Acid gas adsorption device

Abstract

This invention provides a new adsorption device for mounting adsorbent materials. [Solution] The acid gas adsorption device 100 comprises a heat transfer section 10 and an adsorption structure 20 arranged in a space 40 adjacent to the heat transfer section 10. The adsorption structure 20 comprises an acid gas adsorbent 21 and has a ventilation path 22. The acid gas adsorbent 21 contains an amine compound. The acid gas adsorption device 100 comprises, for example, a plurality of units 30, each including a heat transfer section 10 and an adsorption structure 20, and the plurality of units 30 are stacked.

Description

[Technical Field]

[0001] This invention relates to an acid gas adsorption device. [Background technology]

[0002] In recent years, carbon capture and storage (CCS) and carbon capture and utilization (CCU) have been considered as ways to reduce the amount of carbon dioxide in the atmosphere. In CCS and CCU, carbon dioxide is sometimes captured by separating it from the atmosphere.

[0003] Adsorption methods have been developed to separate acidic gases such as carbon dioxide from the atmosphere by adsorbing them onto an adsorbent. Adsorbents used in adsorption methods can adsorb acidic gases, for example, by coming into contact with the atmosphere. For example, Patent Document 1 describes an adsorbent in which an amine compound is supported in the pores of a porous support. Patent Document 1 also describes desorption and recovery of carbon dioxide adsorbed on the adsorbent by methods such as a pressure swing method and a temperature swing method. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2015-9185 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention aims to provide a novel adsorption device for mounting adsorbent materials. [Means for solving the problem]

[0006] The present invention Heat transfer section, an adsorbent structure disposed in a space adjacent to the heat transfer section, , wherein the adsorbent structure includes an acidic gas adsorbent and has a ventilation path, and the acidic gas adsorbent contains an amine compound, the acidic gas adsorption device is provided. [Advantageous Effects of the Invention]

[0007] According to the present invention, a novel adsorption device for mounting an adsorbent can be provided. [Brief Description of the Drawings]

[0008] [Figure 1] It is a perspective view schematically showing an example of the acidic gas adsorption device of the present invention. [Figure 2] It is a cross-sectional view of the acidic gas adsorption device of Figure 1. [Figure 3] It is a perspective view schematically showing an example of the adsorbent structure. [Figure 4A] It is a perspective view schematically showing an example of the heat transfer section. [Figure 4B] It is a perspective view schematically showing another example of the heat transfer section. [Figure 5] It is a perspective view showing a support section together with the heat transfer section. [Figure 6] It is a partial cross-sectional view showing the heat transfer section together with the adsorbent structure. [Figure 7] It is a diagram for explaining the attachment and detachment of the adsorbent structure in the acidic gas adsorption device. [Figure 8] It is a cross-sectional view schematically showing a part of the acidic gas adsorbent. [Figure 9] It is a perspective view schematically showing Modification Example 1 of the adsorbent structure. [Figure 10] It is a cross-sectional view schematically showing Modification Example 2 of the adsorbent structure. [Figure 11] It is a cross-sectional view schematically showing Modification Example 3 of the adsorbent structure. [Figure 12] It is a cross-sectional view schematically showing Modification Example 4 of the adsorbent structure. [Figure 13]This is a schematic perspective view showing a modified example 1 of the acidic gas adsorption apparatus of the present invention. [Figure 14] Figure 13 is a cross-sectional view of the acid gas adsorption apparatus. [Figure 15] This is a schematic perspective view showing a modified example 2 of the acidic gas adsorption apparatus of the present invention. [Modes for carrying out the invention]

[0009] The acid gas adsorption apparatus according to the first aspect of the present invention is Heat transfer section, An adsorption structure is arranged in the space adjacent to the heat transfer section, Equipped with, The adsorption structure comprises an acidic gas adsorbent and has a ventilation path. The acidic gas adsorbent contains an amine compound.

[0010] In a second aspect of the present invention, for example, in the acid gas adsorption apparatus according to the first aspect, the heat transfer section is in contact with at least a part of the adsorption structure.

[0011] In a third embodiment of the present invention, for example, in an acid gas adsorption apparatus according to the first or second embodiment, the heat transfer section has a planar portion, and the adsorption structure is arranged in the space facing the planar portion of the heat transfer section.

[0012] In a fourth aspect of the present invention, for example, in an acidic gas adsorption apparatus according to any one of the first to third aspects, the heat transfer section and the adsorption structure are stacked, and the ventilation path extends in a direction perpendicular to the stacking direction of the heat transfer section and the adsorption structure.

[0013] In a fifth embodiment of the present invention, for example, in an acid gas adsorption apparatus according to any one of the first to fourth embodiments, the heat transfer section has a first medium path through which a heat transfer medium flows.

[0014] In a sixth embodiment of the present invention, for example, the acid gas adsorption apparatus according to the fifth embodiment further comprises a support portion, the support portion having a second medium path communicating with the first medium path, a heat medium inlet for introducing the heat medium into the second medium path, and a heat medium outlet for discharging the heat medium from the second medium path.

[0015] In a seventh aspect of the present invention, for example, in an acid gas adsorption apparatus according to the fifth or sixth aspect, the heat transfer medium passes through the first medium path during a desorption operation in which the acid gas adsorbed on the acid gas adsorbent is desorbed from the acid gas adsorbent.

[0016] In the eighth aspect of the present invention, for example, an acid gas adsorption apparatus according to any one of the first to seventh aspects comprises a plurality of units including the heat transfer section and the adsorption structure, and the plurality of such units are stacked.

[0017] In the ninth aspect of the present invention, for example, in an acid gas adsorption device according to any one of the first to eighth aspects, the adsorption structure is detachable from the acid gas adsorption device.

[0018] In the tenth embodiment of the present invention, for example, in an acidic gas adsorption apparatus according to any one of the first to ninth embodiments, the adsorption structure has a porosity of 59 vol% or more and 91 vol% or less.

[0019] In the 11th aspect of the present invention, for example, in an acid gas adsorption apparatus according to any one of the first to tenth aspects, the adsorption structure is 350 m 2 / m 3 More than 2000m 2 / m 3 It has the following specific surface area.

[0020] In a twelfth aspect of the present invention, for example, in an acidic gas adsorption apparatus according to any one of the first to eleventh aspects, the amine compound includes a polymer having an amino group.

[0021] In a thirteenth aspect of the present invention, for example, in the acid gas adsorption apparatus according to the twelfth aspect, the polymer includes an amine polymer having constituent units derived from epoxy monomers.

[0022] In a fourteenth aspect of the present invention, for example, in an acid gas adsorption device according to the twelfth or thirteenth aspect, the acid gas adsorbent has a three-dimensional network structure composed of the polymer.

[0023] In a 15th aspect of the present invention, for example, in an acidic gas adsorption apparatus according to any one of the 1st to 14th aspects, the acidic gas adsorbent includes a corrugated body portion and a flat body portion.

[0024] The details of the present invention will be described below, but the following description is not intended to limit the present invention to any particular embodiment.

[0025] [Acid gas adsorption device] Figure 1 is a schematic perspective view showing an example of the acid gas adsorption apparatus of the present invention. Figure 2 is a cross-sectional view of the acid gas adsorption apparatus 100 shown in Figure 1. The acid gas adsorption apparatus 100 (hereinafter simply referred to as the adsorption apparatus 100) comprises a heat transfer section 10 and an adsorption structure 20 arranged in a space 40 adjacent to the heat transfer section 10. Figure 3 is a schematic perspective view showing an example of the adsorption structure 20. As shown in Figure 3, the adsorption structure 20 comprises an acid gas adsorbent 21 (hereinafter simply referred to as the adsorbent 21) and has a ventilation path 22. The ventilation path 22 is a path through which the raw material gas containing the acid gas moves during adsorption operation in which the acid gas is adsorbed onto the adsorbent 21. The adsorbent 21 contains an amine compound. The adsorption apparatus 100 of this embodiment provides a new adsorption apparatus for mounting an adsorbent.

[0026] In the adsorption device 100, the adsorption structure 20 is positioned in the space 40 adjacent to the heat transfer section 10, so that the heat transfer section 10 and the adsorption structure 20 can be thermally connected. That is, heat can be transferred to the adsorption structure 20 by heat conduction from the heat transfer section 10. Therefore, for example, during a desorption operation in which acidic gas adsorbed on the adsorbent 21 is desorbed from the adsorbent 21, the desorption of the acidic gas can be promoted by heat conduction from the heat transfer section 10. This improves the desorption efficiency.

[0027] The space 40 may be the space located between the two heat transfer sections 10. That is, the adsorption structure 20 may be positioned so as to be sandwiched between the two heat transfer sections 10. With such a configuration, heat can be transferred to the adsorption structure 20 more effectively.

[0028] It is preferable that the heat transfer section 10 is in contact with at least a portion of the adsorption structure 20. With such a configuration, heat can be transferred to the adsorption structure 20 more effectively.

[0029] The heat transfer section 10 may support the adsorption structure 20. As a result, the heat transfer section 10 may be in direct contact with the adsorption structure 20.

[0030] As shown in Figures 1 and 2, it is preferable that the adsorption structure 20 has a planar portion 20f. With such a configuration, it is easier to increase the contact area between the heat transfer section 10 and the adsorption structure 20.

[0031] As shown in Figure 3, when the adsorption structure 20 has a planar portion 20f, the ventilation path 22 of the adsorption structure 20 extends along a direction parallel to the planar portion 20f.

[0032] The adsorption structure 20 may be, for example, a block shape having a planar portion 20f. In this specification, block shape means rectangular parallelepiped shape and cubic shape, and includes those in which the shape defined by the outer edge is a rectangular parallelepiped shape and a cubic shape, as illustrated in Figure 3.

[0033] As shown in Figures 1 and 2, it is preferable that the heat transfer section 10 has a planar portion 10f. In this case, the adsorption structure 20 is placed in the space 40 facing the planar portion 10f of the heat transfer section 10. With this configuration, it is easy to increase the contact area between the heat transfer section 10 and the adsorption structure 20.

[0034] If the adsorption structure 20 has a planar portion 20f and the heat transfer portion 10 has a planar portion 10f, the planar portion 10f of the heat transfer portion 10 can be in surface contact with the planar portion 20f of the adsorption structure 20.

[0035] As shown in Figures 1 and 2, the heat transfer section 10 and the adsorption structure 20 may be stacked. In this case, the ventilation path 22 of the adsorption structure 20 extends along a direction perpendicular to the stacking direction of the heat transfer section 10 and the adsorption structure 20. With such a configuration, adsorption and desorption operations can be carried out more effectively.

[0036] As shown in Figures 1 and 2, the adsorption device 100 may comprise a plurality of units 30, each containing a heat transfer section 10 and an adsorption structure 20. The plurality of units 30 may be stacked. More specifically, the adsorption device 100 may comprise a plurality of heat transfer sections 10 and a plurality of adsorption structures 20, with the plurality of heat transfer sections 10 and the plurality of adsorption structures 20 being stacked alternately. With such a configuration, the amount of acidic gas adsorbed during adsorption operation can be increased. This improves the adsorption efficiency.

[0037] The number of units 30 is not particularly limited. For example, the number of units 30 may be set appropriately depending on the size of the adsorption structure 20. The number of units 30 may be in the range of, for example, 5 to 100.

[0038] As shown in Figure 2, in this embodiment, the heat transfer section 10 has a first medium path 51 through which a heat transfer medium M flows. That is, the first medium path 51 is formed inside the heat transfer section 10. In Figure 2, the first medium path 51 is shown by a dashed line. With this configuration, the heat transfer section 10 can function as a heat transfer tube, so that heat can be transferred to the adsorption structure 20 more effectively.

[0039] During desorption operation, it is preferable that the heat transfer medium M passes through the first medium path 51. With this configuration, the desorption of acidic gases during desorption operation can be promoted. This improves the desorption efficiency.

[0040] Figure 4A is a schematic perspective view showing an example of the heat transfer section 10. Figure 4B is a schematic perspective view showing another example of the heat transfer section 10. As shown in Figures 4A and 4B, the heat transfer sections 10A and 10B have a flattened shape with a long side 10a and a short side 10b, and have a planar portion 10f. When the heat transfer section 10 has a flattened shape, it is easy to increase the contact area between the heat transfer section 10 and the adsorption structure 20.

[0041] As shown in Figure 4A, the heat transfer section 10 (10A) may be a flattened multi-hole tube having multiple paths formed parallel to the longitudinal direction. Each of the multiple paths functions as a first medium path 51.

[0042] As shown in Figure 4B, the heat transfer section 10 (10B) may be a flattened tube having a single flattened path formed in the longitudinal direction. The flattened path functions as the first medium path 51.

[0043] As shown in Figures 1 and 2, the adsorption device 100 may further include a support section 60. The support section 60 may have a second medium path 52, a heat medium inlet 60a for introducing a heat medium M into the second medium path 52, and a heat medium outlet 60b for discharging the heat medium M from the second medium path 52. The second medium path 52 is in communication with the first medium path 51. With this configuration, during desorption operation, the heat medium M introduced from the heat medium inlet 60a can be supplied to the first medium path 51 via the second medium path 52. In addition, the heat medium M that has passed through the first medium path 51 can be discharged from the heat medium outlet 60b via the second medium path 52.

[0044] As the heat transfer medium M, hot water, high-temperature gas, etc., can be used. Specific examples of gases contained in high-temperature gas include chlorofluorocarbons (CFCs), carbon dioxide, air, and water vapor. The heat transfer medium M can be prepared, for example, using waste heat, a heat pump, or self-heat regeneration.

[0045] The support portion 60 has, for example, a flat lower portion 61 and an upper portion 63. Multiple units 30 may be stacked between the lower portion 61 and the upper portion 63.

[0046] The support portion 60 may further have a pair of side portions 62 (621, 622) that connect to the lower portion 61 and the upper portion 63. That is, the support portion 60 may be frame-shaped. Multiple units 30 may be stacked in the internal space of the frame-shaped support portion 60. In this case, the adsorption structure 20 is arranged such that the ventilation path 22 is not obstructed by the pair of side portions 62 (621, 622).

[0047] In the example shown in Figure 2, the heat transfer medium inlet 60a and heat transfer medium outlet 60b are located on one side portion 621. The heat transfer medium inlet 60a is located below the heat transfer medium outlet 60b. A second medium path 52 is formed inside the side portions 62 (621, 622). However, the location of the second medium path 52 is not limited to the example shown in Figure 2.

[0048] In the example shown in Figure 2, a U-shaped flow path is formed by the second medium path 52 and the first medium path 51. Specifically, the interior of one side portion 621 is divided by a partition plate 65, thereby forming a first flow path from one side portion 621 to the other side portion 622 and a second flow path from the other side portion 622 to one side portion 621, with the partition plate 65 as the boundary. The first and second flow paths are in communication within the interior of the other side portion 622. However, the shape of the flow path formed by the second medium path 52 and the first medium path 51 is not limited to the example shown in Figure 2. For example, an S-shaped flow path may be formed by dividing the interior of both one side portion 621 and the interior of the other side portion 622 by a partition plate. In this case, the heat medium inlet 60a and the heat medium outlet 60b are located on different sides 62.

[0049] Figure 5 is a perspective view showing the support section 60 together with the heat transfer section 10. In other words, Figure 5 is a diagram of the adsorption device 100 of Figure 1 with the adsorption structure 20 omitted. As shown in Figure 5, a plurality of heat transfer sections 10 may be arranged in the internal space SP of the support section 60 at intervals 10c. The interval 10c corresponds to the width (height) of the space 40. It is preferable that a plurality of flat-shaped heat transfer sections 10 be arranged in the internal space SP of the support section 60 at intervals 10c. In other words, it is preferable that a plurality of flat-shaped heat transfer sections 10 be arranged in a shelf-like manner in the internal space SP of the support section 60.

[0050] Figure 6 is a partial cross-sectional view showing the heat transfer section 10 together with the adsorption structure 20. The spacing 10c between adjacent heat transfer sections 10 can be appropriately set according to the thickness of the heat transfer section 10, the thickness of the adsorption structure 20, etc.

[0051] The spacing 10c can be, for example, in the range of 5 mm to 50 mm. With this configuration, a sufficient amount of adsorption structure 20 can be secured. The thickness of the adsorption structure 20 may be the same as the length of the spacing 10c, or it may be less than the length of the spacing 10c.

[0052] As illustrated in Figure 2, when a first medium path 51 is formed inside the heat transfer section 10, that is, when the heat transfer section 10 functions as a heat transfer tube, the thickness of the heat transfer section 10 is preferably, for example, 1 mm to 2 mm. With such a configuration, sufficient thermal conductivity of the heat transfer section 10 can be ensured.

[0053] The heat transfer section 10 is preferably made of metal. In this case, the thermal conductivity of the heat transfer section 10 can be improved. Examples of metals include aluminum, copper, and stainless steel. Aluminum is lightweight and has excellent sensible heat suppression effects. Copper has high thermal conductivity. Stainless steel has excellent strength.

[0054] It is preferable that the adsorption structure 20 is detachable from the adsorption device 100. In this specification, "detachable from the adsorption device 100" means that the adsorption structure 20 can be attached to and removed without damaging the adsorption device 100. Figure 7 is a diagram illustrating the attachment and detachment of the adsorption structure 20 in the adsorption device 100. As shown in Figure 7, if the adsorption structure 20 is detachable from the adsorption device 100, the adsorption structure 20 can be easily replaced, for example, during maintenance.

[0055] The adsorption structure 20 is preferably in the form of a cartridge that can be attached to and detached from the space 40. With such a configuration, the replacement of the adsorption structure 20 can be made easier.

[0056] As shown in Figure 7, the cartridge-type adsorption structure 20 may be inserted and removed in a drawer-like manner into the space 40 adjacent to the shelf-like heat transfer section 10. In this case, the insertion and removal direction D is parallel to the direction of the ventilation path 22.

[0057] If the suction structure 20 is detachable from the suction device 100, the support portion 60 may be provided with means (not shown) to prevent the suction structure 20 from falling off. Examples of means to prevent the suction structure 20 from falling off include a mesh plate joined to cover one open surface of the frame-shaped support portion 60, and a pin positioned near one open surface of the frame-shaped support portion 60 that functions as a stopper.

[0058] The adsorption structure 20 will be described in more detail below.

[0059] (Adsorption structure) As described above, the adsorption structure 20 comprises an adsorbent 21 and a ventilation path 22. The ventilation path 22 functions as a path through which a raw material gas containing an acidic gas passes. In the adsorption structure 20, it is preferable that the adsorbent 21 is arranged such that the ventilation path 22 extends in the direction of flow of the raw material gas. The adsorption structure 20 includes, for example, a honeycomb structure having a plurality of ventilation paths 22 extending in the same direction. In this specification, "honeycomb structure" means a structure having a cross-section that tiled a plane with certain shapes such as polygons, not limited to regular hexagons. The adsorption structure 20 shown in Figure 3 is a honeycomb structure.

[0060] The ventilation paths 22 penetrate the adsorption structure 20, and multiple ventilation paths 22 are arranged parallel to each other. The shape of the cross-section perpendicular to the direction in which the ventilation paths 22 extend is not particularly limited.

[0061] The adsorbent material 21 has, for example, a main body portion 211 having the shape of a sheet.

[0062] As shown in Figure 3, in the adsorption structure 20, the adsorbent 21 may include, for example, an adsorption unit 211U in which a corrugated main body portion 211A and a flat plate-shaped main body portion 211B are laminated. In the main body portion 211A, a plurality of peak portions 211m and a plurality of valley portions 211v may be arranged alternately. In this case, a ventilation path 22 is formed between the peak portion 211m or the valley portion 211v of the main body portion 211A and the main body portion 211B. As such, the ventilation path 22 may be surrounded by the main body portions 211A and 211B. In the adsorption structure 20 shown in Figure 3, the shape of the cross section perpendicular to the extending direction of the ventilation path 22 is a shape defined by the peak portion 211m or the valley portion 211v of the main body portion 211A and the main body portion 211B.

[0063] The adsorption structure 20 preferably has a porosity of 59 vol% or more and 91 vol% or less. According to such a configuration, the adsorption amount of acidic gas during the adsorption operation can be increased. Thereby, the adsorption efficiency can be improved. In the present specification, the porosity of the adsorption structure 20 refers to the ratio of the volume occupied by portions other than the adsorbent 21 (typically the ventilation path 22) to the volume of the adsorption structure 20.

[0064] The adsorption structure 20 is 350 m 2 / m 3 or more and 2000 m 2 / m 3 or less in specific surface area. In the present specification, the specific surface area of the adsorption structure 20 refers to the ratio of the surface area of the adsorption structure 20 to the volume of the adsorption structure 20. When the specific surface area of the adsorption structure 20 is 350 m 2 / m 3 or more, a sufficient contact area between the adsorption structure 20 and the raw material gas containing acidic gas can be obtained, so that a decrease in the adsorption rate of acidic gas during the adsorption operation can be suppressed. When the specific surface area of the adsorption structure 20 is 2000 m 2 / m 3The following conditions can suppress the increase in pressure loss caused by an excessive increase in the adsorption rate of acidic gases during adsorption operation. This suppresses the increase in load on blowing mechanisms such as fans used to draw in the raw material gas, and thus suppresses the increase in energy loss of the adsorption device 100.

[0065] (Adsorbent material) The adsorbent 21 is not particularly limited, as long as it can desorb acidic gases when it receives thermal energy and adsorb acidic gases contained in the raw material gas when it comes into contact with the raw material gas. Preferably, the adsorbent 21 is suitable for thermal swing adsorption (TSA) methods. For example, the adsorbent 21 adsorbs acidic gases at room temperature (around 25°C) and desorbs the acidic gases when it receives thermal energy from the heat transfer section 10.

[0066] As described above, the adsorbent 21 contains an amine compound. The main body portion of the adsorbent 21 (for example, a sheet-like main body portion 211) may also contain an amine compound. The amine compound contains a polymer P having an amino group. It is preferable that the adsorbent 21 contains a polymer P having an amino group.

[0067] The adsorbent 21 may contain inorganic materials, organic materials other than amine compounds, etc., in addition to amine compounds. Examples of inorganic materials include metal oxides such as cerium oxide, zeolites, silica gel, and activated carbon.

[0068] The main body of the adsorbent 21 may have a porous structure. For example, the main body of the adsorbent 21 may be a porous body S containing polymer P.

[0069] The porous body S preferably has a three-dimensional network-like framework containing polymer P. The three-dimensional network-like framework may further contain other components besides polymer P. For example, in the porous body S, the above-mentioned three-dimensional network-like framework extends continuously. The pores contained in the porous body S are preferably continuous pores formed in a three-dimensional manner. The porous body S may have independent pores or through pores penetrating the porous body S.

[0070] The porous body S preferably has an average pore diameter of 0.1 μm or more and 50 μm or less. The larger the average pore diameter of the porous body S, the better the diffusion of acidic gas can be maintained without pore blockage even when the adsorbent 21 contains water. The lower limit of the average pore diameter of the porous body S may be 0.2 μm or more, 0.3 μm or more, or even 0.5 μm or more. In this specification, the average pore diameter of the porous body S refers to the median diameter measured by the mercury intrusion method. The mercury intrusion method is performed using a commercially available pore distribution analyzer (for example, Autopore V9620 manufactured by Micromeristics) under an initial pressure of 21 kPa.

[0071] The porous body S is 0.5 m 2 / g or more 100m 2 It is preferable that the specific surface area of ​​the porous body S is less than or equal to 0.5 m². The larger the specific surface area of ​​the porous body S, the greater the contact area with the acidic gas, and therefore the faster the rate of adsorption of the acidic gas. The lower limit of the specific surface area of ​​the porous body S is 0.5 m². 2 / g or more, 1.0m 2 / g or more, 2.0m 2 / g or more, 3.0m 2 / g or more, 4.0m 2 / g or more, 5.0m 2 / g or more, 6.0m 2 / g or more, 7.0m 2 / g or more, and even 8.0m 2 It may be greater than or equal to / g. The specific surface area of ​​the porous material S refers to the BET (Brunauer-Emmett-Teller) specific surface area due to nitrogen gas adsorption. The specific surface area of ​​the porous material S can be measured by a method compliant with the provisions of JIS Z8830:2013.

[0072] (Polymer P) The polymer P is preferably an amine polymer containing a constituent unit U1 derived from an epoxy monomer. This amine polymer includes, for example, a reaction product P1 from a group of compounds containing an amine monomer and an epoxy monomer.

[0073] The group of compounds for forming reactant P1 includes amine monomers and epoxy monomers, as described above. Reactant P1 may be, for example, a polymer of the group of monomers including amine monomers and epoxy monomers (particularly a polymer of amine monomers and epoxy monomers). Reactant P1 may also be a crosslinked product in which the amine monomer is crosslinked with the epoxy monomer.

[0074] Examples of amine monomers include ethylamine, ethylenediamine, 1,4-butylenediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, iminobispropylamine, bis(hexamethylene)triamine, 1,3,6-trisaminomethylhexane, tris(2-aminoethyl)amine, N,N'-bis(3-aminopropyl)ethylenediamine, polymethylenediamine, trimethylhexamethylenediamine, poly Examples include aliphatic amines such as ether diamines; alicyclic amines such as isophorone diamine, menthane diamine, piperazine, N-aminoethylpiperazine, 3,9-bis(3-aminopropyl)2,4,8,10-tetraoxaspiro(5,5)undecane adduct, bis(4-amino-3-methylcyclohexyl)methane, bis(4-aminocyclohexyl)methane, and modified versions thereof; aliphatic polyamines such as polyethyleneimines and polyalkylene polyamines; (meth)acrylic polymers having amino groups such as aminoethylated acrylic polymers; and aliphatic polyamidoamines formed by the reaction of polyamines with dimer acids. Amine monomers can be used alone or in combination of two or more.

[0075] Examples of epoxy monomers include monofunctional epoxy compounds such as n-butyl glycidyl ether, higher alcohol glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, and t-butylphenyl glycidyl ether; diepoxyalkanes such as 1,5-hexadiene diepoxide, 1,7-octadiene diepoxide, and 1,9-decadiene diepoxide; and (poly)ethylene glycol diglycidyl ether. Examples include polyfunctional epoxy compounds having an ether group, such as ether, (poly)propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, and sorbitol polyglycidyl ether; and polyfunctional epoxy compounds having an amino group, such as N,N,N',N'-tetraglycidylmetoxylendiamine and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane.

[0076] The epoxy monomer may, in some cases, be an aromatic epoxy resin, a non-aromatic epoxy resin, etc. Examples of aromatic epoxy resins include polyphenyl-based epoxy resins, epoxy resins containing fluorene rings, epoxy resins containing triglycidyl isocyanurate, and epoxy resins containing heteroaromatic rings (e.g., triazine rings). Examples of polyphenyl-based epoxy resins include bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD ​​type epoxy resins, stilbene type epoxy resins, biphenyl type epoxy resins, bisphenol A novolac type epoxy resins, cresol novolac type epoxy resins, diaminodiphenylmethane type epoxy resins, and tetrakis(hydroxyphenyl)ethane-based epoxy resins. Examples of non-aromatic epoxy resins include aliphatic glycidyl ether type epoxy resins, aliphatic glycidyl ester type epoxy resins, alicyclic glycidyl ether type epoxy resins, alicyclic glycidylamine type epoxy resins, and alicyclic glycidyl ester type epoxy resins.

[0077] Epoxy monomers can be used individually or in combination of two or more. When using monofunctional epoxy compounds, it is preferable to use them in combination with other epoxy monomers containing two or more epoxy groups. Monofunctional epoxy compounds can also be used as reactive diluents to adjust the viscosity of the monomer group for forming reactant P1.

[0078] As described above, polymer P as an amine polymer contains constituent units U1 derived from epoxy monomers. When polymer P is reactant P1, polymer P further contains constituent units U2 derived from amine monomers. The content of constituent units U1 in polymer P, particularly reactant P1, is, for example, 20 wt% to 70 wt%. The content of constituent units U2 in polymer P, particularly reactant P1, is, for example, 30 wt% or more, preferably 50 wt% or more. The upper limit of the content of constituent units U2 is not particularly limited, but is, for example, 80 wt%.

[0079] The glass transition temperature Tg of polymer P is not particularly limited, and is, for example, 40°C or lower, preferably 30°C or lower, more preferably 20°C or lower, even more preferably 15°C or lower, and may be 10°C or lower, 5°C or lower, or 0°C or lower. When the glass transition temperature Tg of polymer P is this low, the adsorbent 21 tends to adsorb acidic gases at a high rate. The lower limit of the glass transition temperature Tg of polymer P is, for example, -100°C, preferably -50°C, and more preferably -10°C, from the viewpoint of ensuring sufficient adsorption of acidic gases in the adsorbent 21 and heat resistance. In this specification, the glass transition temperature Tg is the intermediate glass transition temperature (T) determined in accordance with the provisions of JIS K7121:1987. mg This means that polymer P is a solid. Polymer P is typically a thermosetting resin. Polymer P is solid at, for example, 25°C, preferably in the range of 25°C to 80°C.

[0080] The weight-average molecular weight of polymer P is not particularly limited, but is, for example, 500 or more, preferably 1000 or more, more preferably 100000 or more, and even more preferably 100000 or more. The upper limit of the weight-average molecular weight of polymer P is, for example, 10000000 or less.

[0081] The main body of the adsorbent 21 (for example, a sheet-like main body 211) may contain polymer P as its main component, or may be substantially composed solely of polymer P. The main body of the adsorbent 21 (for example, a sheet-like main body 211) may further contain other components besides polymer P. Examples of other components include a carrier for supporting polymer P, a reaction accelerator, a plasticizer, a pigment, a dye, an antioxidant, a conductive material, an antistatic agent, an ultraviolet absorber, a flame retardant, and an antioxidant.

[0082] Examples of carriers include fibers and fiber structures containing fibers. Examples of fibers include glass fibers; natural fibers such as wood pulp, cotton, and hemp (e.g., Manila hemp); and chemical fibers (synthetic fibers) such as polyester fibers, rayon, vinylon, acetate fibers, polyvinyl alcohol (PVA) fibers, polyamide fibers, polyolefin fibers, and polyurethane fibers. Examples of fiber structures include woven fabrics, nonwoven fabrics, and paper. A specific example of a fiber structure is glass paper.

[0083] Reaction accelerators are used, for example, when synthesizing polymer P. Examples of reaction accelerators include tertiary amines such as triethylamine and tributylamine; and imidazoles such as 2-phenol-4-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenol-4,5-dihydroxyimidazole. These reaction accelerators can accelerate reactions, for example, to synthesize polymer P.

[0084] The polymer P content R1 in the adsorbent 21 is, for example, 5 wt% or more, and may be 10 wt% or more, 15 wt% or more, 20 wt% or more, 25 wt% or more, 30 wt% or more, or even 35 wt% or more. The higher the polymer P content R1, the greater the amount of acidic gas adsorbed by the adsorbent 21 tends to be. The upper limit of the polymer P content R1 is, for example, 80 wt% or less, and may be 60 wt% or less.

[0085] The polymer P content R1 can be measured, for example, by the following method. First, the adsorbent 21 is placed in a simultaneous thermal analysis DSC / TGA instrument. At this time, the temperature is set to 30°C. Next, using this instrument, the temperature is raised from 30°C to 100°C at a heating rate of 10°C / min under a nitrogen atmosphere and held at that temperature for 40 minutes (Operation 1). According to Operation 1, water contained in the adsorbent 21 can be removed. Next, the temperature is raised from 100°C to 800°C at a heating rate of 10°C / min and held at that temperature for 5 minutes (Operation 2). According to Operation 2, polymer P can be removed from the adsorbent 21. The ratio (100 × (W1-W2) / W1) of the difference between the weight W1(g) of the adsorbent 21 immediately after Operation 1 and the weight W2(g) of the adsorbent 21 immediately after Operation 2 can be considered as the polymer P content R1 in the adsorbent 21.

[0086] Figure 8 is a schematic cross-sectional view showing a part of the adsorbent material 21. The adsorbent material 21 may include a sheet-like main body portion 211 and a support 212 that supports the main body portion 211.

[0087] (Support) The support 212, for example, supports the sheet-like main body 211 and is in direct contact with the sheet-like main body 211. The adsorbent 21 may or may not further include fixing means for fixing the sheet-like main body 211 and the support 212. Specific examples of fixing means include adhesives, and more specifically, adhesive sheets containing adhesives. In this specification, the term "adhesive" is used to encompass pressure-sensitive adhesives.

[0088] The material of the support 212 is not particularly limited and may include, for example, ceramics such as cordierite, alumina, cordierite-α-alumina, silicon nitride, zircon mullite, siliconite, alumina-silica-magnesia, zirconite silicate, sillimanite, magnesium silicate, zircon, feldspar, and aluminosilicate; metals such as aluminum, titanium, copper, stainless steel, Fe-Cr alloy, and Cr-Al-Fe alloy; and silicone resin, polyolefin, polyester, polyurethane, polycarbonate, and polyetheretherketone. Examples of suitable materials include polyphenylene oxide, polyethersulfone, melamine, polyamide, poly(meth)acrylate, polystyrene, poly(meth)acrylonitrile, polyimide, polyfurfural alcohol, phenolfurfuryl alcohol, melamine formaldehyde, resorcinol formaldehyde, cresol formaldehyde, phenol formaldehyde, polyvinyl alcohol dialdehyde, polycyanurate, poly(meth)acrylamide, epoxy resin, agar, agarose, cellulose, and other resins. The material of the support 212 is preferably excellent in thermal conductivity and durability, and is resistant to deterioration such as rust formation and hydrolysis when in contact with water.

[0089] The support 212 may or may not have a porous structure. Examples of a support 212 having a porous structure include paper, nonwoven fabric, foam, and mesh. If the support 212 has a porous structure, for example, the polymer P can be placed inside the pores of the support 212. However, the polymer P does not necessarily have to be located inside the pores of the support 212. Examples of a support 212 not having a porous structure include non-porous sheets and foils. The support 212 may also be an aluminum sheet, paper, or nonwoven fabric.

[0090] The support 212 may function as a planar heater, and may be a planar thermoelectric heater or a Peltier element. With such a configuration, during desorption operation, the desorption of acidic gas from the adsorbent 21 can be further promoted by heat conduction from the support 212 to the main body 211.

[0091] The adsorption structure 20 is not limited to the example shown in Figure 3. Modified examples of the adsorption structure 20 will be described below with reference to Figures 9 to 12.

[0092] Figure 9 is a schematic perspective view showing a modified example 1 of the adsorption structure 20. In the adsorption structure 20A of modified example 1, the adsorption material 21 comprises a plurality of stacked flat plate-shaped main body portions 211B. Spacers 230 are placed between adjacent main body portions 211B. In the adsorption structure 20A, a ventilation path 22 is ensured by the spacers 230. In the adsorption structure 20A, the shape of the cross-section perpendicular to the direction in which the ventilation path 22 extends is rectangular. The adsorption structure 20A has a block shape with a planar portion 20f.

[0093] Figure 10 is a schematic cross-sectional view showing a modified example 2 of the adsorption structure 20. In Figure 10, the raw material gas is supplied from the front to the back of the paper. The adsorption structure 20B of modified example 2 is a honeycomb structure having a triangular lattice cross-section formed by filling a plane with triangles. A ventilation path 22 is formed inside each triangular lattice. The adsorption structure 20B can be manufactured, for example, by combining a flat plate-shaped main body portion 211B and a sheet-shaped main body portion 211C that is folded in an accordion shape. The adsorption structure 20B has a block shape with a planar portion 20f.

[0094] Figure 11 is a schematic cross-sectional view showing a modified example 3 of the adsorption structure 20. In Figure 11, the raw material gas is supplied from the front to the back of the paper. The adsorption structure 20C of modified example 3 is a honeycomb structure having a square grid-like cross-section formed by filling a plane with squares. A ventilation path 22 is formed inside each square grid. The adsorption structure 20C can be manufactured, for example, by combining flat plate-shaped main body parts 211B vertically and horizontally. The adsorption structure 20C has a block shape with a planar portion 20f.

[0095] Figure 12 is a schematic cross-sectional view showing a modified example 4 of the adsorption structure 20. In Figure 12, the raw material gas is supplied from the front to the back of the paper. The adsorption structure 20D of modified example 4 is a honeycomb structure having a hexagonal lattice cross-section formed by filling a plane with hexagons. A ventilation path 22 is formed inside each hexagonal lattice. The adsorption structure 20D can be manufactured, for example, by combining a flat plate-shaped main body portion 211B and a sheet-shaped main body portion 211D obtained by folding a sheet-shaped main body portion 211 so that its cross-section is hexagonal. The adsorption structure 20D has a block shape with a planar portion 20f.

[0096] The adsorption structures 20 (20A, 20B, 20C, 20D) do not necessarily have to be formed by a sheet-like main body 211. For example, the adsorption structures 20 (20A, 20B, 20C, 20D) may be formed by perforating a block made of an amine compound. For example, the adsorption structures 20 (20A, 20B, 20C, 20D) may be honeycomb structures formed from a porous material such as zeolite. A liquid amine compound may be supported on the honeycomb structure.

[0097] The adsorption structure 20 may be an aggregate of bead-shaped adsorbents.

[0098] [Methods for recovering acidic gases] Next, with reference to Figure 1, a method for recovering acidic gas using the adsorption device 100 described above will be explained.

[0099] A method for recovering acidic gas using an adsorption device 100 (hereinafter simply referred to as the recovery method) includes bringing an adsorption structure 20 (adsorbent 21) into contact with a raw material gas containing acidic gas to adsorb the acidic gas contained in the raw material gas onto the adsorbent 21 (adsorption step), and desorbing the acidic gas from the adsorbent 21 (desorption step). The adsorption step and the desorption step may be repeated in this order.

[0100] The adsorption process is carried out, for example, in the adsorption apparatus 100 shown in Figure 1, as follows. First, the raw material gas is supplied to the adsorption apparatus 100 in the direction indicated by the dashed arrow. The raw material gas supplied to the adsorption apparatus 100 is, for example, the atmosphere.

[0101] Examples of acidic gases include carbon dioxide, hydrogen sulfide, carbonyl sulfide, sulfur oxides (SOx), hydrogen cyanide, nitrogen oxides (NOx), etc., with carbon dioxide being preferred.

[0102] The raw material gas supplied to the adsorption device 100 moves through the adsorption structure 20 and comes into contact with the adsorbent material 21. The adsorbent material 21, upon contact with the raw material gas, adsorbs the acidic gases contained in the raw material gas. The raw material gas processed by the adsorption device 100 is discharged to the outside from the adsorption device 100.

[0103] The desorption process is carried out, for example, in the adsorption device 100 shown in Figure 1, as follows. First, the heat transfer medium M is supplied from the heat transfer medium inlet 60a to a second medium path 52 provided inside the support section 60. The heat transfer medium M supplied to the second medium path 52 is then supplied to a first medium path 51 provided inside the heat transfer section 10. As a result, heat is transferred to the adsorption structure 20 by heat conduction from the heat transfer section 10, thereby promoting the desorption of adsorbed gas from the adsorbent material 21. In addition, during the desorption process, an operation to reduce the internal space of the adsorption device 100 may be performed. The reduction operation can be carried out, for example, by a pressure reducing device connected to the desorption gas outlet of the housing (not shown).

[0104] The desorbed gas (adsorbed gas containing acidic gas) is discharged from the adsorption device 100 to the outside and stored, for example, in a storage container (not shown). The acidic gas content in the desorbed gas is, for example, 0.1 vol% or more and less than 100 vol%. It is also possible to recover gas with an acidic gas content of approximately 100 vol% as the desorbed gas discharged from the adsorption device 100.

[0105] The process may include a cooling step after the desorption step, in which the adsorption structure 20 from which the acidic gas has been desorbed is cooled. The adsorption step, desorption step, and cooling step may be repeated in this order.

[0106] In the cooling process, a cooling medium may be circulated through the second medium path 52 and the first medium path 51 instead of the heat transfer medium M. This may cool the adsorption structure 20 via the heat transfer section 10.

[0107] An example of the adsorption device 100 of this embodiment has been described above using Figures 1 to 12, but the adsorption device 100 of this embodiment is not limited to the example shown in Figures 1 to 12. A modified example of the adsorption device 100 will be described below using Figures 13 to 15.

[0108] [Modified example of adsorption device 1] Figure 13 is a schematic perspective view showing a modified example 1 of the adsorption device 100. In the adsorption device 100A shown in Figure 13, the heat transfer section 10 does not have a first medium path 51 through which the heat transfer medium M flows. In the following, the same reference numerals are used for elements that are the same as those in the adsorption device 100, and explanations may be omitted.

[0109] Figure 14 is a cross-sectional view of the adsorption device 100A. In Figure 14, the second medium path 52 is shown by a dashed line. As shown in Figure 14, in the adsorption device 100A, the heat transfer section 10 and the second medium path 52 are thermally connected, allowing the heat transfer section 10 to function as a heat transfer fin. This allows heat to be transferred to the adsorption structure 20 by heat conduction from the second medium path 52 to the heat transfer section 10.

[0110] During desorption operation, it is preferable that the heat transfer medium M passes through the second medium path 52. With this configuration, the desorption of acidic gas during desorption operation can be promoted via the heat transfer section 10, thereby improving the desorption efficiency.

[0111] In the example shown in Figure 14, the heat transfer medium inlet 60a and heat transfer medium outlet 60b are provided at the upper ends of the side portions 62 (621, 622), and a second medium path 52 is formed inside one side portion 621, the lower portion 61, and the other side portion 622. However, the location of the second medium path 52 is not limited to the example shown in Figure 14.

[0112] In the example shown in Figure 14, a U-shaped flow path is formed by the second medium path 52. Specifically, a first flow path is formed from the upper end of one side portion 621 toward the lower portion 61, and a second flow path is formed from the lower portion 61 toward the upper end of the other side portion 622. The first and second flow paths are in communication inside the lower portion 61. However, the shape of the flow path formed by the second medium path 52 is not limited to the example shown in Figure 14. For example, a heat medium inlet 60a and a heat medium outlet 60b may be provided on one side portion 621. This may form a substantially U-shaped flow path. Specifically, a first flow path may be formed from one side portion 621 through the lower portion 61 toward the other side portion 622, and a second flow path may be formed from the other side portion 622 through the upper portion 63 toward the one side portion 621. The first and second flow paths are in communication inside the other side portion 622. For example, a heat transfer medium inlet 60a and a heat transfer medium outlet 60b located above or below the heat transfer medium inlet 60a may be provided on one side 621 and the other side 622, respectively. This may form two independent flow paths. Specifically, a first flow path may be formed that flows from below to above (or from above to below) on one side 621, and a second flow path may be formed that flows from below to above (or from above to below) on the other side 622.

[0113] As illustrated in Figures 13 and 14, when the first medium path 51 is not formed inside the heat transfer section 10, that is, when the heat transfer section 10 functions as a heat transfer fin, the thickness of the heat transfer section 10 is preferably, for example, 0.1 mm to 0.5 mm. With such a configuration, it is easy to secure space 40 for arranging the adsorption structure 20 while ensuring the thermal conductivity of the heat transfer section 10.

[0114] Although not shown in the diagram, the adsorption device 100A may not have both the first medium path 51 and the second medium path 52, and the heat transfer unit 10 itself may function as a planar heater. The heat transfer unit 10 may be a planar thermoelectric heater or a Peltier element.

[0115] [Modified example of the adsorption device 2] Figure 15 is a schematic perspective view showing a modified example 2 of the adsorption device 100. The adsorption device 100B shown in Figure 15 further comprises a heat transfer section 10, an adsorption structure 20, and a housing 70 that houses a support section 60 on which the heat transfer section 10 and the adsorption structure 20 are arranged. In Figure 15, the heat transfer section 10 and the adsorption structure 20 are omitted. The dashed arrow in Figure 15 indicates the direction of supply of the raw material gas. In the following, the same reference numerals are used for elements that are the same as those in the adsorption device 100, and explanations may be omitted.

[0116] The housing 70 has, for example, a raw material gas inlet 70a for supplying a raw material gas containing an acidic gas to the adsorption device 100 during adsorption operation, and a raw material gas outlet 70b for discharging the raw material gas, after the adsorbent 21 has been moved, to the outside of the adsorption device 100. If the raw material gas is the atmosphere, the raw material gas inlet 70a may be open to the atmosphere and configured to continuously draw in the atmosphere. The raw material gas outlet 70b may be provided with a blowing mechanism such as a fan for drawing in the raw material gas from the raw material gas inlet 70a. The housing 70 may further have a desorption gas outlet (not shown) for discharging the desorbed gas desorbed from the adsorbent 21 to the outside of the adsorption device 100 during desorption operation.

[0117] The descriptions of each embodiment and each modification described above are interchangeable, insofar as they do not conflict with technical standards. Furthermore, each embodiment and each modification may be combined with each other, insofar as they do not conflict with technical standards. [Industrial applicability]

[0118] The adsorption apparatus of this embodiment is suitable for recovering acidic gases, particularly carbon dioxide. [Explanation of Symbols]

[0119] 100, 100A, 100B Adsorption Device 10 Heat transfer section 10f Planar part 10a Long side 10b Short side 10c spacing 20 Adsorption structure 20f Planar part 21 Acid gas adsorbent 211 Main body 211m Yamabe 211v Tanibe 211U Suction Unit 212 Support 22 Ventilation paths 230 Spacer 30 units 40 space 51. First media route 52 Second media route 60 Support part 60a Heat medium inlet 60b Heat medium outlet 61 Lower part 62 Side 63 Top 65 partition plates 70 cabinets 70a Raw material gas inlet 70b Raw material gas outlet SP interior space D Direction of insertion and removal M Heat medium

Claims

1. Heat transfer section, An adsorption structure is arranged in the space adjacent to the heat transfer section, Equipped with, The adsorption structure comprises an acidic gas adsorbent and has a ventilation path. The acidic gas adsorbent contains an amine compound. Acid gas adsorption device.

2. The heat transfer section is in contact with at least a part of the adsorption structure. The acid gas adsorption apparatus according to claim 1.

3. The heat transfer section has a planar portion, The adsorption structure is arranged in the space facing the planar portion of the heat transfer section. The acid gas adsorption apparatus according to claim 1.

4. The heat transfer section and the adsorption structure are stacked, The ventilation path extends along a direction perpendicular to the stacking direction of the heat transfer section and the adsorption structure. The acid gas adsorption apparatus according to claim 1.

5. The heat transfer section has a first medium path through which a heat transfer medium flows. The acid gas adsorption apparatus according to claim 1.

6. With additional support sections, The support portion has a second medium path communicating with the first medium path, a heat medium inlet for introducing the heat medium into the second medium path, and a heat medium outlet for discharging the heat medium from the second medium path. The acid gas adsorption apparatus according to claim 5.

7. During a desorption operation in which the acidic gas adsorbed on the acidic gas adsorbent is desorbed from the acidic gas adsorbent, the heat transfer medium passes through the first medium path. The acid gas adsorption apparatus according to claim 5.

8. The system comprises a plurality of units including the heat transfer section and the adsorption structure. Multiple of the above units are stacked, The acid gas adsorption apparatus according to claim 1.

9. The adsorption structure is detachable from the acid gas adsorption device. The acid gas adsorption apparatus according to claim 1.

10. The adsorption structure has a porosity of 59 vol% to 91 vol%. The acid gas adsorption apparatus according to claim 1.

11. The adsorption structure is 350 m 2 / m 3 More than 2000m 2 / m 3 Having the following specific surface area, The acid gas adsorption apparatus according to claim 1.

12. The amine compound comprises a polymer having an amino group. The acid gas adsorption apparatus according to claim 1.

13. The polymer includes an amine polymer having structural units derived from epoxy monomers. The acid gas adsorption apparatus according to claim 12.

14. The acidic gas adsorbent has a three-dimensional network structure composed of the polymer, The acid gas adsorption apparatus according to claim 12.

15. The acidic gas adsorbent includes a corrugated body portion and a flat body portion. The acid gas adsorption apparatus according to claim 1.

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