Acid gas adsorption device

Abstract

Provided is an acid gas adsorption device capable of suppressing the outflow of an acid gas adsorption material. An acidic gas adsorption device according to an embodiment of the present invention is provided with an acidic gas adsorption unit and an adsorbent outflow suppression unit. The acid gas adsorption part contains an acid gas adsorption material capable of adsorbing an acid gas. And the acid gas adsorption part can allow fluid to pass through. The adsorbent outflow suppression part is located on the downstream side of the acid gas adsorption part in the direction in which the fluid passes. The adsorbent outflow suppression part contains an outflow suppression material. At 25 DEG C, the absolute value of the difference between the Hilbert solubility of the acid gas adsorbing material and the Hilbert solubility of the outflow suppressing material is 1.0 (cal / cm3) 1 / 2 or more.

Description

Technical Field

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

[0002] In recent years, efforts have been made to separate and recover acidic gases contained in the atmosphere in order to reduce environmental impact. A prime example of such acidic gases is carbon dioxide (hereinafter sometimes referred to as CO2), which contributes to global warming. As a representative example of these efforts, the Carbon dioxide Capture, Utilization and Storage (CCUS) cycle is known.

[0003] As a carbon dioxide adsorption device used in the separation and recovery of carbon dioxide, a gas separation unit having a carbon dioxide adsorption section with a particulate structure has been proposed (see, for example, Patent Document 1). In the carbon dioxide adsorption device, the carbon dioxide adsorption material contained in the carbon dioxide adsorption section adsorbs CO2 at a predetermined adsorption temperature and releases CO2 at a release temperature exceeding the adsorption temperature.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2014 / 170184 Summary of the Invention

[0007] In a carbon dioxide adsorption apparatus as described in Patent Document 1, a method is proposed whereby a desorbed gas heated to its desorption temperature is passed through a carbon dioxide adsorption section, and CO2 is recovered along with the desorbed gas. In such a CO2 recovery method, since heat energy is transferred from the passing desorbed gas to the carbon dioxide adsorption section, the temperature of the carbon dioxide adsorption section sometimes decreases as it moves downstream in the direction of the desorbed gas's passage. In this case, in the downstream portion of the carbon dioxide adsorption section, condensable components (typically water) contained in the desorbed gas condense and liquefy, and the carbon dioxide adsorbent material may dissolve and / or disperse in this liquid. Therefore, there is a problem that the liquid containing the carbon dioxide adsorbent material flows out of the carbon dioxide adsorption apparatus along with the desorbed gas.

[0008] The main objective of this invention is to provide an acid gas adsorption device capable of suppressing the outflow of acid gas adsorption materials.

[0009] [1] The acid gas adsorption apparatus according to the embodiments of the present invention includes an acid gas adsorption section and an adsorption material outflow suppression section. The acid gas adsorption section includes an acid gas adsorption material capable of adsorbing acid gases. The acid gas adsorption section is capable of allowing fluid to pass through. The adsorption material outflow suppression section is located downstream of the acid gas adsorption section in the direction of fluid passage. The adsorption material outflow suppression section includes an outflow suppression material. At 25°C, the absolute value of the difference between the Hildebrand solubility parameter of the acid gas adsorption material and the Hildebrand solubility parameter of the outflow suppression material is 1.0 (cal / cm³). 3 ) 1／2 above.

[0010] [2] In the acidic gas adsorption device described in [1] above, the acidic gas can be carbon dioxide.

[0011] [3] In the acidic gas adsorption device described in [1] or [2] above, the solubility of the above-mentioned effluent suppression material in water at 25°C can be less than 0.1 g / 100 g H2O.

[0012] Invention Effects

[0013] According to embodiments of the present invention, an acid gas adsorption device capable of suppressing the outflow of acid gas adsorption materials can be realized. Attached Figure Description

[0014] Figure 1 This is a schematic diagram of an acid gas adsorption device according to one embodiment of the present invention.

[0015] Figure 2 This is a schematic diagram of an acid gas adsorption device according to another embodiment of the present invention.

[0016] Figure 3 This is a schematic diagram of an acid gas adsorption device according to another embodiment of the present invention.

[0017] Figure 4 yes Figure 3 A schematic diagram of the first adsorption block of the acid gas adsorption device.

[0018] Figure 5 This is a schematic perspective view of another embodiment of the first adsorption block.

[0019] Figure 6 yes Figure 5 A schematic cross-sectional view of the first adsorption block.

[0020] Figure 7 yes Figure 3 A schematic cross-sectional view of the suppression block in the acid gas adsorption device. Detailed Implementation

[0021] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings; however, the present invention is not limited to these embodiments. Furthermore, to make the description clearer, the drawings sometimes schematically represent the width, thickness, shape, etc., of various parts compared to the embodiments; however, these are merely examples and do not limit the interpretation of the present invention.

[0022] A. Overview of the Acid Gas Adsorption Device

[0023] Figure 1 This is a schematic diagram of an acid gas adsorption device according to one embodiment of the present invention.

[0024] The acid gas adsorption apparatus 100 illustrated in the figure includes an acid gas adsorption section 1 and an adsorption material effluent suppression section 2. The acid gas adsorption section 1 contains an acid gas adsorption material capable of adsorbing acid gases. The acid gas adsorption section 1 is permeable to fluid. The adsorption material effluent suppression section 2 is located downstream of the acid gas adsorption section 1 in the direction of fluid flow. The adsorption material effluent suppression section 2 contains effluent suppression material. At 25°C, the absolute value of the difference between the Hildebrand solubility parameter of the acid gas adsorption material and the Hildebrand solubility parameter of the effluent suppression material (hereinafter referred to as the SP value difference between the acid gas adsorption material and the effluent suppression material) is 1.0 (cal / cm³). 3 ) 1／2 above.

[0025] It should be noted that the acidic gas adsorbent materials contained in the acidic gas adsorption section are determined, for example, by mass analysis, gas chromatography, liquid chromatography, nuclear magnetic resonance spectrometry, or infrared spectrometry. When the acidic gas adsorption section contains multiple acidic gas adsorbent materials, the Hildebrand solubility parameter (hereinafter referred to as SP value) of each acidic gas adsorbent material is calculated as the sum of the product of the volume ratio of each acidic gas adsorbent material and the SP value.

[0026] More specifically, firstly, a cylindrical sample is collected from the portion of the acidic gas adsorption section containing the acidic gas adsorption material (typically the acidic gas adsorption material layer described later, or the particulate adsorption material described later). Next, for example, elemental mapping images of the following nine locations in the sample are obtained at 300x magnification using an electron probe microanalyzer (EPMA) capable of detecting light elements such as nitrogen.

[0027] First position: the center of one end face of the sample; Second position: the end of the one end face; Third position: the midpoint of the line segment connecting the first position and the second position;

[0028] Fourth position: The center of the section obtained by cutting the sample along a direction orthogonal to the length direction; Fifth position: The end of the section; Sixth position: The midpoint of the line segment connecting the fourth and fifth positions;

[0029] Seventh position: the center of the other end face of the sample; Eighth position: the end of the other end face; Ninth position: the midpoint of the line segment connecting the seventh and eighth positions.

[0030] Next, based on the elemental mapping images from the first to the ninth position, the area ratios (elemental ratios) of the multiple acidic gas adsorbent materials are calculated. Then, the average of the obtained area ratios (elemental ratios) is calculated. Next, the volume of each acidic gas adsorbent material relative to the total volume of the multiple acidic gas adsorbent materials (100Vol%) is calculated from the average of the area ratios (elemental ratios) of the multiple acidic gas adsorbent materials.

[0031] Next, the product of the volume ratio and SP value of each acid gas adsorbent material is added together. For example, if the acid gas adsorption section includes a first acid gas adsorbent material A (SP value 15, volume ratio 70 Vol%) and a second acid gas adsorbent material B (SP value 10, volume ratio 30 Vol%), the SP value of the acid gas adsorbent materials included in the acid gas adsorption section is calculated using the following formula (1) as 13.5 (cal / cm). 3 ) 1／2 .

[0032] (15×70 / 100) + (10×30 / 100) = 13.5···(1)

[0033] Furthermore, the effluent suppressing material contained in the effluent suppressing section of the adsorbent material is determined, for example, by mass analysis, gas chromatography, liquid chromatography, nuclear magnetic resonance spectrometry, or infrared spectrometry. When the effluent suppressing section of the adsorbent material contains multiple effluent suppressing materials, a sample is collected from the portion of the effluent suppressing section containing the effluent suppressing material (typically the effluent suppressing material layer described later). In addition, the SP value of the effluent suppressing material is calculated in the same manner as the SP value of the acidic gas adsorbent material described above.

[0034] According to one embodiment of the present invention, since the adsorbent material outflow suppression section located downstream of the acid gas adsorption section includes an outflow suppression material whose SP value differs from that of the acid gas adsorption material by the aforementioned value, even if liquid is generated in the downstream portion of the acid gas adsorption section, causing the acid gas adsorption material to dissolve and / or disperse in the liquid, it is possible to suppress the liquid containing the acid gas adsorption material (hereinafter referred to as liquid containing adsorption material) from flowing out of the adsorbent material outflow suppression section and out of the acid gas adsorption device. As a result, it is possible to suppress the unintentional discharge of the acid gas adsorption material from the acid gas adsorption device. In one embodiment, even if a substance harmful to the human body is used as the acid gas adsorption material, since the outflow of the acid gas adsorption material from the acid gas adsorption device is suppressed, the safety of the acid gas adsorption device can be improved and the environmental impact can be reduced.

[0035] The SP value difference between the acidic gas adsorbent and the efflux suppressant at 25°C is preferably 1.5 (cal / cm³). 3 ) 1／2 That's all. If the acidic gas adsorbent and the outflow suppressing material have such a difference in SP value, then the liquid containing the adsorbent material can be stably suppressed from passing through the outflow suppressing section of the adsorbent material.

[0036] On the other hand, the SP value difference between the acidic gas adsorbent and the efflux suppressor at 25°C is, for example, 12 (cal / cm). 3 ) 1／2 The following is preferred: 8 (cal / cm) 3 ) 1／2 The following is more preferably 5 (cal / cm). 3 ) 1／2 The following is a further preferred value: 3 (cal / cm³). 3 ) 1／2 The following applies. If the acidic gas adsorbent and the effluent suppression material have a SP value difference like this, the effluent suppression material can be dissolved, thereby stably forming an adsorbent material effluent suppression section. In particular, when the adsorbent material effluent suppression section has the effluent suppression material layer described later, an effluent suppression material layer with sufficient thickness can be stably formed.

[0037] At 25°C, the SP value of the acidic gas adsorbent material can be higher or lower than that of the effluent suppression material. In one embodiment, the SP value of the acidic gas adsorbent material exceeds that of the effluent suppression material.

[0038] The SP value of the acidic gas adsorbent at 25°C is, for example, 10.0 (cal / cm³). 3 ) 1／2 ~18.0 (cal / cm) 3 )1／2 The preferred value is 11.0 (cal / cm³). 3 ) 1／2 ~17.0 (cal / cm) 3 ) 1／2 More preferably, it is 11.9 (cal / cm³). 3 ) 1／2 ~14.5 (cal / cm) 3 ) 1／2 .

[0039] For example, based on information from functional groups detected by structural analysis such as infrared spectroscopy and Raman spectroscopy, the SP value is calculated using the Fedors method described in "Polymer Engineering and Science, February, 1974, Vol.14 No.2 Page147-154".

[0040] The SP value of the effluent suppression material at 25°C is, for example, 5.0 (cal / cm³). 3 ) 1／2 ~13.4 (cal / cm) 3 ) 1／2 The preferred value is 6.2 (cal / cm³). 3 ) 1／2 ~10.4 (cal / cm) 3 ) 1／2 More preferably 8.0 (cal / cm³) 3 ) 1／2 ~10.4 (cal / cm) 3 ) 1／2 .

[0041] The acid gas adsorbent material can be selected arbitrarily and appropriately based on the acid gas that is the target of adsorption in the acid gas adsorption device.

[0042] Examples of acidic gases include carbon dioxide (CO2), hydrogen sulfide, sulfur dioxide, nitrogen dioxide, dimethyl sulfide (DMS), and hydrogen chloride. In one embodiment, the acidic gas is carbon dioxide (CO2), and the gas to be processed as a fluid is a CO2-containing gas. In addition to CO2, the CO2-containing gas may also contain nitrogen. Air (atmosphere) is a representative example of a CO2-containing gas. The case where the acidic gas is carbon dioxide (CO2) will be described in detail below.

[0043] When the acidic gas is CO2, the acidic gas adsorbent material is a carbon dioxide adsorbent material.

[0044] As a carbon dioxide adsorbent, any suitable compound capable of adsorbing and desorbing CO2 can be used. Examples of carbon dioxide adsorbents include nitrogen-containing compounds.

[0045] More specifically, examples of nitrogen-containing compounds include: primary amines such as monoethanolamine and polyethyleneamine; secondary amines such as diethanolamine, cyclic amines, and N-(3-aminopropyl)diethanolamine; tertiary amines such as methyldiethylamine and triethanolamine; ethylene pentamine and other ethylidene amine compounds; aminosilane coupling agents such as aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyl-trimethoxysilane, and polyethyleneimine-trimethoxysilane; organic monomers with primary to tertiary amino groups such as ethyleneimine and styrene endowed with amino groups; organic polymers with primary to tertiary amino groups such as linear polyethyleneimine, branched polyethyleneimine with primary to tertiary amino groups, polyamide amine, and polyethyleneamine; piperazine compounds such as piperazine and 1-(2-hydroxyethyl)piperazine; and organic / inorganic compounds endowed with amino groups as substituents.

[0046] Among carbon dioxide adsorbent materials, preferred examples include: methyldiethylamine, monoethanolamine, cyclic amine, diethanolamine, tetraethylenepentamine, ethyleneimine, linear polyethyleneimine, branched polyethyleneimine, organic / inorganic compounds with amino groups as substituents, and piperazine; more preferred examples include: linear polyethyleneimine, branched polyethyleneimine, and piperazine.

[0047] Carbon dioxide adsorbents like these can be used alone or in combination.

[0048] The efflux suppression material can be arbitrarily and appropriately selected based on the acid gas adsorbent (carbon dioxide adsorbent) with the SP value difference within the range mentioned above. The efflux suppression material may or may not have acid gas adsorption capacity.

[0049] Organic adhesives can be cited as examples of effusion-inhibiting materials. These effusion-inhibiting materials can be used alone or in combination.

[0050] Organic adhesives typically do not have the ability to adsorb acidic gases.

[0051] Examples of organic adhesives include: fluoropolymers such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene-propylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), and polyvinyl fluoride (PVF); and amorphous plastics such as polyethersulfone (PES), polysulfone, polyvinylidene chloride, polyimide, and polyvinyl chloride. Organic adhesives can be used alone or in combination.

[0052] The weight-average molecular weight (Mw, converted from polystyrene) of the organic adhesive is, for example, 10,000 or more, preferably 200,000 or more, for example, 10,000,000 or less, preferably 1,000,000 or less.

[0053] Plastics and resins containing nitrogen atoms are typically characterized by their ability to adsorb acidic gases. Examples of nitrogen-containing plastics and resins include ion exchange resins with amino groups. Nitrogen-containing plastics and resins can be used alone or in combination.

[0054] Among such effusion-suppressing materials, organic adhesives are preferred, fluoropolymers are more preferred, and PVF and PVDF are even more preferred.

[0055] The solubility of the effluent suppressing material (typically an organic binder) in water at 25°C is, for example, 0.1 g / 100 g H₂O or less, preferably 0.05 g / 100 g H₂O or less. The lower limit of the solubility of the effluent suppressing material in water at 25°C is typically 0.01 g / 100 g H₂O or more. If the solubility of the effluent suppressing material in water at 25°C is within such a range, even if water is generated downstream of the acidic gas adsorption section, causing the acidic gas adsorption material to dissolve, the aqueous solution of the acidic gas adsorption material can be stably suppressed from flowing through the adsorption material effluent suppressing section and out of the acidic gas adsorption device. The solubility in water is measured, for example, by immersing the object in water at 25°C for 3 hours and allowing it to dissolve by mass change.

[0056] The following describes the specific structure of the acid gas adsorption device.

[0057] B. Acidic gas adsorption section

[0058] The acid gas adsorption section 1 typically includes an upstream end face 1a and a downstream end face 1b in the direction of fluid flow. The direction of fluid flow is typically orthogonal to the upstream end face 1a and the downstream end face 1b of the acid gas adsorption section 1.

[0059] The size of the acid gas adsorption section 1 in the direction of fluid flow is not particularly limited, for example, it is 0.5m to 2.0m, preferably 0.6m to 1.0m. The size of the acid gas adsorption section 1 in the direction orthogonal to the direction of fluid flow is not particularly limited, for example, it is 0.5m to 4.0m, preferably 1.0m to 2.0mm.

[0060] The acid gas adsorption section 1 can be divided into multiple parts in the direction of fluid flow, or it can be divided into multiple parts in a direction that intersects (typically orthogonal) the direction of fluid flow.

[0061] like Figure 2As shown, in one embodiment, the acid gas adsorption section 1 is divided into multiple sections in the direction of fluid flow. The acid gas adsorption section 1 may be composed of multiple adsorption sections. The multiple adsorption sections include a first adsorption section to an nth adsorption section. n represents, for example, an integer from 2 to 20.

[0062] In the example shown, the acidic gas adsorption section 1 is divided into a first adsorption section 11 and a second adsorption section 12 in the direction of fluid flow. The first adsorption section 11 and the second adsorption section 12 are configured as separate units.

[0063] The fluid supplied to the acid gas adsorption device sometimes contains poisoning or degrading components that cause the acid gas adsorption material to deteriorate. Since the fluid passes sequentially through the first and second adsorption sections, the poisoning or degrading components in the fluid tend to adhere more easily to the first adsorption section, causing the acid gas adsorption material in the first section to deteriorate more easily than that in the second section. Therefore, the lifespan of the first adsorption section is sometimes shorter than that of the second. According to one embodiment, since a first adsorption section with a relatively short lifespan and a second adsorption section with a relatively long lifespan are separated, the first and second adsorption sections can be replaced separately according to their lifespans. Therefore, compared to replacing the entire acid gas adsorption section, the acid gas adsorption section can be replaced locally and smoothly. As a result, the time required to replace the acid gas adsorption section can be reduced, thus shortening the downtime of the acid gas adsorption device. Furthermore, since the first and second adsorption sections can be replaced at appropriate times corresponding to their lifespans, operating costs (specifically, the preparation cost of a new adsorption section and the disposal cost of the used adsorption section) can be reduced.

[0064] The dimensions of the first adsorption section 11 and the second adsorption section 12 in the direction of fluid flow can be arbitrarily and appropriately adjusted according to the acidic gas adsorption material to be used.

[0065] In the multiple adsorption sections, gaps can be formed between adjacent adsorption sections (between the first and second adsorption sections in the example shown in the figure) in the direction of fluid flow. Typically, in acidic gas adsorption sections, fluid tends to flow more readily near the center and less readily in the outer portions. In this respect, forming gaps between adjacent adsorption sections reduces the flow rate deviation of the fluid in the acidic gas adsorption sections. In the direction of fluid flow, the size of this gap is, for example, 30% or less, preferably 10% or less, relative to the total length of the acidic gas adsorption section in the direction of fluid flow (the sum of the sizes of the multiple adsorption sections in the example shown in the figure). Adjusting the gap size in this way prevents fluid from stagnating between adjacent adsorption sections, allowing fluid to pass smoothly even in divided acidic gas adsorption sections.

[0066] Alternatively, multiple adsorption sections may all contain the same acidic gas adsorbent material, or a portion of the multiple adsorption sections may contain different acidic gas adsorbent materials. That is, the first adsorption section 11 and the second adsorption section 12 may contain the same acidic gas adsorbent material or may contain different acidic gas adsorbent materials.

[0067] like Figure 3 As shown, multiple adsorption sections can be divided into multiple parts in a direction that intersects (typically orthogonal) the flow direction of the fluid. In the example shown, the first adsorption section 11 and the second adsorption section 12 are each divided into multiple parts in a direction orthogonal to the flow direction of the fluid. The first adsorption section 11 is composed of multiple first adsorption blocks 11a. Thus, relatively small first adsorption blocks can be manufactured to form the first adsorption section. Therefore, the first adsorption section can be manufactured smoothly, and the particularly easily deteriorated parts (first adsorption blocks) in the first adsorption section can be replaced separately.

[0068] The size of the first adsorption block 11a can be adjusted arbitrarily and appropriately. The size of the first adsorption block 11a in the direction of fluid flow is, for example, 0.10m to 0.30m, preferably 0.15m to 0.20m. The size of the first adsorption block 11a in the direction orthogonal to the direction of fluid flow is, for example, 0.10m to 0.80m, preferably 0.15m to 0.60m.

[0069] In the example shown, the first adsorption section 11 is divided into four parts in a first orthogonal direction (the direction up and down on the paper) orthogonal to the fluid flow direction. The number of divisions of the first adsorption section in the first orthogonal direction is not limited to this. Alternatively, the first adsorption section 11 can also be divided into multiple parts in a second orthogonal direction (the direction of paper depth) orthogonal to both the fluid flow direction and the first orthogonal direction. The number of divisions of the first adsorption section in the direction orthogonal to the fluid flow direction is, for example, 2 or more and 300 or less.

[0070] Regarding the first adsorption blocks 11a that are adjacent to each other among the plurality of first adsorption blocks 11a, gaps may be formed between them, or they may contact each other in a direction orthogonal to the direction of fluid flow.

[0071] Alternatively, multiple first adsorption blocks 11a may contain the same acidic gas adsorption material, or a portion of multiple first adsorption blocks 11a may contain different acidic gas adsorption materials.

[0072] Furthermore, the second adsorption section 12 is composed of a plurality of second adsorption blocks 12a. The second adsorption section 12 composed of a plurality of second adsorption blocks 12a is described in the same manner as the first adsorption section 11 composed of a plurality of first adsorption blocks 11a described above.

[0073] B-1. Details of the adsorption block (acid gas adsorption section)

[0074] about Figure 1 The acidic gas adsorption section shown is integrally formed. Figure 2 The adsorption section shown Figure 3 The adsorption blocks shown differ in size, but otherwise have the same structure. Therefore, the following examples illustrate this. Figure 3 The first adsorption block 11a shown will be described in detail.

[0075] B-1-1. Adsorption block containing particulate adsorption material (acid gas adsorption section)

[0076] like Figure 4 As shown, in one embodiment, the first adsorption block 11a has a plurality of adsorption material-containing portions 61.

[0077] The adsorbent material portion 61 extends in a representative manner along the direction of fluid flow and has a thickness in a first orthogonal direction (the direction above and below the paper) that is orthogonal to the direction of fluid flow.

[0078] Multiple adsorbent material-containing sections 61 are stacked with spacing between them in their thickness direction. In the example shown, five adsorbent material-containing sections 61 are arranged side by side; however, the number of adsorbent material-containing sections 61 is not limited to this. The number of adsorbent material-containing sections 61 is, for example, five or more, preferably ten or more, and more preferably twenty or more. The spacing between adjacent adsorbent material-containing sections 61 is, for example, 0.5 cm to 1.5 cm.

[0079] Each of the multiple adsorbent material-containing sections 61 has a flexible fiber component 63 and multiple granular adsorbent materials 62.

[0080] The flexible fiber component 63 allows fluid to pass through while restricting the passage of particulate adsorbent material. The flexible fiber component 63 is typically shaped as a hollow structure (bag shape) capable of accommodating multiple particulate adsorbent materials 62. The flexible fiber component 63 can be a fabric or a non-woven fabric. Examples of materials for the flexible fiber component 63 include organic fibers and natural fibers; preferred materials include polyethylene terephthalate fibers, polyethylene fibers, and cellulose fibers. The thickness of the flexible fiber component 63 is, for example, 25 μm to 500 μm.

[0081] Multiple granular adsorbent materials 62 are filled inside a flexible fiber component 63 having a hollow shape (bag shape). The granular adsorbent materials 62 function as acid gas adsorbents, and typically function as carbon dioxide adsorbents. Examples of materials used as granular adsorbent materials 62 include materials modified with the aforementioned acid gas adsorbents, preferably cellulose modified with the aforementioned acid gas adsorbents, and more preferably nanofiberized cellulose modified with the aforementioned acid gas adsorbents. The average primary particle size of the granular adsorbent materials 62 is, for example, 60 μm to 1200 μm. The filling ratio of the granular adsorbent materials 62 in the adsorbent material portion 61 can be any suitable value.

[0082] The acid gas adsorption device 1 shown in the figure also includes a plurality of spacers 64. The spacers 64 are sandwiched between adjacent adsorbent material portions 61. This ensures a stable spacing between adjacent adsorbent material layers. In one embodiment, the plurality of adsorbent material portions 61 and the plurality of spacers 64 are arranged such that they extend from a second orthogonal direction (orthogonal to the thickness direction of the adsorbent material portions 61)... Figure 1 Observing from the depth direction of the paper, it appears to be roughly Z-shaped.

[0083] As a first adsorption block 11a (acid gas adsorption section 1) like this, a gas separation unit described in International Publication No. 2014 / 170184 can be cited as an example. The entire description of that publication is incorporated herein by reference.

[0084] B-1-2. Adsorption block (acid gas adsorption section) including acid gas adsorption material layer.

[0085] In another embodiment, such as Figure 5 and Figure 6 As shown, the first adsorption block 11a typically includes a substrate 4 and an acid gas adsorption material layer 5.

[0086] The structure of the substrate 4 is not particularly limited; for example, it can be a honeycomb structure, a filter cloth, or a granular structure. The acid gas adsorption material layer 5 can be disposed on the surface of the substrate 4 without any particular limitation.

[0087] In one embodiment, the substrate 4 is a honeycomb substrate 4a. The honeycomb substrate 4a has partitions 42 defining a plurality of compartments 43.

[0088] The compartment 43 extends along the length (axial direction) of the honeycomb substrate 4a from the first end face E1 (inflow end face) to the second end face E2 (outflow end face) (see reference). Figure 6The compartment 43 has any suitable shape in the cross-section of the honeycomb substrate 4a in a direction orthogonal to the length direction. Examples of cross-sectional shapes for the compartments include triangles, quadrilaterals, pentagons, polygons with more than one hexagon, circles, and ellipses. The cross-sectional shapes and dimensions of the compartments can be all the same or at least some different. Among such cross-sectional shapes of compartments, hexagons and quadrilaterals are preferred, and squares, rectangles, or hexagons are more preferred.

[0089] The cell density (i.e., the number of cells per unit area) in the cross-section of the honeycomb substrate in a direction orthogonal to the length direction can be appropriately set according to the purpose. For example, the cell density can be 4 cells / cm². 2 ~320 compartments / cm 2 If the cell density is within this range, the strength and effective GSA (geometric surface area) of the honeycomb substrate can be adequately ensured.

[0090] The honeycomb substrate 4a has any suitable shape (overall shape). Examples of honeycomb substrate shapes include: a cylindrical shape with a circular base, an elliptical cylindrical shape with an elliptical base, a prismatic shape with a polygonal base, and a columnar shape with an irregular base. The honeycomb substrate 4a in the illustration has a prismatic shape. The outer diameter and length of the honeycomb substrate can be appropriately set according to the purpose. Although not shown, the honeycomb substrate may have a hollow region at the center of a cross-section in a direction orthogonal to the length direction.

[0091] Typically, the honeycomb substrate 4a includes an outer wall 41 and a partition wall 42 located inside the outer wall 41. In the example shown, the outer wall 41 and the partition wall 42 are integrally formed. The outer wall 41 and the partition wall 42 may also be separate components.

[0092] In the example shown, the outer wall 41 has a rectangular shape. The thickness of the outer wall 41 can be set arbitrarily and appropriately. For example, the thickness of the outer wall 41 is 0.1 mm to 10 mm.

[0093] The partition 42 defines a plurality of compartments 43. More specifically, the partition 42 has a first partition 42a and a second partition 42b orthogonal to each other, which define a plurality of compartments 43. The cross-sectional shape of the compartments 43 is approximately quadrilateral. It should be noted that the configuration of the partition is not limited to the partition 42 described above. The partition may have a first partition extending in a radial direction and a second partition extending in a circumferential direction, which define a plurality of compartments.

[0094] The thickness of the partition wall 42 can be appropriately set according to the application of the acid gas adsorption device. Typically, the thickness of the partition wall 42 is thinner than the thickness of the outer wall 41. The thickness of the partition wall 42 is, for example, 0.03 mm to 0.6 mm. The thickness of the partition wall is determined, for example, by cross-sectional observation based on SEM (scanning electron microscopy). If the thickness of the partition wall is within such a range, the mechanical strength of the honeycomb substrate can be sufficiently ensured, and the opening area (the total area of ​​the compartments in the cross-section) can be sufficiently ensured.

[0095] The porosity of the partition wall 42 can be appropriately set according to the purpose. The porosity of the partition wall 42 is, for example, 15% to 70%, preferably 20% to 45%. It should be noted that the porosity can be determined by, for example, the mercury injection method.

[0096] The bulk density of the partition 42 can be appropriately set according to the purpose. Their bulk density is, for example, 0.10 g / cm³. 3 ~0.60g / cm 3 The preferred value is 0.20 g / cm³. 3 ~0.50g / cm 3 It should be noted that bulk density can be determined using, for example, the mercury infiltration method.

[0097] Ceramic materials are representative examples of materials constituting the partition 42. Examples of ceramic materials include: silicon carbide, silicon-silicon carbide composites, cordierite, andalusite, alumina, silicon nitride, spinel, silicon-cordierite composites, lithium aluminum silicate, and aluminum titanate. The materials constituting the partition can be used alone or in combination. Among the materials constituting the partition, cordierite, alumina, andalusite, silicon carbide, silicon-silicon carbide composites, and silicon nitride are preferred, and silicon carbide and silicon-silicon carbide composites are more preferred.

[0098] Typically, such a honeycomb substrate 4a is manufactured using the following method. First, a binder and water or organic solvent are added as needed to a material powder containing the aforementioned ceramic powder. The resulting mixture is then kneaded to form a blank. The blank is shaped (typically by extrusion molding) into the desired shape, dried, and then fired as needed to produce the honeycomb substrate 4a. Firing is performed, for example, at 1200°C to 1500°C. The firing time is, for example, 1 hour to 20 hours.

[0099] In one embodiment, an acidic gas adsorbent material layer 5 is formed on the surface of the partition 42. The thickness of the acidic gas adsorbent material layer 5 is not particularly limited. The thickness of the acidic gas adsorbent material layer 5 is, for example, 10 μm to 1000 μm, preferably 50 μm to 500 μm, and more preferably 150 μm to 250 μm.

[0100] In the first adsorption block 11a, a flow path 44 is formed in the portion of the cross-section of the compartment 43 where the acid gas adsorption material layer 5 is not formed (typically the central portion). The acid gas adsorption material layer 5 can be formed on the entire inner surface of the partition wall 42 (i.e., in a manner that surrounds the flow path 44), as shown in the example, or it can be formed on a portion of the surface of the partition wall. If the acid gas adsorption material layer 5 is formed on the entire inner surface of the partition wall 42, the adsorption efficiency of acid gases (typically CO2) can be improved.

[0101] Like the compartment 43, the flow path 44 extends from the first end face E1 (inflow end face) to the second end face E2 (outflow end face). Typically, the direction in which the flow path 44 extends is parallel to the direction of fluid flow. As for the cross-sectional shape of the flow path 44, it can be the same as that of the compartment 43 described above; preferably, it can be hexagonal or quadrilateral, and more preferably, it can be square, rectangular, or hexagonal. The cross-sectional shape and dimensions of the flow path 44 can be entirely the same, or at least partially different.

[0102] Typically, in the adsorption process described later, the target gas containing acidic gas is supplied to compartment 43 (more specifically, flow path 44), and in the desorption process described later, the desorbed gas is supplied to compartment 43 (more specifically, flow path 44).

[0103] The acid gas adsorbent layer 5 comprises the acid gas adsorbent described above. In one embodiment, the acid gas adsorbent layer 5, in addition to comprising the acid gas adsorbent described above, also comprises a porous support. In this case, the acid gas adsorbent is typically supported on the porous support and faces the flow path. If the acid gas adsorbent layer comprises a porous support, it is possible to prevent the acid gas adsorbent from detaching from the acid gas adsorbent layer during the adsorption and / or desorption processes.

[0104] Porous supports can form mesopores within the acidic gas adsorption material layer. Examples of porous supports include: metal-organic structures (MOFs) such as MOF-74, MOF-200, and MOF-210; activated carbon; nitrogen-doped carbon; mesoporous silica; mesoporous alumina; zeolite; carbon nanotubes; and fluorinated resins such as polyvinylidene fluoride (PVDF). Preferably, these include: metal-organic structures (MOFs), activated carbon, PVDF, zeolite, mesoporous silica, and mesoporous alumina. Porous supports can be used alone or in combination.

[0105] The BET specific surface area of ​​the porous support is, for example, 50 m². 2 / g or more, preferably 500m 2 / g or more. If the surface area of ​​the porous support is adjusted in this way, it is possible to stably support acidic gas adsorbent materials and improve the adsorption efficiency of acidic gases. The upper limit of the BET specific surface area of ​​the porous support is typically 2000 m². 2 / g or less.

[0106] When the acidic gas adsorbent layer comprises an acidic gas adsorbent and a porous support, the total content of the acidic gas adsorbent and the porous support in the acidic gas adsorbent layer is, for example, 30% by mass or more, preferably 50% by mass or more. On the other hand, the total content of the acidic gas adsorbent and the porous support is, for example, 100% by mass or less, preferably 99% by mass or less.

[0107] The content of acidic gas adsorbent material in the acidic gas adsorbent material layer is, for example, 30% by mass or more, preferably 50% by mass or more. On the other hand, the content of acidic gas adsorbent material in the acidic gas adsorbent material layer is, for example, 99% by mass or less. The content of the porous support relative to 1 part by mass of acidic gas adsorbent material is, for example, 0.01 parts by mass to 0.7 parts by mass, preferably 0.3 parts by mass to 0.5 parts by mass. If the content of the porous support is in such a range, the acidic gas adsorbent material can be supported more stably.

[0108] Alternatively, the acidic gas adsorbent layer may consist solely of acidic gas adsorbent material. In this case, the acidic gas adsorbent material is directly supported on the partition wall 42 and faces the flow path. When the acidic gas adsorbent layer consists solely of acidic gas adsorbent material, the content of acidic gas adsorbent material in the acidic gas adsorbent layer is typically 95.0% to 100% by mass. If the content of acidic gas adsorbent material is within such a range, excellent adsorption efficiency of acidic gases can be reliably ensured.

[0109] Such acidic gas adsorbent material layers are typically fabricated using the following method. The acidic gas adsorbent material described above is dissolved in a solvent to prepare a solution. Additionally, the porous support described above is added to the solvent as needed. The order of addition of the acidic gas adsorbent material and the porous support is not particularly limited. Then, the solution of the acidic gas adsorbent material is coated onto a substrate (specifically, a partition wall), and the coating is dried and sintered as needed to form the acidic gas adsorbent material layer.

[0110] C. Adsorbent material effluent suppression section

[0111] like Figure 1As shown, the adsorbent material outflow suppression section 2 typically suppresses the passage of liquid containing acidic gas adsorbent material (liquid containing adsorbent material) while allowing the passage of fluids other than liquid containing adsorbent material.

[0112] The size of the adsorbent material outflow suppression section 2 in the direction of fluid flow is, for example, 0.01 m to 2 m, preferably 0.1 m to 0.5 m. If the size of the adsorbent material outflow suppression section in the direction of fluid flow is within such a range, the passage of liquid containing adsorbent material can be sufficiently suppressed.

[0113] The size of the adsorbent material outflow suppression section 2, which is perpendicular to the direction of fluid flow, is not particularly limited, for example, it is 0.5m to 4.0m, preferably 1.0m to 2.0m. In one embodiment, when viewed from the direction of fluid flow, the shape and size of the adsorbent material outflow suppression section 2 are substantially the same as the shape and size of the acid gas adsorption section 1.

[0114] In the example shown, the adsorbent material outflow suppression section 2 is arranged with an open gap relative to the downstream end face 1b of the acid gas adsorption section 1.

[0115] The size of the gap between the acid gas adsorption section 1 and the adsorbent material outflow suppression section 2 in the direction of fluid flow is, for example, 0% to 50% of the total length of the adsorbent material outflow suppression section in the direction of fluid flow, preferably 5% to 20%. If such a gap is formed between the acid gas adsorption section and the adsorbent material outflow suppression section, the liquid containing the adsorbent material can be stably held in the gap.

[0116] Although not illustrated, the adsorbent material outflow suppression section 2 can be tilted vertically upwards along the downstream side in the direction of fluid flow. If the adsorbent material outflow suppression section is tilted in this way, it can stably prevent liquid containing adsorbent material from passing through the adsorbent material outflow suppression section and being discharged from the acid gas adsorption device. In particular, when a gap is formed between the acid gas adsorption section and the adsorbent material outflow suppression section, the liquid containing adsorbent material can be smoothly guided into that gap.

[0117] The adsorbent material outflow suppression section 2 can be divided into multiple parts in the direction of fluid flow, or it can be divided into multiple parts in a direction that intersects (typically orthogonal) the direction of fluid flow.

[0118] like Figure 3As shown, in one embodiment, the adsorbent material outflow suppression section 2 is divided into multiple parts in a direction intersecting (typically orthogonal) with the flow direction of the fluid. The adsorbent material outflow suppression section 2 is composed of multiple suppression blocks 2a. Accordingly, relatively small suppression blocks can be manufactured to form the adsorbent material outflow suppression section. Therefore, the adsorbent material outflow suppression section can be manufactured smoothly, and particularly easily deteriorated parts (suppression blocks) in the adsorbent material outflow suppression section can be replaced separately.

[0119] The size of the suppression block 2a can be adjusted arbitrarily and appropriately. The range of the size of the suppression block 2a is, for example, the same as the range of the size of the first adsorption block 11a described above.

[0120] In the example shown, the adsorbent material outflow suppression section 2 is divided into four parts in a first orthogonal direction (the vertical direction on the paper) orthogonal to the fluid flow direction. The number of divisions of the adsorbent material outflow suppression section 2 in the first orthogonal direction is not limited to this. Alternatively, the adsorbent material outflow suppression section 2 may also be divided into multiple parts in a second orthogonal direction (the depth direction on the paper) orthogonal to both the fluid flow direction and the first orthogonal direction. The number of divisions of the adsorbent material outflow suppression section 2 in the direction orthogonal to the fluid flow direction is, for example, 2 or more and 300 or less.

[0121] The adjacent suppression blocks 2a in the plurality of suppression blocks 2a can form gaps between them, or they can contact each other in a direction orthogonal to the direction of fluid flow.

[0122] Alternatively, multiple suppression blocks 2a may contain the same effluent suppression material, or a portion of multiple suppression blocks 2a may contain different effluent suppression materials.

[0123] Regarding the adsorption material effluent suppression section 2, it includes an effluent suppression material instead of the acid gas adsorption material; otherwise, it can be described in the same manner as the acid gas adsorption section 1 described above. Furthermore, regarding... Figure 1 The adsorbent material outflow suppression section (integrated) shown and Figure 3 The suppression blocks shown differ in size, but otherwise have the same structure. Therefore, the following are examples. Figure 3 The structure of the suppression block 2a shown will be explained in detail.

[0124] like Figure 7 As shown, in one embodiment, the suppression block 2a includes the honeycomb substrate 4a and the outflow suppression material layer 8 described above.

[0125] In the example shown, the effluent suppression material layer 8 is formed on the surface of the partition 42. The thickness of the effluent suppression material layer 8 is not particularly limited. In one embodiment, the thickness of the effluent suppression material layer 8 is less than the thickness of the acid gas adsorption material layer 5. The thickness of the effluent suppression material layer 8 is, for example, 0.5 μm to 800 μm, preferably 1.5 μm to 500 μm, more preferably 20 μm to 300 μm, and even more preferably 50 μm to 150 μm.

[0126] In the suppression block 2a, a flow path 44 is formed in the portion of the cross-section of the compartment 43 where the outflow suppression material layer 8 is not formed (typically the central portion). The flow path 44 of the suppression block 2a is described in the same manner as the flow path 44 of the first adsorption block 11a described above. The outflow suppression material layer 8 can be formed on the entire inner surface of the partition wall 42 (i.e., in a manner that surrounds the flow path 44), as shown in the example, or it can be formed on a portion of the surface of the partition wall. If the outflow suppression material layer 8 is formed on the entire inner surface of the partition wall 42, the flow of liquid containing adsorbent material can be stably suppressed from passing through the adsorbent material outflow suppression section.

[0127] The outflow inhibition material layer 8 contains the aforementioned outflow inhibition material.

[0128] The proportion of effluent suppressing material in the effluent suppressing material layer 8 is, for example, 1% to 100% by mass, preferably 10% to 50% by mass. If the proportion of effluent suppressing material in the effluent suppressing material layer is in such a range, it is possible to more stably suppress the flow of liquid containing adsorbent material from the adsorbent material effluent suppressing section.

[0129] Such an efflux suppression material layer 8 is typically manufactured using the following method: The aforementioned efflux suppression material is dissolved in a solvent to prepare an efflux suppression material solution. Then, the efflux suppression material solution is coated onto a substrate (specifically, a partition wall), and the coating is dried and sintered as needed to form the efflux suppression material layer 8.

[0130] D. Storage Department

[0131] like Figure 1 As shown, in one embodiment, the acid gas adsorption device 100 includes a housing 3 that houses the acid gas adsorption section 1 and the adsorption material outflow suppression section 2. The housing 3 is sometimes referred to as a casing. In other words, one housing 3 (casing) houses both the acid gas adsorption section 1 and the adsorption material outflow suppression section 2. Since one housing 3 houses both the acid gas adsorption section 1 and the adsorption material outflow suppression section 2, compared to the case where the acid gas adsorption section 1 and the adsorption material outflow suppression section 2 are housed in separate housing 3s, the acid gas adsorption device can be miniaturized. Therefore, equipment costs can be reduced, and the acid gas recovery per unit area can be increased.

[0132] In the example shown, the receiving section 3 has a cylindrical shape extending along the direction of fluid flow. The receiving section 3 has an inlet 31 and an outlet 32.

[0133] The inlet 31 is located at the upstream end of the receiving section 3 in the direction of fluid flow. The inlet 31 is located on the opposite side of the adsorption material outflow suppression section 2, relative to the acid gas adsorption section 1. The inlet 31 allows the target gas to pass through during the adsorption process described later.

[0134] The outlet 32 ​​is located at the downstream end of the receiving section 3 in the direction of fluid flow. The outlet 32 ​​is located on the opposite side of the acid gas adsorption section 1 relative to the adsorption material outflow suppression section 2. During the adsorption process, the outlet 32 ​​allows the treated gas, whose acid gas concentration has been reduced from passing through the acid gas adsorption section 1, to pass through.

[0135] E. Discharge section

[0136] In one embodiment, the acid gas adsorption device 100 further includes a discharge section 7. The discharge section 7 can discharge liquid containing adsorbent material from the receiving section 3. With this configuration, liquid containing adsorbent material retained inside the acid gas adsorption device can be smoothly discharged from the receiving section. Therefore, the impact of liquid containing adsorbent material retention on the adsorption performance of the acid gas adsorption section can be reduced. Furthermore, the liquid containing adsorbent material can be collected and recycled, and thus, the recycled liquid containing adsorbent material can be properly processed. Therefore, even when the liquid containing adsorbent material is discharged from the receiving section, the impact of the acid gas adsorbent on human health and / or the environment can be sufficiently suppressed.

[0137] The discharge section 7 typically discharges liquid containing adsorbent material through an opening provided in the receiving section 3. Although not shown, the opening is located downstream of the acid gas adsorption section 1 in the fluid flow direction. The opening preferably communicates with the gap between the acid gas adsorption section 1 and the adsorbent material outflow suppression section 2. Accordingly, the discharge section can smoothly discharge liquid containing adsorbent material that is retained between the acid gas adsorption section and the adsorbent material outflow suppression section.

[0138] F. Methods for recovering acidic gases

[0139] Next, a method for recovering acidic gas using the acidic gas adsorption apparatus according to one embodiment of the present invention will be described. Typically, the acidic gas recovery method includes an adsorption step and a separation step.

[0140] In the adsorption process, the target gas containing acidic gas is supplied to the acidic gas adsorption unit 1, which is adjusted to a specified adsorption temperature. When the target gas is CO2-containing gas, the CO2 concentration in the CO2-containing gas supplied to the acidic gas adsorption unit is, for example, 100 ppm (volume basis) to 2% by volume.

[0141] In the example shown, the target gas containing acidic gas is supplied to the acidic gas adsorption unit 1 through the inlet 31 of the receiving unit 3. Next, the target gas containing acidic gas passes through the acidic gas adsorption unit 1 (typically, the flow path 44 provided in the acidic gas adsorption unit 1). At this time, the acidic gas adsorption material included in the acidic gas adsorption unit 1 adsorbs the acidic gas from the target gas containing acidic gas (typically CO2). Accordingly, acidic gas is efficiently adsorbed from the target gas supplied to the acidic gas adsorption unit.

[0142] The temperature (adsorption temperature) of the acidic gas adsorption section in the adsorption process is, for example, 0°C to 50°C, preferably 10°C to 40°C. In one embodiment, the adsorption temperature is the same as the ambient temperature. The duration of the adsorption process (adsorption time) is, for example, 15 minutes to 3 hours, preferably 30 minutes to 2 hours.

[0143] If the adsorption temperature and / or adsorption time are within the above range, the acid gas adsorbent material can efficiently adsorb acid gases.

[0144] Afterwards, the treated gas that has passed through the acid gas adsorption section passes sequentially through the adsorption material outflow suppression section 2 (typically the flow path 44 provided by the adsorption material outflow suppression section 2) and the outlet 32 ​​of the receiving section 3, and is discharged from the acid gas adsorption device 100.

[0145] The acid gas adsorption rate in the adsorption process (=100-(acid gas concentration in the treated gas / acid gas concentration in the target gas before being supplied to the acid gas adsorption unit×100)) is, for example, 60% or more, preferably 75% or more, and more preferably 80% or more. On the other hand, the upper limit of the acid gas adsorption rate in the adsorption process is typically 90%.

[0146] In the separation process, typically, the separation gas heated to a separation temperature exceeding the adsorption temperature is supplied to the acid gas adsorption section 1.

[0147] The gas that escapes sometimes contains condensable components. Examples of condensable components include: water vapor; alcohols such as methanol and ethanol; and carboxylic acids such as formic acid and acetic acid.

[0148] The concentration of condensable components in the gas is, for example, 0.1 vol% to 100 vol%, or, for example, 0.0001 vol% to 1 vol%.

[0149] Specifically, examples of gases to be removed include: water vapor, CO2, and acidic gases that have been recovered by an acidic gas adsorption device (hereinafter referred to as recovered gases). These gases can be used alone or in combination.

[0150] The detachment temperature is, for example, 70°C to 200°C, preferably 80°C to 110°C.

[0151] When the detached gas passes through the acid gas adsorption section 1 (typically the flow path 44 provided in the acid gas adsorption section 1), heat energy is transferred to the acid gas adsorption section 1. Therefore, the temperature in the acid gas adsorption section 1 sometimes decreases downstream in the direction of the flow of the fluid (detached gas). Therefore, in the downstream portion of the acid gas adsorption section 1, the aforementioned condensable components may liquefy, and the acid gas adsorbent material dissolves and / or disperses in the condensable components in a liquid state, producing a liquid containing adsorbent material. In contrast, in one embodiment, an adsorbent material outflow suppression section 2 is provided downstream of the acid gas adsorption section 1. Therefore, even if a liquid containing adsorbent material is produced, it is possible to prevent the liquid containing adsorbent material from passing through the adsorbent material outflow suppression section 2 along with the detached gas and being discharged from the acid gas adsorption device 100.

[0152] By supplying the aforementioned detachment gas, the upstream end of the acid gas adsorption section 1 is heated to the detachment temperature and maintained in this state for a predetermined detachment time. Accordingly, the acid gas adsorbed by the acid gas adsorption material during the adsorption process is detached from the acid gas adsorption material. Therefore, the detached acid gas can be recovered along with the detachment gas. It should be noted that in the detachment process, the detachment gas and a pressure reducing pump can be used in combination. For example, a pressure reducing pump can be used to draw and recover the detached acid gas along with the detachment gas.

[0153] The execution time of the separation process (the separation time during which the upstream end of the acid gas adsorption section is maintained at the separation temperature) is, for example, 1 minute to 1 hour, preferably 5 minutes to 30 minutes. If the separation temperature and / or separation time are within the above range, the acid gas can be fully separated from the acid gas adsorption material.

[0154] Through the above operations, the unintentional discharge of liquid containing adsorbent material can be prevented, and acidic gases can be efficiently recovered. The adsorption and desorption processes can be repeated sequentially.

[0155] Example

[0156] The present invention will now be specifically described using examples and comparative examples; however, the present invention is not limited to these examples. The methods for measuring the various properties of the degradation-inhibiting materials used in the examples and comparative examples are as follows.

[0157] <Example 1>

[0158] A preform containing alumina, silicon dioxide, and magnesium oxide (i.e., cordierite) is extruded, dried, and then prepared. Figure 5 The honeycomb substrate shown is prismatic in shape. One side of the honeycomb substrate at its bottom surface has a length of 120 mm. Additionally, the length of the honeycomb substrate is 100 mm. The honeycomb substrate includes partitions defining multiple compartments and an outer peripheral wall surrounding the partitions. The cross-sectional shape of each compartment is quadrilateral. The compartment density of the honeycomb substrate is 62 cells / cm³. 2 The thickness of the partition wall is 0.1 mm, and the porosity of the partition wall is 40%.

[0159] Next, piperazine, which serves as the acid gas adsorbent, is dissolved in a solvent to prepare a piperazine solution. It should be noted that the Hildebrand solubility parameters (SP values) of the acid gas adsorbent are shown in Table 1.

[0160] Next, a porous support was added to the piperazine solution and mixed. Then, at room temperature and pressure (23°C, 0.1 MPaA (absolute pressure)), the piperazine solution containing the porous support was coated onto the partitions of the honeycomb substrate. The piperazine solution coating was then dried to form an acidic gas adsorbent material layer containing piperazine and the porous support. The thickness of the acidic gas adsorbent material layer was 200 μm.

[0161] Thus, the acidic gas adsorption section is obtained.

[0162] In addition, a honeycomb substrate is prepared in the same manner as described above. The honeycomb substrate has the same structure as the honeycomb substrate used for acid gas adsorption, except for its length. The length of the honeycomb substrate is 100 mm.

[0163] Next, polyvinyl fluoride (PVF), which serves as the effluent suppression material, is dissolved in a solvent to prepare a PVF solution. It should be noted that the Hildebrand solubility parameters (SP values) of the effluent suppression material are shown in Table 1.

[0164] Next, at room temperature and pressure (23°C, 0.1 MPaA (absolute pressure)), the PVF solution was coated onto the partitions of the honeycomb substrate. The PVF solution coating was then dried to form a PVF-containing efflux-inhibiting material layer. The thickness of the efflux-inhibiting material layer was 100 μm.

[0165] Thus, the effluent suppression section of the adsorbent material is obtained.

[0166] Additionally, prepare a storage compartment (shell) with a square or cylindrical shape. Next, as follows... Figure 1 As shown, the acid gas adsorption section and the adsorption material outflow suppression section are housed in the housing section (shell).

[0167] The above operations are used to prepare an acidic gas adsorption device.

[0168] <Example 2>

[0169] The acid gas adsorption device was prepared in the same manner as in Example 1, except that piperazine, which was used as the acid gas adsorption material, was replaced with polyethyleneimine (PEI).

[0170] <Example 3>

[0171] The acid gas adsorption device was prepared in the same manner as in Example 2, except that the PVF used as the effluent suppression material was replaced with polyvinylidene fluoride (PVDF).

[0172] <Example 4>

[0173] The acid gas adsorption device was prepared in the same manner as in Example 1, except that piperazine, used as the acid gas adsorption material, was replaced with tetraethylenepentamine (TEPA), and PVF, used as the effluent suppression material, was replaced with polytetrafluoroethylene (PTFE). The thickness of the effluent suppression material layer was less than 1 μm.

[0174] <Comparative Example 1>

[0175] The acid gas adsorption device was prepared in the same manner as in Example 1, except that the PVF used as the effluent suppression material was replaced with vinylidene chloride.

[0176] <Eluting Inhibition Evaluation of Acid Gas Adsorption Materials>

[0177] After the receiving part of the acid gas adsorption device obtained in each embodiment and comparative example is vented in nitrogen at 100°C, water vapor at 120°C is allowed to flow through the gas flow path of the acid gas adsorption device at a flow rate of 2 m / s, thereby raising the temperature of the acid gas adsorption part and the outflow suppression part of the adsorption material to 100°C.

[0178] The exhaust gas from the acid gas adsorption device is recovered when the acid gas adsorption section and the adsorption material effluent suppression section reach 100°C. Then, the concentration of the acid gas adsorption material in the exhaust gas is measured, and the effluent suppression effect of the acid gas adsorption material is evaluated according to the following criteria. The results are shown in Table 1.

[0179] A: The concentration of acidic gas adsorbent material in the exhaust gas is less than 5 ppm.

[0180] B: The concentration of acidic gas adsorbent material in the exhaust gas is above 5 ppm and below 60 ppm.

[0181] C: The concentration of acidic gas adsorbent material in the exhaust gas exceeds 60 ppm.

[0182] Table 1

[0183]

[0184] Table 1 shows that at 25℃, the absolute value (SP value difference) of the difference between the Hildebrand solubility parameter of the acid gas adsorbent and the Hildebrand solubility parameter of the effluent suppression material is 1.0 (cal / cm³). 3 ) 1／2 The above measures can prevent the acidic gas adsorption material from being unintentionally released from the acidic gas adsorption device.

[0185] Industrial availability

[0186] The acid gas adsorption device according to the embodiments of the present invention is used for the separation and recovery of acid gases, and is particularly well used for carbon dioxide recovery, utilization and storage (CCUS) cycles.

[0187] Explanation of reference numerals in the attached figures

[0188] 1. Acidic gas adsorption section

[0189] 2. Adsorbent material outflow suppression section

[0190] 100 Acidic Gas Adsorption Device

Claims

1. An acidic gas adsorption device, comprising: An acidic gas adsorption section, comprising an acidic gas adsorption material capable of adsorbing acidic gases and allowing fluid to pass through; and An adsorbent effluent suppression section is located downstream of the acidic gas adsorption section in the direction of fluid flow, and the adsorbent effluent suppression section comprises effluent suppression material. At 25°C, the absolute value of the difference between the Hildebrand solubility parameter of the acidic gas adsorbent and the Hildebrand solubility parameter of the effluent suppression material is 1.0 (cal / cm³). 3 ) 1／2 above.

2. The acidic gas adsorption device according to claim 1, wherein, The acidic gas is carbon dioxide.

3. The acidic gas adsorption device according to claim 1 or 2, wherein, The effluent suppression material has a water solubility of less than 0.1 g / 100 g H2O at 25°C.

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