite materials, silicon nitride or a combination thereof.

[0011] [5] In the regeneration method of the acid gas adsorption device described in any one of [1] to [4] above, the acid gas adsorption material is selected from nitrogen-containing compounds, organic metal structures, activated carbon, nitrogen-doped carbon, alkaline compounds, carbonates, bicarbonates, zeolites, ionic liquids or combinations thereof.

[0012] [6] In the method for regenerating an acidic gas adsorption device according to any one of [1] to [5] above, the acidic gas adsorption layer may further include a porous carrier.

[0013] [7] In the method for regenerating an acid gas adsorbent device according to any one of [1] to [6] above, the acid gas adsorbent layer may include particles containing at least the acid gas adsorbent material and an organic binder capable of binding the particles. The organic binder may be soluble in an aprotic polar solvent and substantially insoluble in a protic polar solvent. In the step of supplying the acid gas adsorbent material to the acid gas adsorbent layer and causing it to adhere, the particles containing at least the acid gas adsorbent material may be supplied to the acid gas adsorbent layer.

[0014] [8] Another aspect of the present invention relates to a method for manufacturing an acid gas adsorption device, comprising the following steps: supplying acid gas to the acid gas adsorption device in a manner that the acid gas adsorption layer of the acid gas adsorption device has a substrate and an acid gas adsorption layer so as to be in contact with the acid gas adsorption layer and causing the acid gas to be adsorbed on an acid gas adsorption material contained in the acid gas adsorption layer, wherein the acid gas adsorption layer is arranged on the surface of the substrate; causing the acid gas to be desorbed from the acid gas adsorption material; and supplying the acid gas adsorption material to the acid gas adsorption layer of the acid gas adsorption device that has been subjected to the steps of adsorbing the acid gas and desorbing the acid gas and causing the acid gas to adhere thereto.

[0015] [9] Another aspect of the present invention relates to a method for operating an acid gas adsorption device, comprising the following steps: supplying acid gas to the acid gas adsorption device in a manner that the acid gas adsorption layer of the acid gas adsorption device has a substrate and an acid gas adsorption layer so that the acid gas is adsorbed on an acid gas adsorption material contained in the acid gas adsorption layer, wherein the acid gas adsorption layer is arranged on the surface of the substrate; and causing the acid gas to be separated from the acid gas adsorption material, wherein in the step of causing the acid gas to be adsorbed on the acid gas adsorption material, the acid gas adsorption material is supplied together with the acid gas and adheres to the acid gas adsorption layer.

[0016] Effects of the Invention

[0017] According to an embodiment of the present invention, a regeneration method of an acid gas adsorption device and an operation method of an acid gas adsorption device that can smoothly restore the acid gas recovery performance and reduce the operating cost, as well as a manufacturing method of an acid gas adsorption device that can manufacture an acid gas adsorption device with excellent acid gas recovery performance can be realized. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is a schematic perspective view of a carbon dioxide adsorption device according to one embodiment of the present invention.

[0019] Figure 2 yes Figure 1 A schematic cross-sectional view of a carbon dioxide adsorption device. DETAILED DESCRIPTION

[0020] Hereinafter, embodiments of the present invention will be described with reference to the drawings; however, the present invention is not limited to these embodiments.

[0021] A. Overview of the regeneration method of the acid gas adsorption device

[0022] Figure 1 This is a schematic perspective view of a carbon dioxide adsorption device according to one embodiment of the present invention. Figure 2 yes Figure 1A schematic cross-sectional view of a carbon dioxide adsorption device.

[0023] A regeneration method for an acid gas adsorption device according to one embodiment of the present invention includes the following steps: supplying acid gas to an acid gas adsorption device 100 in a manner that contacts an acid gas adsorption layer 15 so that the acid gas is adsorbed on an acid gas adsorption material, the acid gas adsorption device 100 comprising a substrate 1 and an acid gas adsorption layer 15, the acid gas adsorption layer 15 being arranged on the surface of the substrate 1 and containing the acid gas adsorption material (adsorption step); desorbing the acid gas from the acid gas adsorption material (desorption step); and supplying the acid gas adsorption material to the acid gas adsorption layer 15 of the acid gas adsorption device 100 subjected to the adsorption step and the desorption step and causing the acid gas adsorption material to adhere (adhesion step).

[0024] The inventors of the present invention have found that the life of the substrate is longer than that of the acid gas adsorbent, and have completed the present invention. More specifically, the acid gas adsorbent is resupplied to and attached to the acid gas adsorption layer of the acid gas adsorption device that has been subjected to the adsorption process and the desorption process. Thus, even if the acid gas recovery performance of the acid gas adsorption layer is reduced during the adsorption process and the desorption process, the acid gas recovery performance of the acid gas adsorption layer can be smoothly restored by the attachment process. As a result, the substrate can be reused, and the running cost can be reduced.

[0025] Examples of the acidic gas include carbon dioxide (CO 2 ), hydrogen sulfide, sulfur dioxide, nitrogen dioxide, and hydrogen chloride.

[0026] In one embodiment, the acidic gas is carbon dioxide (CO2). In this embodiment, the acidic gas adsorption device 100 is a carbon dioxide adsorption device 100, the acidic gas adsorption layer 15 is a carbon dioxide adsorption layer 15, and the acidic gas adsorption material is a carbon dioxide adsorption material. Hereinafter, the carbon dioxide adsorption device 100 as one embodiment of the acidic gas adsorption device will be described in detail.

[0027] B. Carbon dioxide adsorption device

[0028] 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 thereof include: a filter structure such as a honeycomb or a filter cloth; a particle 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.

[0029] B-1. Substrate (honeycomb substrate)

[0030] In one embodiment, the substrate 1 is a honeycomb substrate 10 having a plurality of cells 14 .

[0031] The cells 14 extend 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 longitudinal direction (axial direction) of the honeycomb substrate 10 (see Figure 2 ). The cell 14 has any appropriate shape in the cross section of the honeycomb substrate 10 in a direction perpendicular to the longitudinal direction. Examples of the cross-sectional shape of the cell include: a triangle, a quadrilateral, a pentagon, a polygon larger than a hexagon, a circle, and an ellipse. The cross-sectional shape and size of the cell may be all the same, or at least part of them may be different. Among the cross-sectional shapes of such cells, preferably, a hexagon or a quadrilateral may be mentioned, and more preferably, a square, a rectangle or a hexagon may be mentioned.

[0032] The cell density in the cross section of the honeycomb substrate in a direction perpendicular to the longitudinal direction (i.e., the number of cells 14 per unit area) can be appropriately set according to the purpose. The cell density can be, for example, 4 cells / cm 2 ~320 compartments / cm 2 When the cell density is within such a range, the strength and effective GSA (geometric surface area) of the honeycomb substrate can be sufficiently ensured.

[0033] 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 prism shape with a polygonal bottom, and a column shape with an irregular bottom. The honeycomb substrate 10 shown in the figure has a cylindrical shape. The outer diameter and length of the honeycomb substrate can be appropriately set according to the purpose. Although not shown in the figure, the honeycomb substrate may have a hollow area in the center of the cross section in a direction perpendicular to the longitudinal direction.

[0034] Typically, the honeycomb substrate 10 includes an outer peripheral wall 11 and partition walls 13 located inside the outer peripheral wall 11. In the example shown in the figure, the outer peripheral wall 11 and the partition walls 13 are formed integrally. The outer peripheral wall 11 and the partition walls 13 may be separate bodies.

[0035] 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 is, for example, 0.1 mm to 10 mm.

[0036] The partition wall 13 defines a plurality of compartments 14. More specifically, the partition wall 13 includes a first partition wall 13a and a second partition wall 13b, which are orthogonal to each other, and the first partition wall 13a and the second partition wall 13b define a plurality of compartments 14. The cross-sectional shape of the compartment 14 is a quadrilateral except for the portion where the first partition wall 13a and the second partition wall 13b contact the outer peripheral wall 11. It should be noted that the configuration of the partition wall is not limited to the above-mentioned partition wall 13. The partition wall may include: a first partition wall extending in a radial direction, and a second partition wall extending in a circumferential direction, which define a plurality of compartments.

[0037] The thickness of the partition wall 13 can be appropriately set according to the purpose of the honeycomb substrate. Typically, the thickness of the partition wall 13 is thinner than the thickness of the peripheral wall 11. The thickness of the partition wall 13 is, for example, 0.03 mm to 0.6 mm. For example, the thickness of the partition wall is measured by cross-sectional observation using a SEM (scanning electron microscope). If the thickness of the partition wall is within such a range, the mechanical strength of the honeycomb substrate can be sufficient, and the opening area (the total area of ​​the cells in the cross section) can be sufficient.

[0038] The porosity of the partition walls 13 can be appropriately set according to 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, for example, by mercury intrusion porosimetry.

[0039] The density of the partition walls 13 can be appropriately set according to the purpose. For example, the density of the partition walls 13 is 1.7 g / cm 3 Above, preferably 1.8 g / cm 3 Above, for example, 2.8 g / cm 3 Below, preferably 2.6 g / cm 3 It should be noted that, for example, the density can be measured by mercury intrusion porosimetry.

[0040] As the material constituting the partition wall 13, representatively, ceramics can be cited. As ceramics, for example, silicon carbide, silicon-silicon carbide composite materials, cordierite, mullite, alumina, silicon nitride, spinel, silicon carbide-cordierite composite materials, lithium aluminum silicate and aluminum titanate can be cited. The materials constituting the partition wall can be used alone or in combination. Among the materials constituting the partition wall, preferably, cordierite, alumina, mullite, silicon carbide, silicon-silicon carbide composite materials and silicon nitride can be cited, and more preferably, silicon carbide and silicon-silicon carbide composite materials can be cited.

[0041] Typically, the honeycomb substrate 10 is manufactured by the following method. First, a binder and water or an organic solvent are added to the material powder containing the ceramic powder as required, and the obtained mixture is kneaded to form a blank. The blank is molded (typically extrusion molded) into a desired shape, and then dried and fired as required to manufacture the honeycomb substrate 10. In the case of firing, the firing is performed at, for example, 1200° C. to 1500° C. The firing time is, for example, 1 hour or more and 20 hours or less.

[0042] B-2. Carbon dioxide adsorption layer

[0043] 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 (representatively, a central portion) of 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., surrounding the gas flow path 16) as shown in the example shown in the figure, or may be formed on a portion of the surface of the partition wall. If the carbon dioxide adsorption layer 15 is formed on the entire inner surface of the partition wall 13, the removal efficiency of CO2 can be improved.

[0044] The gas flow path 16 extends from the first end face 1a (inflow end face) to the second end face 1b (outflow end face) in the same manner as the compartment 14. The cross-sectional shape of the gas flow path 16 may be the same as that of the compartment 14, preferably a hexagon or a quadrilateral, more preferably a square, a rectangle or a hexagon. The cross-sectional shape and size of the gas flow path 16 may be the same in all or may be at least partially different.

[0045] The thickness of the carbon dioxide adsorption layer 15 is not particularly limited, and is, for example, 10 μm or more, preferably 50 μm or more, and, for example, 1000 μm or less, preferably 500 μm or less.

[0046] B-2-1. Carbon dioxide adsorption layer formed by carbon dioxide adsorbing material

[0047] The carbon dioxide adsorbing layer 15 contains a carbon dioxide adsorbing material as an example of an acidic gas adsorbing material. In one embodiment, the carbon dioxide adsorbing layer is formed of the carbon dioxide adsorbing material and is directly supported on the partition wall so as to face the gas flow path.

[0048] As the carbon dioxide adsorbent, any appropriate compound that can adsorb and desorb CO2 can be used. Examples of carbon dioxide adsorbents 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 hydrogen carbonate and potassium hydrogen carbonate; organometallic structures (MOFs) such as MOF-74, MOF-200, and MOF-210; zeolites; activated carbon; nitrogen-doped carbon; ionic liquids, etc.

[0049] Among the carbon dioxide adsorbents, nitrogen-containing compounds are more preferably mentioned. As nitrogen-containing compounds, more specifically, amine compounds such as monoethanolamine, diethanolamine, triethanolamine, N-(3-aminopropyl)diethanolamine, aminopropyltrimethoxysilane, polyethyleneamine, methyldiethylamine, and tetraethylenepentamine; piperazine compounds such as 1-(2-hydroxyethyl)piperazine; aminosilane coupling agents such as polyethyleneiminetrimethoxysilane, aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane; organic polymers having primary to tertiary amino groups such as polyethyleneimine, polyamideamine, and polystyrene endowed with amino groups; organic monomers having primary to tertiary amino groups such as ethyleneimine and styrene endowed with amino groups; and organic / inorganic compounds endowed with amino groups as substituents. The carbon dioxide adsorbents can be used alone or in combination.

[0050] In this embodiment, the carbon dioxide adsorption layer does not substantially contain any component other than the carbon dioxide adsorption material. When the carbon dioxide adsorption layer is formed of the carbon dioxide adsorption material, the content of the carbon dioxide adsorption material in the carbon dioxide adsorption layer is typically 95.0 mass % or more and 100 mass % or less. If the content of the carbon dioxide adsorption material is within the above range, an excellent CO2 recovery rate can be stably ensured.

[0051] Typically, the following method is used to prepare a carbon dioxide adsorption layer formed by a carbon dioxide adsorbent. First, the above-mentioned carbon dioxide adsorbent is dissolved in a solvent to prepare a carbon dioxide adsorbent solution. Examples of the solvent include: water, alcohols, and glycols. The solvent can be used alone or in combination. Among the solvents, preferably, an aqueous solvent (water and a mixed solvent containing water) can be used. Next, the carbon dioxide adsorbent solution is applied to a substrate (specifically, a partition), and then the coating is dried and sintered as needed to form a carbon dioxide adsorption layer formed by the carbon dioxide adsorbent.

[0052] B-2-2. Carbon dioxide adsorption layer comprising an ionic liquid and a carbon dioxide adsorbing material other than an ionic liquid

[0053] 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 material other than the ionic liquid (hereinafter referred to as other carbon dioxide adsorbent material). Typically, the ionic liquid coats other carbon dioxide adsorbent materials (e.g., nitrogen-containing compounds). If the carbon dioxide adsorption layer contains an ionic liquid, it is possible to achieve improved performance and longer life of the carbon dioxide adsorbent material.

[0054] Ionic liquids are liquid "salts" composed only of ions (anions and cations), and are in a liquid state at normal temperature and pressure (23°C, 0.1 MPa). Examples of cations of ionic liquids include: ammonium ions such as imidazolium salts and pyridinium salts, phosphonium ions, sulfonium salts, inorganic ions, and the like. Examples of anions of ionic liquids include: halogen ions such as bromide ions and trifluoromethanesulfonates; boron ions such as tetraphenylborate; phosphorus ions such as hexafluorophosphate; sulfur ions such as alkyl sulfonates. The above ionic liquids can be used alone or in combination. Among the ionic liquids, preferably, a combination of imidazolium salts as cations and trifluoromethanesulfonates as anions can be mentioned.

[0055] When the carbon dioxide adsorption layer uses an ionic liquid and other carbon dioxide adsorbents in combination, the content ratio of the total of the ionic liquid and other carbon dioxide adsorbents in the carbon dioxide adsorption layer (i.e., the total of the carbon dioxide adsorbents) is, for example, 30 mass % or more, preferably 50 mass % or more, for example, 100 mass % or less, preferably 99 mass % or less.

[0056] In this embodiment, the content ratio of the ionic liquid is, for example, 0.000001 parts by mass or more, preferably 0.00001 parts by mass or more, for example, 0.1 parts by mass or less, preferably 0.05 parts by mass or less, relative to 1 part by mass of other carbon dioxide adsorbents. If the content ratio of the ionic liquid is within the above range, the performance improvement and long life of the carbon dioxide adsorbent can be stably achieved.

[0057] B-2-3. Carbon dioxide adsorption layer including carbon dioxide adsorbent and porous body

[0058] In one embodiment, the carbon dioxide adsorption layer includes a porous carrier in addition to the above-mentioned carbon dioxide adsorption material. In this case, the carbon dioxide adsorption material is typically carried on the porous carrier and faces the gas flow path. If the carbon dioxide adsorption layer includes a porous carrier, a new carbon dioxide adsorption material can be stably attached to the carbon dioxide adsorption layer (specifically, the porous carrier) in the attachment process.

[0059] The porous carrier can form mesopores in the carbon dioxide adsorption layer. As the porous carrier, for example, there can be mentioned: organometallic structures (MOFs) such as MOF-74, MOF-200, and MOF-210; activated carbon; nitrogen-doped carbon; mesoporous silica; mesoporous alumina; zeolite; carbon nanotubes, preferably, there can be mentioned: organometallic structures (MOFs), activated carbon, zeolite, mesoporous silica, and mesoporous alumina. The porous carrier can be used alone or in combination. The porous carrier preferably uses a material different from the carbon dioxide adsorption material.

[0060] The BET specific surface area of ​​the porous carrier is, for example, 50 m 2 / g or more, preferably 500m 2 If the surface area of ​​the porous carrier is greater than the above lower limit, the carbon dioxide adsorbent can be stably supported, thereby improving the CO2 recovery rate. The upper limit of the BET specific surface area of ​​the porous carrier is typically 2000 m 2 / g or less.

[0061] When the carbon dioxide adsorption layer contains a carbon dioxide adsorbent and a porous carrier, the total content ratio of the carbon dioxide adsorbent and the porous carrier in the carbon dioxide adsorption layer is, for example, 30 mass % or more, preferably 50 mass % or more, for example, 100 mass % or less, preferably 99 mass % or less.

[0062] In this embodiment, the content ratio of the porous carrier in the carbon dioxide adsorption layer is, for example, 0.1 mass % or more, preferably 10 mass % or more, for example, 70 mass % or less, preferably 50 mass % or less. In addition, the content ratio of the porous carrier is, for example, 0.01 mass part or more, preferably 0.3 mass part or more, for example, 0.7 mass part or less, preferably 0.5 mass part or less, relative to 1 mass part of the carbon dioxide adsorbent. If the content ratio of the porous carrier is within the above range, the carbon dioxide adsorbent can be more stably attached in the attachment process.

[0063] Typically, the following method is used to prepare a carbon dioxide adsorption layer comprising a carbon dioxide adsorbent and a porous carrier. First, the porous carrier is dispersed in a dispersion medium as required to prepare a dispersion of the porous carrier, and the carbon dioxide adsorbent is added to the dispersion. The dispersion medium is the same as, for example, the solvent described in item B-2-1 above. Next, the dispersion comprising the carbon dioxide adsorbent and the porous carrier is applied to a substrate (specifically, a partition), and then the coating is dried and sintered as required to form a carbon dioxide adsorption layer.

[0064] Alternatively, a dispersion containing a carbon dioxide adsorbent other than an ionic liquid and a porous carrier is applied to a substrate, the coating is dried and sintered as necessary, and then only the ionic liquid is applied to the substrate to form a carbon dioxide adsorbing layer.

[0065] The method for preparing a carbon dioxide adsorption layer comprising a carbon dioxide adsorbent and a porous carrier is not limited to the above method. For example, the above-mentioned porous carrier is dispersed in a dispersion medium to prepare a dispersion of the porous carrier, and the dispersion is applied to a substrate. After that, the coating is dried and heated to, for example, 400°C or more and 800°C or less to sinter it to form a carrier-containing film. Thereafter, a liquid carbon dioxide adsorbent or a solution of a carbon dioxide adsorbent is applied to the carrier-containing film at normal temperature and pressure. Thus, the carbon dioxide adsorbent infiltrates and is carried on the porous carrier containing the carrier film to form a carbon dioxide adsorption layer.

[0066] B-2-4. Carbon dioxide adsorption layer comprising carbon dioxide adsorbing particles and an organic binder

[0067] In another embodiment, the carbon dioxide adsorption layer includes: particles containing at least the above-mentioned carbon dioxide adsorption material, and an organic binder. The particles containing the above-mentioned carbon dioxide adsorption material have carbon dioxide adsorption capacity, and are hereinafter referred to as particles with carbon dioxide adsorption capacity. The organic binder can bond the particles with carbon dioxide adsorption capacity, and typically, fix and bond them to a substrate. The organic binder can be dissolved in aprotic polar solvents and is substantially insoluble in protic polar solvents. That is, the organic binder has tolerance (water resistance) relative to water as 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, for example, water vapor in the atmosphere. Therefore, the volume expansion and / or strength reduction of the organic binder can be suppressed, and further, the change in the structure maintained by the organic binder bonding the particles with carbon dioxide adsorption capacity can be suppressed. As a result, regardless of the use environment, an excellent carbon dioxide adsorption capacity can be maintained.

[0068] The surface of the carbon dioxide adsorption layer on the opposite side to the substrate preferably has a three-dimensional mesh structure or a porous layer structure. Therefore, acidic gases such as carbon dioxide can be efficiently diffused from the surface of the carbon dioxide adsorption layer toward the inside. In particular, since the organic binder has water resistance, such a fine structure can be stably maintained on the surface that can contact with acidic gases regardless of the use environment.

[0069] Typically, the carbon dioxide adsorbing particles are in a solid state at normal temperature and pressure (23°C, 0.1 MPa). The carbon dioxide adsorbing layer includes a plurality of carbon dioxide adsorbing particles. The carbon dioxide adsorbing particles contained in the carbon dioxide adsorbing layer may be primary particles or secondary particles formed by agglomeration of a plurality of primary particles.

[0070] In one embodiment, the carbon dioxide adsorbing particle includes: the carbon dioxide adsorbing material and a carrier that supports the carbon dioxide adsorbing material. However, the carbon dioxide adsorbing particle may be composed only of the carbon dioxide adsorbing material without containing a carrier. That is, the acidic gas adsorbing particle may be composed only of the carbon dioxide adsorbing material that is solid at normal temperature and pressure.

[0071] The carbon dioxide adsorbing material contained in the carbon dioxide adsorbing particles preferably includes the nitrogen-containing compounds mentioned above, and more preferably includes the organic monomers having primary to tertiary amino groups and the organic polymers having primary to tertiary amino groups mentioned above. The weight average molecular weight M of the organic polymer is w The molecular weight (in terms of polystyrene) 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.

[0072] In one embodiment, the carbon dioxide adsorbing material contained in the carbon dioxide adsorbing particles is substantially insoluble in a protic polar solvent (typically water) and an aprotic polar solvent.

[0073] 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. It should be noted that the lower limit of the solubility of the carbon dioxide adsorbent in water is typically 0.01 g / 100 g-H2O or more.

[0074] The solubility of the carbon dioxide adsorbent in the 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 the aprotic polar solvent is below the above upper limit, the carbon dioxide adsorbent can be suppressed from dissolving in the aprotic polar solvent during the manufacture of the carbon dioxide adsorption device. It should be noted that the lower limit of the solubility of the carbon dioxide adsorbent in the aprotic polar solvent is typically 0.01 g / 100 g-aprotic polar solvent or more.

[0075] The solubility parameter of the carbon dioxide adsorbent is, for example, 7 or more, preferably 8 or more, and, for example, 20 or less, preferably 15 or less. For example, the solubility parameter can be calculated by the Hildebrand method.

[0076] As the carrier, any suitable carrier that can support the carbon dioxide adsorbent can be used. The carrier is preferably the above-mentioned porous carrier. In addition, from the viewpoint of thermal conductivity, a metal material is sometimes used. For example, steel materials such as carbon steel and alloy steel; non-ferrous metals such as copper, aluminum, nickel, and their alloys can be cited. In the case of a metal material, it is not limited to a porous shape.

[0077] As an organic binder, any appropriate organic compound that can bind particles with carbon dioxide adsorption capacity can be used. The organic binder can be dissolved in aprotic polar solvents and is substantially insoluble in protic polar solvents. As an organic binder, for example, fluoropolymers such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene propylene copolymer (FEP), ethylene tetrafluoroethylene copolymer (ETFE); amorphous plastics such as polyethersulfone (PES). The organic binder can be used alone or in combination.

[0078] Among the organic binders, preferably, an organic binder having at least water as a poor solvent (an organic binder substantially insoluble in water) can be cited, more preferably, a fluoropolymer can be cited, and further preferably, polyvinylidene fluoride can be cited. If the organic binder contains a fluoropolymer (polyvinylidene fluoride), excellent heat resistance and water resistance can be imparted to the carbon dioxide adsorption device.

[0079] The solubility of the organic binder in the protic polar solvent (representatively 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 the protic polar solvent (representatively water) is below the above upper limit, excellent water resistance can be stably imparted to the acidic gas adsorption device. It should be noted that the lower limit of the solubility of the organic binder in the protic polar solvent (representatively water) is typically 0.01 g / 100 g-H2O or more.

[0080] The solubility parameter of the organic binder is, for example, 9 or more, preferably 10 or more, and for example, 15 or less, preferably 13 or less.

[0081] The carbon dioxide adsorbing layer may contain any appropriate additive material in addition to the carbon dioxide adsorbing particles and the organic binder.

[0082] The total content of the carbon dioxide adsorbing particles and the organic binder in the carbon dioxide adsorbing 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 % can be measured, for example, by microstructural observation or elemental analysis.

[0083] The content of the carbon dioxide adsorbing 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 the carbon dioxide adsorbing particles is greater than the above 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.

[0084] The content of the organic binder in the carbon dioxide adsorption layer is, for example, 5% by volume or more, preferably 15% by volume or more. If the content of the organic binder is greater than the above lower limit, the carbon dioxide adsorption particles can be prevented from falling off from the carbon dioxide adsorption layer in the adsorption step and / or the desorption step described later. The upper limit of the content of the organic binder is typically 70% by volume or less.

[0085] Typically, the carbon dioxide adsorption layer 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%.

[0086] Typically, the carbon dioxide adsorbing layer including carbon dioxide adsorbing particles and an organic binder can be produced by the following method: First, the organic binder is dissolved in an aprotic polar solvent to prepare a binder solution.

[0087] The aprotic polar solvent can dissolve the organic binder but cannot dissolve the carbon dioxide adsorbing particles (more specifically, the carbon dioxide adsorbing material).

[0088] As the aprotic polar solvent, any appropriate organic solvent can be used. Examples of the aprotic polar solvent include: N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF). The aprotic polar solvent can be used alone or in combination.

[0089] Among the aprotic polar solvents, N-methyl-2-pyrrolidone (NMP) is preferably used. If the aprotic polar solvent contains NMP, the organic binder (particularly PVDF) can be dissolved more smoothly, and the dissolution of the carbon dioxide adsorbent can be stably suppressed.

[0090] 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.

[0091] 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 greater than the above lower limit, the carbon dioxide adsorbent can be suppressed 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.

[0092] Next, the carbon dioxide adsorbing particles are added to the binder solution and dispersed.

[0093] A solution in which an organic binder is dissolved in an aprotic polar solvent and particles having a carbon dioxide adsorbing capacity are dispersed (particle-dispersed binder solution) is applied to the surface of the substrate by any appropriate method in the same manner as described above.

[0094] Thus, the particle-dispersed binder solution is applied to the surface of the substrate (typically, the surface of the partition wall) to form a precursor film. The precursor film contains the carbon dioxide adsorbing particles, the organic binder, and the aprotic polar solvent.

[0095] Next, the aprotic polar solvent contained in the precursor film is replaced with a poor solvent for the organic binder.

[0096] The poor solvent is less likely to dissolve the organic binder than the aprotic polar solvent (good solvent), and the organic binder is substantially insoluble in the poor solvent. Typically, the solubility parameter distance between the organic binder and the poor solvent is 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.

[0097] Examples of the poor solvent include: protic polar solvents such as water, ethanol, butanol, isopropyl alcohol (IPA) and other alcohols; and freons such as hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), and hydrofluoroolefins (HFOs). The poor solvent may be used alone or in combination. Among the poor solvents, water is preferably used.

[0098] By replacing the aprotic polar solvent, a membrane that is stable with respect to the protic solvent is obtained.

[0099] In this way, a carbon dioxide adsorption layer including carbon dioxide adsorbing particles and an organic binder can be formed on the surface of the substrate (typically, the surface of the partition wall). Thereafter, the carbon dioxide adsorption layer is dried as necessary.

[0100] The method for forming the carbon dioxide adsorption layer including carbon dioxide adsorbing particles and an 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 is added to the binder solution and dispersed.

[0101] Thus, 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.

[0102] Next, the carrier-dispersed binder solution is applied to the surface of the substrate using the above-mentioned coating method. Thus, the carrier-dispersed binder solution is applied to the surface of the substrate (representatively, the surface of the partition wall) to form a precursor film. The precursor film includes the above-mentioned porous carrier, the above-mentioned organic binder, and the above-mentioned aprotic polar solvent.

[0103] Next, the aprotic polar solvent contained in the precursor film is replaced with the above-mentioned poor solvent.

[0104] Thus, a carrier-containing film is formed on the surface of the substrate (typically, the surface of the partition wall). Thereafter, the carrier-containing film is dried as necessary. The carrier-containing film includes the porous carrier and the organic binder.

[0105] 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 pressure. More specifically, the carbon dioxide adsorbent that is liquid at room temperature and pressure is applied to the carrier-containing membrane using the above-mentioned coating method. As a result, the carbon dioxide adsorbent infiltrates and is supported on the porous carrier of the carrier-containing membrane, forming carbon dioxide adsorbent particles composed of the acidic gas adsorbent compound and the porous carrier. That is, the carbon dioxide adsorption layer is composed of carbon dioxide adsorbent particles and an organic binder.

[0106] By the above operation, a carbon dioxide adsorbing layer including the carbon dioxide adsorbing particles and the organic binder can be formed.

[0107] Although not shown in the figure, the carbon dioxide adsorption device 100 can be equipped in a carbon dioxide adsorption device. In one embodiment, the carbon dioxide adsorption device includes: a plurality of carbon dioxide adsorption devices; a fan for supplying a gas containing CO2 (CO2-containing gas) to the carbon dioxide adsorption layer; and a pump for sucking CO2 desorbed from the carbon dioxide adsorption layer.

[0108] C. Adsorption process and separation process

[0109] As described above, the regeneration method of the carbon dioxide adsorbent according to one embodiment includes the following steps: an adsorption step in which CO 2 is adsorbed on the carbon dioxide adsorbent provided in the carbon dioxide adsorbent 100 ; and a desorption step in which CO 2 is desorbed from the carbon dioxide adsorbent.

[0110] In the adsorption process, typically, a CO2-containing gas is caused to flow through the gas flow path 16 so that CO2 contacts 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, greater than 100 ppm and less than 2% by volume. In addition to CO2, the CO2-containing gas typically also contains nitrogen. The temperature of the CO2-containing gas in the adsorption process is, for example, greater than 0°C and less than 40°C. The pressure of the CO2-containing gas in the adsorption process is, for example, 0.3×10 5 Pa or more and 2.0×10 5 Pa or less. 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 implementation time 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.

[0111] Thus, the carbon dioxide adsorbent material facing the gas flow path 16 adsorbs CO2. The CO2 recovery rate in the adsorption process (=100-(CO2 concentration in the gas that has passed through the gas flow path / CO2 concentration in the gas before flowing into the gas flow path × 100)) is, for example, 80% or more, preferably 85% or more, more preferably 90% or more, for example, 100% or less.

[0112] The separation process (sometimes also called the desorption process) is carried out after the adsorption process. In the separation process, typically, the carbon dioxide adsorption device is heated and the separated CO2 is sucked and recovered by a pump or the like, or the recovered CO2 is pumped into the carbon dioxide adsorption device again, heated, and the separated CO2 is recovered.

[0113] The temperature in the desorption step is, for example, higher than 40° C., preferably higher than 70° C., and is, for example, lower than 200° C., preferably lower than 110° C. The desorption step is performed for, for example, 1 minute to 1 hour.

[0114] As a result, CO 2 retained by the carbon dioxide adsorbent is released (released, desorbed) from the carbon dioxide adsorbent. Therefore, CO 2 can be recovered and utilized for various purposes (for example, metallization).

[0115] The above-mentioned adsorption step and desorption step are preferably repeated. In one embodiment, the adsorption step and desorption step are cyclically performed, for example, 10 times or more, preferably 30 times or more, more preferably 50 times or more, and further preferably 100 times or more.

[0116] D. Attachment process

[0117] In one embodiment, the attachment step is performed after the adsorption step and the desorption step are performed (preferably after the adsorption step and the desorption step are cycled within the above range). In addition, the attachment step can be performed after the CO2 recovery rate in the adsorption step is less than the above lower limit.

[0118] After the adsorption process and the separation process and before the attachment process, a pretreatment process for removing impurities attached to the carbon dioxide adsorption device can be performed. If the pretreatment process is performed, impurities contained in the carbon dioxide adsorption device (for example, garbage and dust attached to the surface of the carbon dioxide adsorption layer) are removed before the attachment process, so that in the subsequent attachment process, new carbon dioxide adsorption material can be evenly applied to the carbon dioxide adsorption layer.

[0119] Examples of the pretreatment method include a method of passing a larger amount of air than the CO 2 -containing gas in the adsorption step through the gas flow path, and a method of passing water vapor through the gas flow path.

[0120] In the attachment process, a new carbon dioxide adsorbent is supplied to and attached to (supported on) the carbon dioxide adsorbent layer 15 of the carbon dioxide adsorbent device 100 that has been subjected to the adsorption process and the desorption process. It should be noted that the carbon dioxide adsorbent supplied in the attachment process and the carbon dioxide adsorbent contained in the carbon dioxide adsorbent layer 15 may be the same or different. The carbon dioxide adsorbent supplied in the attachment process is preferably the same as the carbon dioxide adsorbent contained in the carbon dioxide adsorbent layer 15.

[0121] The method for supplying the carbon dioxide adsorbent may be any appropriate method depending on the material of the substrate and the type of the carbon dioxide adsorbent. Examples of the supply method include: a method of spraying a carbon dioxide adsorbent solution onto the carbon dioxide adsorbent layer (spraying method); a method of immersing the carbon dioxide adsorbent device in the carbon dioxide adsorbent solution (wet coating method); a method of allowing the carbon dioxide adsorbent solution to flow into the gas flow path of the carbon dioxide adsorbent device (flow method); and a method of electrostatically coating the carbon dioxide adsorbent onto the carbon dioxide adsorbent layer (electrostatic coating method).

[0122] The method for supplying the carbon dioxide adsorbent is preferably implemented by configuring the carbon dioxide adsorbent device in such a manner that one end (inlet) of the gas flow path is located above the other end (outlet). Thus, the supplied carbon dioxide adsorbent actively falls due to gravity, and can be evenly applied to the carbon dioxide adsorption layer, thereby improving the carbon dioxide adsorption performance of the regenerated carbon dioxide adsorbent device.

[0123] D-1. Spraying method

[0124] When the attachment process is performed by the spraying method, it is not necessary to remove the carbon dioxide adsorption device from the carbon dioxide adsorption equipment (not shown), and the carbon dioxide recovery performance of the carbon dioxide adsorption device can be restored on site. Therefore, there is no need to replace the carbon dioxide adsorption device, which can reduce the maintenance cost of the carbon dioxide adsorption equipment. When the thickness of the carbon dioxide adsorption layer is less than 1 mm, the spraying method is preferably selected in the attachment process.

[0125] In the spray coating method, the carbon dioxide adsorbent solution is first misted and applied to the carbon dioxide adsorbent layer. Thus, the surface of the carbon dioxide adsorbent layer is coated with the carbon dioxide adsorbent solution. Thereafter, the coating is dried at, for example, 20°C to 200°C as required.

[0126] Typically, the carbon dioxide adsorbent is dissolved in a solvent to prepare a carbon dioxide adsorbent solution. Examples of the solvent include water, alcohols, and glycols, and preferably, an aqueous solvent (water and a mixed solvent containing water). The solvents may 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, for example, 50% by mass or less, and preferably 30% by mass or less.

[0127] The spraying method includes, for example, air spraying and ultrasonic spraying, preferably air spraying. The amount of carbon dioxide adsorbent solution applied is typically such that the thickness of the carbon dioxide adsorbent applied by spraying is less than 1 mm, preferably less than 0.1 mm.

[0128] D-2. Wet coating method

[0129] When the attachment process is performed by wet coating, although it is a simple method, the carbon dioxide recovery performance can be smoothly restored. When the thickness of the carbon dioxide adsorption layer is 0.1 mm or more and is required to have a uniform thickness in the longitudinal direction of the adsorption device, the wet coating method is preferably selected in the attachment process.

[0130] In the wet coating method, first, the carbon dioxide adsorbent is immersed in the carbon dioxide adsorbent solution. Thus, the carbon dioxide adsorbent solution adheres to the surface of the carbon dioxide adsorbent layer. After that, the carbon dioxide adsorbent is taken out from the carbon dioxide adsorbent solution and dried, for example, at 20°C or higher and 200°C or lower, as required.

[0131] The carbon dioxide adsorbent solution is the same as the carbon dioxide adsorbent solution described in the above D-1. The immersion time is typically 10 minutes to 24 hours, which is the immersion time for the carbon dioxide adsorbent applied by wet coating to have a thickness of 0.01 mm or more, preferably 0.1 mm or more.

[0132] D-3. Circulation Law

[0133] When the attachment step is performed by the flow method, the carbon dioxide recovery performance of the carbon dioxide adsorption device can be restored on site, similarly to the above-mentioned spray method, and the maintenance cost of the carbon dioxide adsorption equipment can be reduced.

[0134] When the thickness of the carbon dioxide adsorption layer is 0.1 mm or more, it is preferable to select a flow method in the attachment step.

[0135] In the flow method, first, a carbon dioxide adsorbent solution is flowed into the gas flow path of the carbon dioxide adsorbent. Thus, the carbon dioxide adsorbent solution is applied to the surface of the carbon dioxide adsorption layer. Thereafter, the coating is dried at, for example, 20°C to 200°C as required.

[0136] The carbon dioxide adsorbent solution is the same as the carbon dioxide adsorbent solution described in the above section D-1, for example. 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 becomes 0.01 mm or more, preferably 0.1 mm or more.

[0137] D-4. Electrostatic coating method

[0138] When the attachment process is performed by electrostatic coating, the yield of the applied carbon dioxide adsorbent solution is high, so the cost of the coating material can be reduced. When the thickness of the carbon dioxide adsorption layer is less than 1 mm and a uniform thickness is required, the electrostatic coating method is preferably selected in the attachment process. The coating amount of the carbon dioxide adsorbent solution is typically such that the thickness of the carbon dioxide adsorbent applied by the electrostatic coating method becomes less than 1 mm, preferably less than 0.1 mm.

[0139] D-5. Particle supply method

[0140] The carbon dioxide adsorption particles can be supplied to the carbon dioxide adsorption layer using an organic binder (particle supply method). This also allows the carbon dioxide recovery performance of the carbon dioxide adsorption device to be restored on site, thereby reducing the maintenance cost of the carbon dioxide adsorption equipment.

[0141] In the particle supply method, first, a dispersion of carbon dioxide adsorbing particles is flowed into the gas flow path of the carbon dioxide adsorption device. Next, a protic polar solvent (typically water) is flowed into the gas flow path. As a result, the carbon dioxide adsorbing particles are supplied to the surface of the carbon dioxide adsorption layer, and the carbon dioxide adsorbing particles are attached to the organic binder facing the gas flow path. Thereafter, the carbon dioxide adsorption layer is dried as needed.

[0142] Through the above operation, the carbon dioxide adsorption device 100 is regenerated. In other words, the regeneration method of the above carbon dioxide adsorption device (acid gas adsorption device) is a method for manufacturing a carbon dioxide adsorption device (acid gas adsorption device) having a carbon dioxide adsorption layer (acid gas adsorption layer) whose performance has been restored. The method for manufacturing a carbon dioxide adsorption device (acid gas adsorption device) includes: the above adsorption step, the above separation step, and the above attachment step. In the method for manufacturing the above carbon dioxide adsorption device (acid gas adsorption device), a carbon dioxide adsorption device having excellent CO2 recovery performance (acid gas recovery performance) can be manufactured.

[0143] E. Operation method of carbon dioxide adsorption device

[0144] In the above embodiment, the attachment process is performed after the adsorption process and the desorption process are performed, but the attachment process may be performed simultaneously with the adsorption process. In this way, the operation method of the carbon dioxide adsorption device (acid gas adsorption device) includes the above adsorption process and the above desorption process, and in the adsorption process, the carbon dioxide adsorption material (acid gas adsorption material) is supplied together with CO2 (acid gas) and attached to the carbon dioxide adsorption layer (acid gas adsorption layer). When the attachment process and the adsorption process are performed simultaneously, the excellent performance of the carbon dioxide adsorption device (acid gas adsorption device) can be maintained without performing maintenance of the carbon dioxide adsorption device (acid gas adsorption device) separately.

[0145] More specifically, in the adsorption process, a mist-like carbon dioxide adsorbent solution is sprayed onto the CO2-containing gas flowing into the gas flow path, so that the CO2-containing gas is entrained with the carbon dioxide adsorbent solution. As a result, when the CO2-containing gas passes through the gas flow path, droplets of the carbon dioxide adsorbent solution adhere to the surface of the carbon dioxide adsorption layer, and new carbon dioxide adsorbent is supplied to the carbon dioxide adsorption layer. Therefore, it is possible to reduce the reduction in CO2 recovery performance caused by repeated implementation of the adsorption process and the desorption process.

[0146] The carbon dioxide adsorbent solution is the same as the carbon dioxide adsorbent solution described in the above section D-1, for example. The method of spraying the carbon dioxide adsorbent solution is the same as the spraying method described in the above section D-1, for example.

[0147] In addition, in the adsorption process, the CO2-containing gas flowing into the gas flow path may be entrained with powdered carbon dioxide adsorbing particles or a dispersion obtained by dispersing carbon dioxide adsorbing particles in an aprotic solvent. Thus, when the CO2-containing gas passes through the gas flow path, the carbon dioxide adsorbing particles adhere to the organic binder on the surface of the carbon dioxide adsorbing layer. Therefore, new carbon dioxide adsorbing particles can be supplied to the carbon dioxide adsorbing layer.

[0148] Industrial Applicability

[0149] The acid gas adsorption device regeneration method according to the embodiment of the present invention can be used to regenerate an acid gas adsorption device used for separation and recovery of acid gas, and can be particularly preferably used to regenerate a carbon dioxide adsorption device used in a carbon dioxide recovery, utilization and storage (CCUS) cycle.

[0150] Explanation of symbols

[0151] 10 Honeycomb substrate

[0152] 13 Next Door

[0153] 14 compartments

[0154] 15 Carbon dioxide adsorption layer

[0155] 100 Carbon dioxide adsorption device

Claims

1. A method for regenerating an acid gas adsorption device, comprising the following steps: supplying acid gas to the acid gas adsorption device so as to contact the acid gas adsorption layer of the acid gas adsorption device including a substrate and an acid gas adsorption layer, so that the acid gas is adsorbed on the acid gas adsorption material contained in the acid gas adsorption layer, wherein the acid gas adsorption layer is arranged on the surface of the substrate; allowing acid gas to be separated from the acid gas adsorbent material; as well as An acid gas adsorbing material is supplied to and attached to the acid gas adsorbing layer of the acid gas adsorbing device that has been subjected to the step of adsorbing the acid gas and the step of desorbing the acid gas.

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

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

4. The method for regenerating an acid gas adsorption device 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 acid gas adsorption device according to claim 1, wherein: The acidic gas adsorbent material is selected from nitrogen-containing compounds, organic metal structures, activated carbon, nitrogen-doped carbon, alkaline compounds, carbonates, bicarbonates, zeolites, ionic liquids or combinations thereof.

6. The method for regenerating an acid gas adsorption device according to claim 1, wherein: The acid gas adsorption layer further includes a porous carrier.

7. The method for regenerating an acid gas adsorption device according to claim 1, wherein: The acid gas adsorbing layer includes particles containing at least the acid gas adsorbing material and an organic binder capable of binding the particles. The organic binder is soluble in an aprotic polar solvent and substantially insoluble in a protic polar solvent. In the step of supplying the acidic gas adsorbent to the acidic gas adsorbent layer to allow the acidic gas adsorbent to adhere, particles containing at least the acidic gas adsorbent are supplied to the acidic gas adsorbent layer.

8. A method for manufacturing an acid gas adsorption device, comprising the following steps: supplying acid gas to the acid gas adsorption device so as to contact the acid gas adsorption layer of the acid gas adsorption device including a substrate and an acid gas adsorption layer, so that the acid gas is adsorbed on the acid gas adsorption material contained in the acid gas adsorption layer, wherein the acid gas adsorption layer is arranged on the surface of the substrate; allowing acid gas to be separated from the acid gas adsorbent material; as well as An acid gas adsorbing material is supplied to and attached to the acid gas adsorbing layer of the acid gas adsorbing device that has been subjected to the step of adsorbing the acid gas and the step of desorbing the acid gas.

9. A method for operating an acid gas adsorption device, comprising the following steps: supplying acid gas to the acid gas adsorption device so as to contact the acid gas adsorption layer of the acid gas adsorption device including a substrate and an acid gas adsorption layer, so that the acid gas is adsorbed on the acid gas adsorption material contained in the acid gas adsorption layer, wherein the acid gas adsorption layer is arranged on the surface of the substrate; as well as allowing acid gas to be separated from the acid gas adsorbent material, In the step of causing the acid gas to be adsorbed on the acid gas adsorbent, the acid gas adsorbent is supplied together with the acid gas and adheres to the acid gas adsorbent layer.

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