Adsorption sheet, corrugating sheet, corrugating sheet laminate, adsorption element, and dehumidifier

Abstract

The purpose of this invention is to provide a novel adsorption sheet, a corrugated sheet, a corrugated laminate, an adsorption element, and a dehumidifier.

Description

Technical Field

[0001] This invention relates to adsorption sheets, corrugated sheets, corrugated laminates, adsorption elements, and dehumidifiers. Background Technology

[0002] Patent Document 1 discloses an adsorption element (honeycomb-shaped) containing 60-85% by weight of zeolite adsorbent material with a pore diameter of 7 Å or more, and an adsorbent containing the following A and B binders, as well as a dehumidification device or waste gas treatment device using the adsorption element. A: At least one polymer selected from polyvinyl alcohol polymers, polyacrylonitrile polymers, polyethylene polymers, and polyester polymers. B: Heat-resistant raw material.

[0003] Patent document 2 discloses an adsorption element and a dehumidification device or waste gas treatment device using the adsorption element. The adsorption element is an element (honeycomb-shaped) containing adsorption material, wherein a modified vinyl acetate adhesive is used, and the content of the adhesive in the element is 1 to 15 wt%.

[0004] Patent document 3 discloses a dehumidifying component and a dehumidifying rotor including the dehumidifying component. The dehumidifying component has a honeycomb structure, wherein the honeycomb structure includes: a flat substrate and a corrugated substrate; an abutting portion where the corrugated substrate's crest abuts against the flat substrate; and a venting portion. The abutting portion includes: an adhesive portion bonded with an adhesive; and silicone formed on the venting portion side relative to the adhesive portion, the composition of which constitutes the adhesive is different from the composition of the silicone formed on the venting portion side relative to the adhesive portion.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Publication No. Japanese Patent Application Publication No. 2004-268020

[0008] Patent Document 2: Publication No. Japanese Patent Application Publication No. 2005-177673

[0009] Patent Document 3: Publication No. Japanese Patent Application Publication No. 2021-181072 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] The purpose of this invention is to provide a new adsorption sheet, a corrugated sheet, a corrugated laminate, an adsorption element, and a dehumidifier.

[0012] Problem-solving methods

[0013] If lithium battery manufacturers do not implement dehumidification, the quality of the lithium batteries will be compromised. Because lithium reacts strongly with moisture, lithium manufacturers need to set a low dew point. Pharmaceutical manufacturers sometimes require low dew points, and such manufacturing processes are carried out in dry rooms.

[0014] To create a dry chamber environment, an adsorption-type dehumidification mechanism using adsorption elements, such as zeolite or silica gel, is employed. This rotor undergoes a high-temperature regeneration process at over 140°C to remove the adsorbed moisture, continuously producing dehumidified air. Therefore, its operation requires a significant amount of energy.

[0015] The need for energy conservation in the context of global warming means that dehumidification performance needs to be improved.

[0016] Previous methods involved directly impregnating a honeycomb structure or sheet with a liquid silica sol to synthesize silica gel (Patent Document 3). In this technology, the silica gel has a high density and low porosity, resulting in poor diffusion of the gas being treated within the adsorption element, and thus the improvement in dehumidification performance cannot be predicted.

[0017] The present invention includes the following: adsorption sheet, corrugated sheet, corrugated laminate, adsorption element, and dehumidifier.

[0018] Project 1.

[0019] An adsorption sheet, wherein,

[0020] As a porous material, it contains silica gel and / or porous metal complexes.

[0021] The pore volume obtained by mercury porosimetry is taken as Ac cc / g.

[0022] When the pore capacity at a relative pressure p / p0 = 0.4, obtained from the N2 adsorption isotherm, is taken as B cc / g,

[0023] The B / A ratio, obtained by dividing B by A, is less than 0.25.

[0024] Project 2.

[0025] An adsorption sheet, wherein,

[0026] As a porous material, it contains silica gel and / or porous metal complexes.

[0027] The pore capacity in the range of pore diameter from 3 nm to 500 μm is defined as Ccc / g.

[0028] When the pore capacity at a relative pressure p / p0 = 0.4, with a pore diameter less than 3 nm, is taken as Dcc / g,

[0029] The D / C ratio obtained by dividing D by C is less than 0.25.

[0030] Project 3.

[0031] The adsorbent sheet according to item 1 or 2 above contains 40% to 85% by mass of the silica gel and / or porous metal complex.

[0032] Project 4.

[0033] A corrugated sheet, wherein the absorbent sheets described in item 1 or 2 are bonded together, and the planar absorbent sheets are bonded together with the corrugated absorbent sheets, thereby forming multiple units of air passages.

[0034] Project 5.

[0035] A corrugated laminate, wherein the corrugated sheets described in item 4 above are stacked together.

[0036] Project 6.

[0037] According to the corrugated laminate described in item 5 above, the number of units per unit area of ​​the air-passing surface is 80 units / cm². 2 Above and 135 / cm 2 the following.

[0038] Project 7.

[0039] (As described in item 5 or 6) a corrugated laminate, wherein it has the following absorbent sheet,

[0040] As a porous material, it contains silica gel and / or porous metal complexes.

[0041] The pore volume obtained by mercury porosimetry is taken as Ac cc / g.

[0042] When the pore capacity at a relative pressure p / p0 = 0.4, obtained from the N2 adsorption isotherm, is taken as B cc / g,

[0043] The B / A ratio, obtained by dividing B by A, is less than 0.25.

[0044] Project 8.

[0045] The ribbed laminate according to any one of items 5 to 7, wherein...

[0046] As a porous material, it contains silica gel and / or porous metal complexes.

[0047] The pore capacity in the range of pore diameter from 3 nm to 500 μm is defined as Ccc / g.

[0048] When the pore capacity at a relative pressure p / p0 = 0.4, with a pore diameter less than 3 nm, is taken as Dcc / g,

[0049] The D / C ratio obtained by dividing D by C is less than 0.25.

[0050] Project 9.

[0051] An adsorption element comprising a corrugated laminate as described in any one of items 5 to 8.

[0052] Project 10.

[0053] A dehumidifier, wherein,

[0054] It features a rotating body, an air intake passage for the adsorption zone, and an air intake passage for the regeneration zone.

[0055] The rotating body is a rotating body that rotates the adsorption element described in item 9 above, with a rotation axis as its center. It is a rotating body that has an adsorption zone and a regeneration zone along the circumferential direction of the rotating body, which is the direction of rotation.

[0056] The air inlet passage of the adsorption zone is a passage that supplies the air to be treated to the adsorption zone, and the adsorption element adsorbs moisture from the air.

[0057] The regeneration zone air intake passage is a regeneration zone air intake passage for supplying regeneration air to the regeneration zone in order to remove moisture from the adsorption element that has adsorbed moisture.

[0058] The adsorption sheet of the present invention adjusts the pore capacity of A (or C): mesopores to macropores (3nm to 500μm) (measured by mercury porosimetry), and the pore capacity of B (or D): micropores (below 3nm) (measured by N2 adsorption method).

[0059] In the adsorption sheet of the present invention, B (or D) is directly related to gas adsorption and affects the adsorption and removal rate, while A (or C) becomes the driving force for entering the micropores.

[0060] The adsorption sheet of the present invention is important in that B << A (or D << C), and gas diffusion within the adsorption sheet can be carried out efficiently when B / A (or D / C) is less than 0.25.

[0061] In the adsorption sheet of the present invention, the range of A (or C) is preferably 1.5 to 3, more preferably 1.5 to 2.8.

[0062] In the adsorption sheet of the present invention, the range of B (or D) is preferably 0.1 to 0.4, more preferably 0.1 to 0.38.

[0063] By applying the adsorption sheet (roughened sheet, roughened laminate and adsorption element) of the present invention to a dehumidifier, the gas diffusion within the adsorption sheet can be improved, thereby enhancing the dehumidification performance.

[0064] The effects of the invention

[0065] This invention provides a novel adsorption sheet, a corrugated sheet, a corrugated laminate, an adsorption element, and a dehumidifier. Attached Figure Description

[0066] Figure 1 This is an illustration of porous metal complexes with open metal sites (coordinatively unsaturated sites).

[0067] Figure 2 This is an illustration of porous metal complexes with OH groups in the metal core unit.

[0068] Figure 3 middle, Figure 3 (A) is a three-dimensional view of the paper-like absorbent sheet. Figure 3 (B) is a three-dimensional view of the corrugated adsorption sheet. Figure 3 (C) is a three-dimensional view of an adsorption sheet with corrugated adsorption sheets stacked on a paper-like adsorption sheet.

[0069] Figure 4 middle, Figure 4 (A) is a perspective view showing the steps of forming the adsorption element. Figure 4 (B) is a three-dimensional view of the adsorption element.

[0070] Figure 5 This is a schematic diagram of the adsorption and removal treatment device. Detailed Implementation

[0071] This invention describes the implementation methods of the adsorption sheet, the corrugated sheet, the corrugated laminate, the adsorption element, and the dehumidifier of the present invention.

[0072] The embodiments described in this invention are provided to better understand the spirit of the invention and are not intended to limit the scope of the invention unless otherwise specified.

[0073] In this specification, "comprise" and "contains" encompass the concepts of "comprise," "consist essentially of," and "consist of." In this specification, when a numerical range is expressed as "A to B," the numerical range means "above A and below B."

[0074] <Adsorption Tablets>

[0075] The adsorption sheet of the present invention,

[0076] As a porous material, it contains silica gel and / or porous metal complexes.

[0077] The pore volume obtained by mercury intrusion porosimetry is taken as Ac cc / g.

[0078] When the pore capacity at a relative pressure p / p0 = 0.4, obtained from the N2 adsorption isotherm, is taken as B cc / g,

[0079] The B / A ratio, obtained by dividing B by A, is less than 0.25.

[0080] The adsorption sheet of the present invention,

[0081] As a porous material, it contains silica gel and / or porous metal complexes.

[0082] The pore capacity in the range of pore diameter from 3 nm to 500 μm is C cc / g.

[0083] When the pore diameter is less than 3 nm and the relative pressure p / p0 = 0.4, the pore capacity is D cc / g.

[0084] The D / C ratio obtained by dividing D by C is less than 0.25.

[0085] The adsorption sheet of the present invention contains 40% to 85% by mass of silica gel and / or porous metal complex.

[0086] The adsorption sheet of the present invention adsorbs a portion of the gases contained in the gas being treated, such as moisture, carbon dioxide, organic solvents, odor components, etc.

[0087] The adsorption sheet of the present invention comprises a porous material, and preferably further comprises a flocculant, fiber, organic binder, etc. The porous material is a raw material used for adsorbing the target substance.

[0088] Adsorbent sheets are sheets containing porous materials such as silica gel and zeolite. Adsorbent sheets are, for example, manufactured using a wet papermaking process that involves mixing porous materials, fibers, and organic binders.

[0089] Fibers are the raw material that forms the skeleton of the absorbent sheet. Organic binders are raw materials used to fix porous materials onto the absorbent sheet, or to improve the strength and flexibility of the absorbent sheet.

[0090] <Porous Materials>

[0091] The adsorption sheet of the present invention can improve the dehumidification performance by increasing the gas diffusivity within the adsorption sheet through the following: (1) adjusting the pore capacity of A (or C): mesopores to macropores (3nm to 500μm) (measured by mercury porosimetry), and B (or D): micropores (below 3nm) (measured by N2 adsorption); (2) B is directly related to gas adsorption and affects the adsorption and removal rate; in addition, A (or C) becomes the driving force for entering the micropores; (3) applying it to a dehumidifier, thereby, as a porous material, it contains silica gel and / or porous metal complexes.

[0092] The porous material contained in the adsorption sheet is not particularly limited, as long as it possesses the adsorption properties of the target substance. It can be appropriately selected from known porous materials depending on the target substance. Preferred examples of porous materials include zeolite, silica gel, and porous materials known as porous coordination polymers (PCP / metalorganic frameworks, MOF).

[0093] (Zeolite)

[0094] Examples of preferred zeolites include natural zeolites, synthetic zeolites (also known as molecular sieves), and artificial zeolites. The zeolite can be selected from these sources depending on the purpose, but synthetic zeolites are preferred for their quality and performance stability.

[0095] (Silicone)

[0096] Examples of preferred silica gel types include type A silica gel and type B silica gel. When the target substance for adsorption is a polar substance such as water or carbon dioxide, from the viewpoint of improving the adsorption performance for the target substance, type A silica gel with a small average pore diameter or type RD silica gel with properties similar to type A silica gel are preferred.

[0097] From the perspective of improving the removal performance of silica gel for adsorbed substances, type B silica gel with a large average pore diameter is preferred. To balance adsorption and removal performance, type A silica gel or type RD silica gel and type B silica gel can be mixed in any proportion according to the target performance.

[0098] (Porous metal complexes, Figure 1 , Figure 2 )

[0099] Porous metal complexes are porous materials that self-assemble by combining metal ions with various coordination modes and organic ligands with two or more coordination sites. Porous metal complexes construct a framework structure by bridging the metal ions, which act as nodes, with the pores within this framework serving as spaces to accommodate the adsorbed substances.

[0100] Compared with inorganic porous materials such as silica gel and zeolite, porous metal complexes have advantages such as higher specific surface area, narrower pore distribution, and higher structural designability, resulting in faster adsorption rates and larger adsorption quantities of target substances.

[0101] Porous metal complexes adsorb and desorb target substances through weak binding forces such as coordination interactions or hydrogen bonds. As a result, the heat of adsorption released during the adsorption of target substances is small, and the adsorbed target substances can be desorbed even at low temperatures of the regeneration gas. Therefore, they have the advantage of low energy required for regeneration.

[0102] By using porous metal complexes in porous materials, adsorption sheets can effectively adsorb the target substances in the treated gas.

[0103] The metal ions constituting porous metal complexes are not particularly limited, but examples include titanium ions, iron ions, cobalt ions, nickel ions, copper ions, zinc ions, aluminum ions, and zirconium ions. For environmental pollution considerations, titanium ions, iron ions, manganese ions, copper ions, zinc ions, aluminum ions, and zirconium ions, which have low toxicity, are preferred as the metal ions constituting porous metal complexes.

[0104] Compounds having organic ligands can be exemplified by the following compounds.

[0105] Dicarboxylic acid, isophthalic acid, 2-aminoterephthalic acid, 2,5-diaminoterephthalic acid, 2,5-dihydroxyterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, fumaric acid, 1H-pyrazole-3,5-dicarboxylic acid, 2,5-furandicarboxylic acid, etc.

[0106] Tricarboxylic acids such as pyromellitic acid.

[0107] Tetracarboxylic acids such as azobenzene-3,3'-5,5'-tetracarboxylic acid.

[0108] Imidazoles such as 2-methylimidazole.

[0109] Specific examples of porous metal complexes:

[0110] A porous metal complex (MOF303) composed of aluminum ions and 1H-pyrazole-3,5-dicarboxylic acid.

[0111] A porous metal complex composed of aluminum ions and 2,5-furandicarboxylic acid (MIL160)

[0112] Porous metal complex (PCN250) composed of iron ions and azobenzene-3,3'-5,5'-tetracarboxylic acid.

[0113] A porous metal complex (MIL100) composed of iron ions and pyromellitic acid.

[0114] Porous metal complexes composed of iron ions and terephthalic acid (MIL53, MIL101).

[0115] Porous metal complex (MOF801) composed of zirconium ions and fumaric acid.

[0116] A porous metal complex (UiO66) composed of zirconium ions and terephthalic acid.

[0117] A porous metal complex (UiO66-NH2) composed of zirconium ions and 2-aminoterephthalic acid.

[0118] A porous metal complex composed of titanium ions and terephthalic acid (MIL125)

[0119] A porous metal complex (MIL125-NH2) composed of titanium ions and 2-aminoterephthalic acid.

[0120] A porous metal complex (MOF74-Ni) composed of nickel and 2,5-dihydroterephthalic acid dicarboxylic acid.

[0121] A porous metal complex (MOF74-Mg) consisting of magnesium and 2,5-dihydroterephthalic acid.

[0122] A porous metal complex composed of chromium and terephthalic acid (MIL101)

[0123] These porous metal complexes, even the same porous metal complexes, have varying BET specific surface areas depending on the synthesis method and purity.

[0124] Porous metal complexes, when the target adsorbate is a polar substance such as water or carbon dioxide, are preferably characterized by adsorption sites to improve adsorption performance. Adsorption sites, for example, include open metal sites (coordinatively unsaturated sites). Open metal sites exhibit high adsorption activity. Therefore, porous metal complexes with open metal sites exhibit very rapid adsorption of the target substance in the treated gas, demonstrating high adsorption performance.

[0125] As one way to open metal sites, for example, the coordination unsaturation of metal ions can be listed, in which the coordination state has at least one vacancy, that is, a coordination unsaturation site.

[0126] Porous metal complexes with coordination unsaturated sites, such as Figure 1 As shown, metal ions ( Figure 1 In metal complexes containing Fe ions, the ligands are unsaturated, and the metal ions have more than one empty coordination site (vacancy). The target substance is adsorbed at this vacancy. Porous metal complexes with coordination-unsaturated sites exhibit high adsorption performance.

[0127] Specific examples of porous metal complexes with coordination unsaturated sites include PCN250, MOF74-Ni, MOF74-Mg, and MIL101. Among these, PCN250 is preferred in terms of using metals with fast adsorption and removal rates, high water resistance, and low toxicity.

[0128] Besides porous metal complexes with open metal sites, porous metal complexes with adsorption sites that exhibit high adsorption performance can also be exemplified by porous metal complexes with OH groups (hydroxyl groups) near the metal.

[0129] Porous metal complexes with OH groups near the metal, such as Figure 2 As shown, the metal core unit contains OH groups. If a porous metal complex has OH groups in its metal core unit, it exhibits excellent adsorption activity for the target substance. Therefore, porous metal complexes with OH groups near the metal exhibit very rapid adsorption and desorption rates of the target substance in the treated gas, demonstrating high adsorption performance.

[0130] A metallic core unit is a cluster of metals constituting a porous metal complex, represented by MxOyHz (where x and y are integers other than 0, and z is an integer including 0). A portion of the oxygen atoms in the metallic core unit MxOyHz are carboxyl oxygen atoms of organic ligands; the metallic core unit forms its framework by sharing oxygen atoms with the organic ligands.

[0131] Specific examples of porous metal complexes with OH groups near the metal include MOF801 and MOF303.

[0132] Porous materials can take various forms, such as powder, granules, and fibers. Adsorbent sheets contain a large amount of powdered or granular porous material.

[0133] (Physical properties of porous materials)

[0134] The size of the porous material is not particularly limited, but it is preferably 0.1 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more. On the other hand, the size of the porous material is not particularly limited, but it is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 100 μm or less, and even more preferably 80 μm or less.

[0135] If the size of the porous material is greater than or equal to 0.1 μm and less than 200 μm, it can ensure good contact between the gas being treated and the porous material, thereby improving the adsorption performance of the porous material. Furthermore, if the size of the porous material is greater than or equal to 0.1 μm and less than 200 μm, it can not only reduce the pressure loss when the gas being treated contacts the porous material, but also allow for high-density loading of the porous material on the adsorption sheet. On the other hand, it can also reduce the shedding of the porous material from the adsorption sheet.

[0136] The size of porous materials is measured by the D50 value obtained from a laser diffraction particle size distribution measuring device or the average particle size obtained from a scanning electron microscope.

[0137] The pore structure of porous materials is not particularly limited. When the porous material is a porous metal complex, the pore structure of the porous metal complex can be one-dimensional or three-dimensional. From the perspective of rapid adsorption of the target substance and easy adsorption, the pores of the porous metal complex are preferably one-dimensional pores. Specific examples of porous metal complexes with one-dimensional pores include PCN250, MOF303, and MOF74.

[0138] Porous metal complexes possess three-dimensional pores and lack open metal sites. To facilitate the adsorption of target substances into the micropores, small crystallite size is preferred for porous metal complexes. MOF801 is a specific example of a porous metal complex with three-dimensional pores but no open metal sites.

[0139] The pore diameter of porous materials is not particularly limited. When the porous material is a porous metal complex, and the target adsorbate is a small-sized polar substance such as water or carbon dioxide, from the viewpoint of improving the adsorption performance for the target substance, the pore diameter of the porous metal complex is preferably 3.0 Å or more, more preferably 3.5 Å or more. On the other hand, the pore diameter of the porous metal complex is preferably 10 Å or less, more preferably 8 Å or less.

[0140] If the pore diameter of the porous metal complex is 3.0 Å or more and 10 Å or less, the target substance can be well adsorbed into the micropores, thus improving the adsorption performance of the porous metal complex. Furthermore, if the pore diameter of the porous metal complex is 3.0 Å or more and 10 Å or less, the adsorbed target substance can also be easily detached from the porous metal complex during regeneration.

[0141] In order to accelerate the removal rate of porous metal complexes and thus preferentially improve the adsorption performance of porous metal complexes, it is preferable that the pore diameter of the porous metal complexes is greater than 10 Å.

[0142] The pore diameter of porous metal complexes can be obtained by measuring the cage diameter or window diameter of the micropores based on X-ray structural analysis.

[0143] When the porous material is silica gel, the pore diameter of the silica gel is not particularly limited. However, from the viewpoint of improving adsorption performance for polar substances such as water and carbon dioxide, the average pore diameter of the silica gel is preferably 30 Å or less. On the other hand, from the viewpoint of improving removal performance for adsorbed substances, the average pore diameter of the silica gel is preferably 70 Å or less. To balance adsorption and removal performance, various types of silica gel with an average pore diameter in the range of 10 Å or more and 70 Å or less can be mixed in any proportion according to the target performance.

[0144] When the porous material is zeolite, since the pore diameter of zeolite is basically determined by its crystal structure, the crystal structure of the zeolite can be selected according to the purpose, or two or more zeolites can be used in combination.

[0145] The specific surface area (BET specific surface area) of porous materials, measured by the BET method, is not particularly limited. However, when the porous material is a porous metal complex, the specific surface area (BET specific surface area) of the porous metal complex, measured by the BET method, is preferably 200 m². 2 / g or more, preferably 300m 2 / g or more, preferably 500m 2 / g or more, preferably 900m 2 / g or more, more preferably 1,000m 2 / g or more, more preferably 1,500m 2 / g or more, preferably 1,800m 2 / g or more.

[0146] The preferred BET specific surface area of ​​the porous metal complex is 6,000 m². 2 / g or less, more preferably 2,500m 2 / g or less, more preferably 2,000m 2 / g or less.

[0147] If the specific surface area of ​​the porous metal complex is 200 m² 2 / g or more and 6,000m 2 If the specific surface area is below a certain value (e.g., g), the target substance can be well adsorbed in the micropores, thus improving the adsorption performance of porous metal complexes. If the specific surface area of ​​the porous metal complex is 200 m² / g... 2 / g or more and 6,000m 2 In addition to being less than / g, it can also easily produce porous metal complexes. If the specific surface area of ​​the porous metal complex is 2,500 m²... 2 Below / g, the strength of porous metal complexes can be fully ensured.

[0148] When the porous material is silica gel, the preferred specific surface area of ​​silica gel, measured by the BET method, is 200 m². 2 / g or more, preferably 300m 2 / g or more, preferably 400m 2 / g or more.

[0149] When the porous material is zeolite, the preferred specific surface area of ​​the zeolite, measured by the BET method, is 200 m². 2 / g or more and 900m 2 / g or less.

[0150] The bulk density of the porous material is not particularly limited, but it is preferably 0.2 g / cc or higher, more preferably 0.23 g / cc or higher. If the bulk density of the porous material is 0.2 g / cc or higher, the gaps between multiple porous materials can be reduced, allowing for high-density loading of porous material on the adsorption sheet. Therefore, if the bulk density of the porous material is 0.2 g / cc or higher, the adsorption sheet can effectively adsorb the target substance from the gas being treated.

[0151] The bulk density of a porous material is measured by filling the porous material into a container of known volume until it is level, and then dividing the weight of the porous material at the time of filling by the volume.

[0152] When the porous material is a porous metal complex, the water adsorption rate of the porous metal complex at 25°C and a relative pressure of 0.5 is not particularly limited, but is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more.

[0153] The pressure at which adsorption appears to stop (number of adsorbed molecules = number of desorbed molecules) under a certain pressure is called the adsorption equilibrium pressure. The relative pressure is the ratio of the adsorption equilibrium pressure to the saturated vapor pressure.

[0154] The adsorption sheet contains a porous metal complex with a water adsorption rate of over 30% by mass at 25°C and a relative pressure of 0.5. This allows for the retention of a large amount of adsorbed substances on the sheet, while also imparting high flexibility during processing. Furthermore, by fully imparting flexibility to the adsorption sheet through the porous metal complex, the content of organic binders, previously used to achieve this flexibility, can be reduced. As a result, the proportion of micropores clogged by adsorbed organic binder side chains and other contaminants can be reduced, thereby improving the adsorption performance of the porous material.

[0155] The water adsorption rate of porous metal complexes at 25°C and a relative pressure of 0.5 was determined by collecting approximately 100 mg of porous metal complexes (before treatment with water or organic solvent), drying them under vacuum at 120°C for 12 hours, weighing them, and then using a high-precision gas and vapor adsorption capacity measuring device (BELSORP-max, manufactured by BEL Corporation, Japan). While gradually increasing the relative pressure in the range of 0.02 to 0.95, the water vapor adsorption capacity was measured at 40 points at 25°C, and adsorption isotherms were plotted.

[0156] At this point, the target relative pressure is set to 0.001, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, and 0.9. The allowable increase or decrease in adsorption capacity is then set to 30 cm³ under a relative pressure of 0–0.3. 2 / g, with a relative pressure of 0.3–0.5, set at 50cm 2 / g, relative pressure 0.5~ set at 30cm 2 / g, and plot the adsorption isotherm. Then, based on the amount of water adsorbed per 1g of porous metal complex at a relative pressure of 0.5 [g], calculate the water adsorption rate [%] using the following formula a.

[0157] Water adsorption rate = Water adsorption capacity per 1g porous metal complex [g] × 100 (Equation a)

[0158] The content of porous material in the adsorption sheet is not particularly limited, but it is preferably 40% by mass or more, more preferably 50% by mass or more. On the other hand, the content of porous material is not particularly limited, but it is preferably 85% by mass or less, more preferably 83% by mass or less. If the content of porous material is 40% by mass or more and 85% by mass or less, porous material can be supported on the adsorption sheet at a high content, and therefore, the adsorption sheet can effectively adsorb the target substance in the gas being treated. If the content of porous material is 40% by mass or more and 85% by mass or less, the shedding of porous material from the adsorption sheet can be reduced, and the strength of the adsorption sheet can be sufficiently ensured.

[0159] Porous materials may include one or more of the aforementioned silica gel, zeolite, and porous metal complexes. Alternatively, porous materials may also include porous materials other than silica gel, zeolite, and porous metal complexes, such as organic polymer porous bodies of activated carbon, activated alumina, aluminophosphate, aluminum silicate phosphate, and styrene-divinylbenzene copolymers.

[0160] (Content of porous materials)

[0161] The adsorption sheet of the present invention can improve the gas diffusivity within the adsorption sheet by the following: (1) adjusting the pore capacity of A: mesopores to macropores (3nm to 500μm) (measured by mercury porosimetry) and B: micropores (below 3nm) (measured by N2 adsorption method); (2) B is directly related to gas adsorption and affects the adsorption and removal rate, while A becomes the driving force for entering the micropores; (3) applying it to a dehumidifier, thereby containing 40% to 85% by mass of silica gel and / or porous metal complex, more preferably 45% to 83% by mass, further preferably 50% to 83% by mass, and particularly preferably 55% to 83% by mass.

[0162] <Fiber>

[0163] The fibers constituting the absorbent sheet are not particularly limited; for example, natural fibers, synthetic fibers, regenerated fibers, semi-synthetic fibers, inorganic fibers, etc., can be used.

[0164] Specific examples of natural fibers include cotton, linen, and pulp.

[0165] Specific examples of synthetic fibers include aramid fibers, meta-aramid fibers, polybenzimidazole fibers, polybenzoxazole fibers, polyimide fibers, polyamide-imide fibers, polyetherketone fibers, polyethylene terephthalate fibers, and nylon fibers.

[0166] Specific examples of regenerated fibers include rayon, polynosic fiber, and cupro fiber. Specific examples of semi-synthetic fibers include cellulose acetate and triacetate fiber.

[0167] Specific examples of inorganic fibers include glass fiber, ceramic fiber, and rock wool fiber.

[0168] The fibers constituting the absorbent sheet may be a combination of two or more of the aforementioned fibers.

[0169] The fibers constituting the absorbent sheet preferably contain both unfibrillated and fibrillated fibers.

[0170] Because the absorbent sheet contains unfibrillated fibers, it can maintain its corrugated shape when subjected to processes such as corrugation.

[0171] If the adsorption sheet contains fibrillated fibers, it can more efficiently support porous materials. The presence of fibrillated fibers also reduces the amount of organic binders needed to fix the porous material onto the sheet, thus preventing the organic binders from clogging the micropores of the porous material and improving its adsorption performance.

[0172] There is no particular limitation on the fiber diameter of the unfibrillated fiber, but it is preferred to be 5 μm or more and 30 μm or less.

[0173] The fiber length of the unfibrillated fiber is not particularly limited, but is preferably 1 mm or more, more preferably 2 mm or more. The fiber length of the unfibrillated fiber is not particularly limited, but is preferably 10 mm or less, more preferably 8 mm or less.

[0174] If the diameter of the unfibrillated fibers is 5 μm or more and the length is 1 mm or more, the strength of the absorbent sheet can be sufficiently ensured, and the absorbent sheet can maintain its corrugated shape when subjected to processes such as corrugation. If the diameter of the unfibrillated fibers is less than 30 μm and the length is less than 10 mm, the absorbent sheet has moderate softness and is easy to process, for example, with corrugation. Unfibrillated fibers can also be mixed with fibers of different diameters and lengths.

[0175] fibrillated fibers are, for example, fibers in which the aforementioned unfibrillated fibers have been fibrillated. The method of fibrillation is not particularly limited; conventionally known methods may be used, such as beating methods using beaters like beaters or pulping machines.

[0176] There are no particular limitations on fibrillated fibers, but when measuring Canadian standard filtration fraction (CSF) according to JIS P 8121-2, the preferred value is 50 mL or more and less than 800 mL.

[0177] The total content of unfibrillated and fibrillated fibers in the absorbent sheet is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more. On the other hand, the total content of unfibrillated and fibrillated fibers in the absorbent sheet is not particularly limited, but is preferably 45% by mass or less.

[0178] If the total content of unfibrillated and fibrillated fibers in the adsorbent sheet is 5% by mass or more and 45% by mass or less, the adsorbent sheet can support a sufficient amount of porous material, reducing the shedding of porous metal complexes from the adsorbent sheet. If the total content of unfibrillated and fibrillated fibers in the adsorbent sheet is 5% by mass or more and 45% by mass or less, the strength of the adsorbent sheet can be sufficiently ensured.

[0179] <Organic Adhesives>

[0180] The organic binder contained in the adsorption sheet is not particularly limited as long as it can fix the porous material onto the adsorption sheet. Examples of organic binders include polyvinyl alcohol (PVA) based polymers, polyacrylonitrile based polymers, polyethylene based polymers, polyester based polymers, and polyphenylene ether based polymers. From an operational point of view, polyvinyl alcohol (PVA) based polymers are preferred examples of organic binders.

[0181] The form of the organic adhesive is not particularly limited, but if a fibrous organic adhesive is used, the absorbent sheet is easy to manufacture and is therefore preferred.

[0182] The content of organic binder in the adsorbent sheet is not particularly limited, but it is preferably 3% by mass or more, more preferably 4% by mass or more. On the other hand, the content of organic binder in the adsorbent sheet is not particularly limited, but it is preferably 20% by mass or less, more preferably 18% by mass or less.

[0183] If the content of organic binder in the adsorption sheet is 3% to 20% by mass, the loading capacity and flexibility of the porous material of the adsorption sheet can be fully ensured. If the content of organic binder in the adsorption sheet is 3% to 20% by mass, the proportion of micropores blocked by adsorbed organic binder side chains can be reduced, thereby improving the adsorption performance of the porous material.

[0184] Organic binders enhance the flexibility of the adsorption sheet. Even in small amounts, as long as the adsorption sheet contains fibrillated fibers, it can exhibit good loading capacity of a porous material. The high water adsorption rate of the porous material contributes to the sheet's flexibility. Therefore, reducing the amount of organic binder in the adsorption sheet is possible. Furthermore, reducing the amount of organic binder inhibits the clogging of micropores in the porous material, thereby improving its adsorption performance.

[0185] The water solubility temperature of organic adhesives is not particularly limited, but it is preferably 65°C or higher, more preferably 70°C or higher. On the other hand, the water solubility temperature of organic adhesives is not particularly limited, but it is preferably 100°C or lower.

[0186] If the water solubility temperature of the organic adhesive is above 65℃ and below 100℃, the proportion of micropore blockage caused by the side chains of the organic adhesive adsorbed in the micropores of the porous material can be reduced, thereby improving the adsorption performance of the porous material. Furthermore, if the water solubility temperature of the organic adhesive is above 65℃ and below 100℃, the adhesive force of the organic adhesive can also be well utilized, allowing the porous material to be effectively supported on the adsorption sheet.

[0187] The water solubility temperature of organic adhesives can be measured using conventionally known methods. One such method involves placing 100 mL of pure water in a beaker, stirring, and heating it in an oil bath until the water temperature reaches 50°C. Then, 0.5 g of the organic adhesive is added to the heated water, and the water temperature is increased at a rate of 2°C / min. The temperature at which the organic adhesive begins to dissolve visually and reaches a semi-transparent state is measured.

[0188] <Catonic Surfactants>

[0189] In addition to the porous materials, fibers, and organic binders mentioned above, the absorbent sheet also contains cationic surfactants as water-repellent agents to provide water repellency. These water-repellent agents give the absorbent sheet its water-repellent properties.

[0190] If the adsorption sheet is water-repellent, when using it to manufacture adsorption elements, such as honeycomb structures, even if a silica-based inorganic binder is attached to the adsorption sheet, it can prevent the silica-based inorganic binder from penetrating the adsorption sheet before hardening. Because the binder is difficult to penetrate the adsorption sheet before hardening, the adsorption sheets can be well bonded to each other, and the adsorption element can be easily manufactured. If the adsorption sheet is water-repellent, it can prevent the binder from penetrating the adsorption sheet and clogging the micropores of the porous material, thus preventing a decrease in the adsorption performance of the porous material in the adsorption element.

[0191] Cationic surfactants are not particularly limited and may include amine salt type, quaternary ammonium salt type, etc. Examples of amine salt type include aliphatic amide amines. Examples of quaternary ammonium salt type include monoalkyl type, monoalkyl ether type, dialkyl type, dialkyl ester type, benzalkonium chloride type, etc.

[0192] Cationic surfactants preferably have a long-chain alkyl chain and an amide site in their primary structure. The long-chain alkyl chain and the amide site may exist in a single compound or as different compounds. Santol KL-2, manufactured by Nichika Chemical Co., Ltd., is a preferred example of a cationic surfactant having a long-chain alkyl chain and an amide site.

[0193] <Catonic surfactants with long-chain alkyl chains and amide sites>

[0194] Cationic surfactants having long-chain alkyl chains and amide sites contain partial structures of the following chemical formulas in their surfactant structures (R... 1 =C,R 2 R 3 =C or H), R 1 It contains alkyl chains with 5 or more carbon atoms and fewer than 30 carbon atoms. Alternatively, R 1 alkyl chain and CO-NR in chemical formula 2 R 3 The amide site can exist in a single compound or as different compounds.

[0195] [Chemical Formula 1]

[0196]

[0197] The adsorbent sheet contains a cationic surfactant with long-chain alkyl chains and amide sites. The long-chain alkyl chains contribute to the adsorbent sheet's excellent water repellency. The amide sites in the cationic surfactant enhance its dispersibility in solvents such as water and its adsorption properties onto fibers during the manufacturing process, thus enabling the cationic surfactant to be uniformly loaded onto the adsorbent sheet.

[0198] Cationic surfactants with long-chain alkyl chains and amide sites are added as water-repellent agents to porous materials, fibers, and organic adhesives used as raw materials in the manufacture of absorbent sheets via wet papermaking.

[0199] Whether the adsorption sheet or the adsorption element made using the adsorption sheet contains a cationic surfactant with a long-chain alkyl chain and an amide site can be confirmed by pyrolysis gas chromatography-mass spectrometry (pyrolysis GC-MS). Specifically, for a 0.1 g sample taken from the adsorption sheet or adsorption element, 1 mL of chloroform is added, and ultrasonic extraction is performed at room temperature for 30 minutes. Then, 0.5 g of the extract obtained by ultrasonic extraction is placed in a sample cup for pyrolysis GC-MS, and after removing the chloroform from the extract, pyrolysis GC-MS is performed.

[0200] The conditions for thermal decomposition GC-MS are as follows. Gas chromatography-mass spectrometry (GC-MS) analysis of the gaseous components generated by the thermal decomposition reaction of the sample confirms that the adsorbent sheet or adsorbent element contains cationic surfactants with long-chain alkyl chains and amide sites by detecting fragment ion peaks with m / z=59 and 72, which are characteristic of compounds with amide sites containing long-chain alkyl chains.

[0201] [Conditions for thermal pyrolysis GC-MS]

[0202] • Device: PY-2020iD (Frontier LAB) / QP-2010Plus (Shimadzu Corporation)

[0203] • Sample heating conditions: 550℃ × 0.5 min

[0204] • Column: Ultra ALLOY-5 (MS / HT) (30m length, 0.25mm inner diameter, 0.25μm film thickness)

[0205] • Column temperature: 50℃ (2 min) - 20℃ / min - 320℃ (10 min)

[0206] • Inlet pressure: 80 kPa

[0207] • Inlet temperature: 320℃

[0208] • Diversion ratio: 30

[0209] • Ion source: EI method

[0210] • Ion source temperature: 250℃

[0211] • Ionization voltage: 70 eV

[0212] • Interface temperature: 320℃

[0213] • MS measurement mode: SIM and / or SCAN

[0214] • Ion measurement: m / z 29-550 in SCAN mode, m / z 59-72 in SIM mode

[0215] <Manufacturing Method of Adsorption Tablets>

[0216] There are no particular limitations on the method of manufacturing the absorbent sheet, but wet papermaking is a preferred example.

[0217] (Wet papermaking process)

[0218] The adsorption sheet of the present invention adjusts the porosity during the manufacturing process and maintains the continuous dispersion of fibers and adsorption material, while preferably containing an appropriate amount of flocculant (wet papermaking method).

[0219] (1) Preparation of dispersion slurry

[0220] When manufacturing absorbent sheets using the wet papermaking process, porous materials, fibers, and organic binders are first dispersed in a solvent such as water or an organic solvent and mixed according to a specified ratio.

[0221] <Flocculant>

[0222] In the manufacture of adsorbent sheets, in addition to porous materials, fibers and organic binders, as well as water-repellent agents, polymeric flocculants can also be added as additives.

[0223] Polymer flocculants are agents used in the manufacture of adsorbent sheets to coagulate and precipitate porous materials, fibers, and organic binders dispersed in a solvent.

[0224] Polymer flocculants can be any known flocculants. Preferred polymer flocculants include cationic, amphoteric, and anionic / nonionic polymer flocculants. Cationic polymer flocculants are more preferred. Organic polymer flocculants, for example, include Tetsufloc (registered trademark) manufactured by Nippon Steel Mining Co., Ltd.

[0225] The suspension is thoroughly stirred while maintaining the dispersion of porous materials, fibers, organic binders, etc., and flocculant is added dropwise to all materials at a rate of approximately 10 ml / g. Adsorption sheets are then produced using a wet papermaking method.

[0226] (2) Sheet forming process

[0227] Secondly, the obtained dispersed slurry is formed using a papermaking machine to obtain sheet-like material.

[0228] In the sheet forming process, it is preferable to mix the porous material with other materials while the solvent molecules have penetrated into the micropores of the porous material.

[0229] When there are no solvent molecules within the micropores of a porous material, the organic binder constituting the adsorption sheet may be trapped within those micropores. In this case, it is difficult to remove the trapped organic binder from the micropores of the porous material after sheeting, and the adsorption performance of the adsorption sheet may decrease.

[0230] By capturing solvent molecules within the micropores of porous materials, the adsorption sheet can prevent organic binders from penetrating into the micropores and being captured during the sheeting process. After the sheeting process, solvent molecules are removed from the micropores through a solvent removal treatment, thus ensuring the adsorption performance of the adsorption sheet.

[0231] When manufacturing an adsorption sheet, if solvent molecules remain in the micropores of the porous material during the manufacturing process, the porous material cannot fully exert its adsorption performance.

[0232] The solvent removal treatment is performed on the adsorption sheet to fully utilize the adsorption performance of the porous material.

[0233] The conditions for solvent removal are not particularly limited. For example, the temperature for solvent removal is not particularly limited, but it is preferably 50°C or higher, more preferably 80°C or higher. The temperature for solvent removal is not particularly limited, but it is preferably 300°C or lower, more preferably 200°C or lower.

[0234] If the temperature for solvent removal is above 50℃ and below 300℃, the microporous structure of the porous material is less likely to be damaged, and the solvent can be efficiently removed from the micropores of the porous material.

[0235] The solvent removal treatment is preferably carried out under reduced pressure. This allows for more effective removal of the solvent from the micropores of the porous material. The pressure of the solvent removal treatment is not particularly limited and can be adjusted appropriately according to the properties of the porous material and the amount of solvent added, but is preferably 10. 3 Pa or less, more preferably 10 Pa -1 The pressure for solvent removal is below 10 Pa. There is no particular limitation on the pressure, but 10 is preferred. -5 Pa or above.

[0236] The solvent removal treatment time is not particularly limited, but preferably 20 seconds or more, more preferably 30 seconds or more. The solvent removal treatment time is not particularly limited, but preferably 5 minutes or less, more preferably 3 minutes or less, and even more preferably 1 minute or less.

[0237] The optimal conditions for solvent removal treatment are: under vacuum conditions, a temperature above 80°C and below 200°C, and a treatment time of above 20 seconds and below 5 minutes.

[0238] (3) Dehydration and drying process

[0239] Then, the obtained flakes are dehydrated and dried to obtain adsorption flakes.

[0240] The methods for dehydration and drying are not particularly limited, and conventionally known methods can be used. Examples of dehydration methods include: passing the sheet material between a pair of rollers to apply pressure for dehydration, or pulling the absorbent sheet onto a mesh and allowing the water to drip off due to its own weight. Examples of drying methods include air drying in the sun, or blowing hot air onto the dehydrated sheet material.

[0241] < Shape and physical properties of the adsorption sheet> Figure 3 (A) >

[0242] Adsorption tablets, such as Figure 3 As shown in (A), it can also be used in the form of a backing paper (flat), but it can also be used in the desired shape by performing pleating, honeycomb (corrugated) processing or corrugation processing.

[0243] The flexibility of the adsorption sheet is not particularly limited, but it is preferred to use the specific tensile elongation as an indicator of flexibility, which is 5%·m / g or higher. If the specific tensile elongation of the adsorption sheet is 5%·m / g or higher, the adsorption sheet has good processability. When using the adsorption sheet to manufacture adsorption elements with structures such as honeycomb structures, even if the adsorption sheet is corrugated, cracks in the adsorption sheet can be suppressed.

[0244] The specific tensile elongation of the adsorption sheet was determined by drying a 15mm × 100mm sample piece from the adsorption sheet at 120°C for 1 hour and measuring its weight. The dried sample piece was then left to stand at 25°C in a 75% RH atmosphere for 1 hour, and the maximum point elongation [%] was measured using a tensile-compression testing machine (TENSILON RTG-1310, manufactured by A&D). The clamp spacing was 50mm, and the tensile speed was 15mm / min. Based on the obtained data, the specific tensile elongation [%·m / g] was calculated using the following formula (equation b).

[0245] Specific tensile elongation = maximum point elongation [%] / sample width [m] / weight of adsorption sheet [g / m] 2 (Formula b)

[0246] The thickness of the adsorption sheet is not particularly limited, but is preferably 0.1 mm or more. The thickness of the adsorption sheet is preferably 0.9 mm or less, more preferably 0.7 mm or less. If the thickness of the adsorption sheet is 0.1 mm or more and 0.9 mm or less, the strength of the adsorption sheet can be sufficiently guaranteed when manufacturing the adsorption element by processing the adsorption sheet, and the increase in pressure loss of the adsorption element manufactured by processing the adsorption sheet can be suppressed.

[0247] The weight of the adsorption tablets is not particularly limited, but is preferably 25 g / m³. 2 The above, more preferably 40g / m 2 The above. The preferred weight of the adsorption sheet is 200 g / m³. 2 The preferred value is 150g / m³. 2 the following.

[0248] If the weight of the adsorption tablet is 25 g / m³ 2 Above and 200g / m 2 The following ensures the thickness of the adsorption sheet, suppressing any decrease in strength, thus facilitating the fabrication of adsorption elements. If the basis weight of the adsorption sheet is 25 g / m³... 2 Above and 200g / m2 The following measures can prevent the thickness of the adsorption sheet from becoming too large, thereby suppressing the increase in pressure loss of the adsorption element manufactured by processing the adsorption sheet.

[0249] <Pore volume determined by mercury intrusion porosimetry: A (or C)

[0250] The pore capacity at a relative pressure p / p0 = 0.4, obtained from the N2 adsorption isotherm, is: B (or D) >

[0251] (Measurement of pore capacity obtained by mercury intrusion porosimetry)

[0252] The sample was cut into pieces approximately 10 mm × 20 mm and then vacuum dried at 150 °C for 24 hours. Porosity was measured using an AutoPoreIV 9520 micrometer manufactured by Micromeritics. The micropore size range was approximately 3 nm to 500 μm.

[0253] The pore capacity of the adsorption sheet (A: mesopores to macropores (3nm to 500μm)) was measured by mercury porosimetry.

[0254] (The pore capacity B at a relative pressure p / p0 = 0.4, obtained from the N2 adsorption isotherm)

[0255] Collect 50mg of sample, dry it under vacuum at 150℃ overnight, and then weigh it.

[0256] Using a high-precision gas / vapor adsorption measurement device (BELSORP-maxII, MicrotracBEL), one side is at 3.0 × 10 -8 The relative pressure was gradually increased within a range of ~0.99, while the amount of nitrogen adsorbed at the boiling point of liquid nitrogen (-195.8℃) at 80 points was measured, and the adsorption isotherm was plotted.

[0257] Using the analysis software (BELMaster Version 7.3.2.0) provided with the device, the BET method was employed, and the relative pressure was set to p / p0 = 0.4, which is equivalent to approximately 3 nm, to determine the pore volume [cm]. 3 / g].

[0258] Based on the N2 adsorption isotherm, the pore capacity of the micropores (below 3 nm) of the adsorption sheet was measured.

[0259] The invented adsorption sheet can improve the dehumidification performance by increasing the gas diffusivity within the adsorption sheet through the following means: (1) adjusting the pore capacity of A: mesopores to macropores (3nm to 500μm) (measured by mercury porosimetry) and B: micropores (below 3nm) (measured by N2 adsorption); (2) B is directly related to gas adsorption and affects the adsorption and removal rate, and also constitutes the driving force for entering the micropores; (3) applying it to a dehumidifier, thereby improving the dehumidification performance.

[0260] The pore volume obtained by mercury porosimetry is taken as Ac cc / g.

[0261] When the pore capacity at a relative pressure p / p0 = 0.4, obtained from the N2 adsorption isotherm, is taken as B cc / g,

[0262] The B / A value obtained by dividing B by A is preferably 0.25 or less, more preferably 0.23 or less, even more preferably 0.2 or less, and particularly preferably 0.18 or less.

[0263] The adsorption sheet of the present invention can improve the dehumidification performance by increasing the gas diffusivity within the adsorption sheet through the following means: (1) adjusting the pore capacity of A: mesopores to macropores (3nm to 500μm) (measured by mercury porosimetry) and B: micropores (below 3nm) (measured by N2 adsorption); (2) B is directly related to gas adsorption and affects the adsorption and removal rate; in addition, A constitutes the driving force for entering the micropores; (3) applying it to a dehumidifier, thereby improving the dehumidification performance.

[0264] The pore capacity in the range of pore diameter from 3 nm to 500 μm is defined as Ccc / g.

[0265] When the pore capacity at a relative pressure p / p0 = 0.4, where the pore diameter is less than 3 nm, is taken as Dcc / g,

[0266] The D / C value obtained by dividing D by C is preferably 0.25 or less, more preferably 0.23 or less, even more preferably 0.2 or less, and particularly preferably 0.18 or less.

[0267] The adsorption sheet of the present invention is important in that B << A (or D << C), and gas diffusion within the adsorption sheet can be carried out efficiently when B / A (or D / C) is less than 0.25.

[0268] In the adsorption sheet of the present invention, the range of A (or C) is preferably 1.5 to 3, more preferably 1.5 to 2.8.

[0269] In the adsorption sheet of the present invention, the range of B (or D) is preferably 0.1 to 0.4, more preferably 0.1 to 0.38.

[0270] <Rack-stamped sheet, Figure 3 (B), (C) >

[0271] The corrugated processing sheet of the present invention has multiple units, which are adsorbent sheets of the present invention bonded together, so that the planar adsorbent sheet and the corrugated adsorbent sheet are bonded together, thereby forming an air passage.

[0272] The corrugated sheet of the present invention has multiple units, which are adsorbent sheets of the present invention bonded together, so that the planar adsorbent sheet and the corrugated adsorbent sheet (processed into a corrugated adsorbent sheet) are bonded together, thereby forming an air passage.

[0273] When processing adsorbent sheets into pleated, honeycomb, or corrugated shapes, to make them easily bendable, the porous material can be fully adsorbed to impart flexibility. Alternatively, adsorbent sheets can be processed in a semi-dry state while still completely dry, and then completely dried after processing.

[0274] Figure 3 (B) shows an example of a processed adsorbent sheet, which is processed into a corrugated adsorbent sheet 1B (corrugated adsorbent sheet).

[0275] Figure 3 As shown in (C), make Figure 3 (B) shows corrugated adsorption sheets 1B stacked on Figure 3 (A) shows a corrugated sheet (C) obtained on a paper-like absorbent sheet 1A. The corrugated sheet (C) is manufactured by bonding multiple bottoms 10 of a corrugated absorbent sheet (corrugated absorbent sheet) 1B to the surface 11 of the paper-like absorbent sheet 1A with an adhesive 12.

[0276] There are no particular limitations on the adhesive 12, but from the viewpoint of heat resistance, a silica-based inorganic adhesive is preferred. Specific examples of silica-based inorganic adhesives include water glass, silica sol, and alumina sol.

[0277] Adhesive 12 may also be an organic adhesive mixed with an inorganic adhesive. Specific examples of organic adhesives include, for instance, one or more organic adhesives selected from phenolic resins, epoxy resins, acrylic resins, polyurethane resins, polyester resins, melamine resins, silicone resins, fluoropolymers, and copolymers thereof.

[0278] <Rack-stitched laminated body> Figure 4 >

[0279] The corrugated laminate of the present invention is formed by stacking corrugated sheets of the present invention.

[0280] In the corrugated laminate of the present invention, the number of units per unit area of ​​the air-passing surface is 80 units / cm. 2 Above and 135 / cm 2 the following.

[0281] The corrugated laminate of the present invention can improve the gas diffusivity within the adsorption sheet by the following: (1) adjusting the pore capacity of A: mesopores to macropores (3nm to 500μm) (measured by mercury porosimetry) and B: micropores (below 3nm) (measured by N2 adsorption); (2) B is directly related to gas adsorption and affects the adsorption and removal rate; in addition, A constitutes the driving force for entering the micropores; (3) applying it to a dehumidifier, thereby preferably having 80 units / cm² per unit area. 2 Above and 135 / cm 2 The following is more preferably 85 per cm. 2 More than 120 per cm 2 The following is a further preferred value: 90 pieces / cm 2 Above and 115 per cm 2 the following.

[0282] The present invention relates to a corrugated laminated body.

[0283] As a porous material, it contains silica gel and / or porous metal complexes.

[0284] The pore volume obtained by mercury intrusion porosimetry is taken as Ac cc / g.

[0285] When the pore capacity with a relative pressure p / p0 = 0.4, obtained from the N2 adsorption isotherm, is taken as Bcc / g,

[0286] The B / A ratio, obtained by dividing B by A, is less than 0.25.

[0287] The present invention relates to a corrugated laminated body.

[0288] As a porous material, it contains silica gel and / or porous metal complexes.

[0289] The pore capacity in the range of pore diameter from 3 nm to 500 μm is defined as Ccc / g.

[0290] When the pore capacity with a relative pressure p / p0 = 0.4 in the range of pore diameters less than 3 nm is taken as Dcc / g,

[0291] The D / C ratio obtained by dividing D by C is less than 0.25.

[0292] The micropore capacity A obtained by mercury porosimetry, the micropore capacity B obtained by the N2 adsorption isotherm at a relative pressure p / p0 = 0.4, the micropore capacity C in the range of micropore diameters from 3 nm to 500 μm, and the micropore capacity D in the range of micropore diameters below 3 nm at a relative pressure p / p0 = 0.4 are as described above.

[0293] The corrugated laminate of the present invention is formed by stacking corrugated sheets of the present invention.

[0294] Figure 4 An example of a laminated body with a ribbed finish is shown in the figure. Figure 4 (B) shows a ribbed laminate, such as Figure 4 As shown in (A), it is... Figure 3 The corrugated sheet (C) shown in (C) is wound into a rotor shape, presenting a honeycomb structure.

[0295] <Adsorption element>

[0296] The adsorption element of the present invention is composed of the corrugated laminate of the present invention.

[0297] Adsorption elements are manufactured by shaping one or more adsorption sheets into a prescribed shape or structure. For example, an adsorption element is manufactured by laminating corrugated adsorption sheets with an adhesive onto a paper-like adsorption sheet (corrugated sheet) and then winding it into a rotor shape, thereby creating a honeycomb-structured corrugated laminate.

[0298] The adsorption element is composed of a corrugated laminate. In a dehumidifier (adsorption and removal treatment device), the adsorption element is positioned in the flow path of the gas being treated. The dehumidifier brings the gas being treated into contact with the adsorption element, thereby adsorbing the target substances contained in the gas onto the porous material within the adsorption element.

[0299] Adsorption elements are manufactured by using one or more corrugated laminates to form a structure corresponding to the intended use and purpose. The type of adsorption element is not particularly limited; any conventionally known type may be used.

[0300] By using adsorption sheets processed into a pleated shape, a direct-flow adsorption element can be manufactured. By using adsorption sheets processed into a honeycomb shape, a parallel-flow adsorption element can be manufactured.

[0301] Direct-flow and parallel-flow adsorption elements have high adsorption performance for the target substances due to their large contact area with the gas being treated, and can also achieve low pressure loss of the adsorption element.

[0302] Compared with direct-flow adsorption elements, parallel-flow adsorption elements are superior in preventing clogging caused by droplets and dust, reducing pressure loss, and reducing weight, and are therefore more suitable for adsorption and removal treatment devices.

[0303] Dehumidifier Figure 5 >

[0304] The dehumidifier of the present invention comprises a rotating body, an air inlet passage for the adsorption zone, and an air inlet passage for the regeneration zone.

[0305] The rotating body is a rotating body that rotates the adsorption element of the present invention with a rotating axis as the center. It is a rotating body that has an adsorption zone and a regeneration zone along the rotation direction of the rotating body, that is, circumferentially.

[0306] The air intake passage of the adsorption zone is a passage that supplies air to the adsorption zone to be treated, and the adsorption element adsorbs moisture from the air.

[0307] The regeneration zone air intake passage is a regeneration zone air intake passage that supplies regeneration air to the regeneration zone to remove moisture from the adsorption element that has adsorbed moisture.

[0308] A dehumidifier (adsorption removal treatment device) is a device constructed in the following manner: it has an adsorption element, and by bringing the gas to be treated into contact with the adsorption element, the adsorbent substance contained in the gas to be treated is adsorbed onto a porous material. By bringing the regenerated gas into contact with the adsorption element on which the adsorbent substance is adsorbed, the adsorbent substance is removed from the porous material.

[0309] The dehumidifier of the present invention comprises a rotating body, an air inlet passage for the adsorption zone, and an air inlet passage for the regeneration zone.

[0310] The rotating body of a dehumidifier is a rotating body with a rotating shaft as the center, which makes the adsorption element rotate. It is a rotating body with an adsorption zone and a regeneration zone along the circumferential direction of the rotation.

[0311] The dehumidifier's air intake passage supplies the air to be treated to the adsorption zone, where the adsorption elements adsorb moisture from the air.

[0312] The air intake passage of the regeneration zone of the dehumidifier supplies regeneration air to the regeneration zone in order to remove moisture from the adsorption elements that have adsorbed moisture.

[0313] Dehumidifier, for example Figure 5 The continuous adsorption and removal processing device 3 shown is a rotor-type device. The continuous adsorption and removal processing device 3 includes a cylindrical adsorption element 4, which can be driven by a motor to rotate around a rotation axis L. The adsorption element 4 has, for example... Figure 4 (B) shows a honeycomb structure for forming a corrugated laminate 2. The adsorption element 4 is divided into an adsorption zone 40 and a removal zone 41 along the circumference around the rotation axis L. The corrugated laminate 2 moves alternately between the adsorption zone 40 and the removal zone 41 by the rotation of the adsorption element 4.

[0314] The gas to be treated is supplied to the adsorption zone 40 of the adsorption element 4 by the drive of the blower 5. As it passes through the corrugated laminate 2 located in the adsorption zone 40, the adsorbent substances contained in the gas are adsorbed by the porous material contained in the corrugated laminate 2. The regeneration gas, heated by a heat source 6 such as a heater, is supplied to the removal zone 41 of the adsorption element 4 by the drive of the blower 7. As it passes through the corrugated laminate 2 located in the removal zone 41, the adsorbent substances are removed from the porous material. Thus, the porous material is regenerated.

[0315] Rotary dehumidifiers are not limited to the examples mentioned above; conventionally known dehumidifiers can also be used. Dehumidifiers are not limited to rotary dehumidifiers.

[0316] Adsorption sheets, corrugated sheets, corrugated laminates, adsorption elements, and dehumidifiers can be used for various purposes such as air dehumidification, air deodorization, air purification, and gas separation. They can be used to reduce odor components in indoor spaces, vehicles, wallpaper, furniture, interior materials, resin moldings, electrical equipment, etc.

[0317] Adsorption sheets, corrugated sheets, corrugated laminates, adsorption elements, and dehumidifiers can be used to separate and recover organic solvents emitted into the air from factories and other sources. These products can be used for air humidity control or dehumidification, and can be applied not only in residences, buildings, apartments, hospitals, factories, and commercial facilities, but also in the spaces inside various vehicles such as cars, trams, and airplanes.

[0318] The adsorption sheet of the present invention adjusts the pore capacity of A: mesopores to macropores (3nm to 500μm) (measured by mercury porosimetry) and B: micropores (below 3nm) (measured by N2 adsorption method).

[0319] In the adsorption sheet of the present invention, B is directly related to gas adsorption and affects the adsorption and removal rate. In addition, A constitutes the driving force for entering the micropores.

[0320] The adsorption sheet of the present invention is important in that B << A (or D << C), and with B / A (or D / C) being less than 0.25, gas diffusion within the adsorption sheet can be carried out with high efficiency.

[0321] In the adsorption sheet of the present invention, the range of A (or C) is preferably 1.5 to 3, more preferably 1.5 to 2.8.

[0322] In the adsorption sheet of the invention, the range of B (or D) is preferably 0.1 to 0.4, more preferably 0.1 to 0.38.

[0323] By applying the adsorption sheet (corrugated sheet, corrugated laminate and adsorption element) of the present invention to a dehumidifier, the dehumidification performance can be improved by increasing the gas diffusion within the adsorption sheet.

[0324] One embodiment of the adsorption sheet, corrugated sheet, corrugated laminate, adsorption element, and dehumidifier of the present invention has been described. The adsorption sheet, corrugated sheet, corrugated laminate, adsorption element, and dehumidifier of the present invention are not limited to the above embodiment, and various modifications can be made without departing from the spirit of the present invention.

[0325] Example

[0326] Examples of the adsorption sheet of the present invention are shown, and the function and effect of the adsorption sheet of the present invention are specifically explained. The adsorption sheet of the present invention is not limited to the examples.

[0327] (Example 1)

[0328] Sodium silicate with a SiO2 / Na2O molar ratio of 2.9 was added dropwise to 18% by weight sulfuric acid to generate hydrated silica gel. After washing the generated hydrated silica gel with a large amount of water, it was immersed in sulfuric acid adjusted to pH=4 at 30°C for about 2 hours. After filtration, it was dried at 150°C to obtain silica gel.

[0329] The above-prepared silica gel (excluding solvent molecules), aramid fibers (16% by mass as unfibrillated fibers), aramid fibers (10% by mass as fibrillated fibers), and polyvinyl alcohol (PVA) fibers (dissolving in water at 70°C, catalog value) as organic binders are mixed in the above ratio and stirred thoroughly.

[0330] The suspension was thoroughly stirred, and while maintaining dispersion, Tetsufloc (manufactured by Nippon Steel Mining Co., Ltd.) was added dropwise at a rate of 10 ml / g as a flocculant to achieve a weight of 75 g / m³. 2 The quality of the absorbent sheets was improved by using a wet papermaking process.

[0331] The adsorbent sheet was then subjected to solvent removal treatment at 130℃ to obtain the adsorbent sheet. The porosity of the obtained adsorbent sheet was measured by mercury intrusion porosimetry.

[0332] Further confirmation revealed that it is possible to bond the prepared flat sheet material and corrugated sheet material to the honeycomb structure using vinyl acetate adhesive to a degree that the bonded portion will not peel off, forming a honeycomb structure (corrugated sheet). Then, using the same vinyl acetate adhesive, to a degree that the bonded portion will not peel off, the corrugated sheet is wound onto the core material (corrugated laminate) to process it into a rotor-shaped cylindrical element (adsorption element) with a thickness of 200 mm and an outer diameter of 300 mm.

[0333] The adhesive content in the rotor-shaped cylindrical adsorption honeycomb element (adsorption element) is 8.2 wt%.

[0334] The dehumidification performance of the rotor-shaped cylindrical adsorption honeycomb element (adsorption element) was evaluated.

[0335] (Example 2)

[0336] 80% by mass of silicone (with solvent molecules removed) prepared by the same treatment as in Example 1, 8% by mass of aramid fiber as unfibrillated fiber, 5% by mass of aramid fiber as fibrillated fiber, and 7% by mass of PVA fiber as organic binder as in Example 1 were mixed in the above ratio and stirred thoroughly.

[0337] For other operations, the same operations as in Example 1 were performed, and the adsorption sheets were made by wet papermaking. For the adsorption sheets, the porosity was measured by mercury intrusion porosimetry.

[0338] In addition, similar to Example 1, the prepared adsorption sheet was used to make a rotor-shaped cylindrical adsorption honeycomb element (adsorption element), and the dehumidification performance was evaluated.

[0339] (Example 3)

[0340] PCN250 was synthesized by dissolving 50g of Fe(NO3)3·9H2O and 10g of azobenzene-3,3'-5,5'-tetracarboxylic acid in 2L of N,N-dimethylformamide and 1L of acetic acid, and heating at 150℃ for 24 hours.

[0341] The above-prepared PCN250 sample (60% by mass, excluding solvent molecules), aramid fiber (16% by mass as unfibrillated fiber), aramid fiber (10% by mass as fibrillated fiber), and PVA fiber (14% by mass as organic binder) from Example 1 were mixed in the above ratio and stirred thoroughly.

[0342] While thoroughly stirring the suspension and maintaining its dispersion, add Tetsufloc (manufactured by Nippon Steel Mining Co., Ltd.) as a flocculant dropwise at a rate of 10 ml / g to all materials to achieve a weight of 65 g / m³. 2 The quality of the absorbent sheets was improved by using a wet papermaking process.

[0343] In addition, the adsorbent sheets were subjected to a solvent removal treatment at 130°C to obtain the adsorbent sheets. The porosity of the obtained adsorbent sheets was measured by mercury intrusion porosimetry.

[0344] In addition, similar to Example 1, the prepared adsorption sheet was used to make a rotor-shaped cylindrical adsorption honeycomb element (adsorption element), and the dehumidification performance was evaluated.

[0345] (Example 4)

[0346] 80% by mass of PCN250 sample (after removing solvent molecules) prepared by the same treatment as in Example 3, 8% by mass of aramid fiber as unfibrillated fiber, 5% by mass of aramid fiber as fibrillated fiber, and 7% by mass of PVA fiber as organic binder from Example 1 were mixed in the above ratio and stirred thoroughly.

[0347] For other operations, the same procedures as in Example 3 were performed, and the adsorption sheets were made by wet papermaking. For the adsorption sheets, the porosity was measured by mercury intrusion porosimetry.

[0348] In addition, similar to Example 1, the prepared adsorption sheet was used to make a rotor-shaped cylindrical adsorption honeycomb element (adsorption element), and the dehumidification performance was evaluated.

[0349] (Compare Examples 1 and 2)

[0350] As a substrate, use 30g / m 2 Glass nonwoven fabric. The glass nonwoven fabric is impregnated with a sodium silicate aqueous solution with a SiO2 / Na2O molar ratio of 2.9, and then semi-dried using a dryer until it is ready for honeycomb (corrugated) processing.

[0351] In Comparative Example 1, an air-passing surface was prepared with a unit number of 95 cells / cm². 2 In Comparative Example 1, the number of units prepared in the waveform sheet was 95 per cm². 2 At that time, because the cell was severely clogged, a clean waveform could not be obtained, so a cellular element could not be obtained.

[0352] In Comparative Example 2, an air-passing surface was prepared with a unit number of 30 units / cm². 2 Waveform.

[0353] In Comparative Example 2, it was confirmed that subsequently, the planar sheet material of the adsorption sheet and the corrugated sheet material are bonded together with an emulsion containing amorphous silica and water to the degree that the bonded portion of the honeycomb does not peel off, thus forming a honeycomb structure. Then, using the same emulsion, the corrugated sheet is wound onto the core material to process it into a rotor-shaped cylindrical element with a thickness of 200 mm and an outer diameter of 300 mm.

[0354] Cylindrical elements were immersed in 18% by weight sulfuric acid to generate honeycomb elements loaded with hydrated silica gel. After washing the generated hydrated silica gel with a large amount of water, it was immersed in sulfuric acid adjusted to pH=4 at 30°C for about 2 hours. After drying at 150°C, the honeycomb elements loaded with silica gel were obtained.

[0355] The dehumidification performance was evaluated using a rotor-shaped cylindrical adsorption honeycomb element.

[0356] (Dehumidification performance evaluation)

[0357] (1) Fix the adsorption element in the adsorption and desorption chamber with an adsorption zone:regeneration zone ratio of 3:1.

[0358] (2) A gas to be treated with a temperature of 25°C and a humidity of 5.4 g / kg-DA is supplied to the adsorption zone at a passing wind speed of 2 m / s.

[0359] (3) Removal zone, temperature 140℃, humidity 5.4g / kg-DA

[0360] The removal rate is calculated using the following calculations.

[0361] Removal rate % = (Inlet humidity of adsorption zone 5.4 g / kg - DA - Outlet humidity of adsorption zone g / kg - DA) / (Inlet humidity of adsorption zone 5.4 g / kg - DA) * 100

[0362] (Metal porosimetry)

[0363] The sample was cut into pieces approximately 10 mm × 20 mm and then vacuum dried at 150 °C for 24 hours. Porosity was measured using an AutoPoreIV 9520 micrometer manufactured by Micromeritics. The micropore size range was approximately 3 nm to 500 μm.

[0364] The pore capacity of the adsorption sheet (A: mesopores to macropores (3nm to 500μm)) was measured by mercury porosimetry.

[0365] (N2 adsorption isotherm)

[0366] Collect 50mg of sample, dry it under vacuum at 150℃ overnight, and then weigh it.

[0367] Using a high-precision gas / vapor adsorption measurement device (BELSORP-maxII, MicrotracBEL), one side is at 3.0 × 10 -8 The relative pressure was gradually increased in the range of ~0.99, while the amount of nitrogen adsorbed at the boiling point of liquid nitrogen (-195.8℃) at 80 points was measured, and the adsorption isotherm was plotted.

[0368] Using the analysis software (BELMaster Version 7.3.2.0) provided with the device, the BET method was employed, and the relative pressure was set to p / p0 = 0.4, which is equivalent to approximately 3 nm, to determine the pore volume [cm]. 3 / g].

[0369] Based on the N2 adsorption isotherm, the pore capacity of the micropores (below 3 nm) of the adsorption sheet was measured.

[0370] Table 1

[0371]

[0372] The change in porosity can be inferred from the amount of fibrillated fibers. For example, when the absorbent content is 80% by weight, the other fibers are 20% by weight. In the example, the amount of fibrillated fibers is 5% by weight.

[0373] In areas where the amount of fibrillated fibers is less than 1% by weight, the amount of dehumidifier will inevitably be less, and the dehumidification performance will tend to decline.

[0374] In areas where fibrillated fibers account for up to 20% by weight, the paper loses strength, thus its corrugating processability tends to decline.

[0375] Industrial availability

[0376] The adsorption sheet of the present invention adjusts the pore capacity of A (or C): mesopores to macropores (3nm to 500μm) (measured by mercury porosimetry), and the pore capacity of B (or D): micropores (below 3nm) (measured by N2 adsorption method).

[0377] In the adsorption sheet of the present invention, B (or D) is directly related to gas adsorption and affects the adsorption and removal rate, while A (or C) constitutes the driving force for entering the micropores.

[0378] The key feature of the adsorption sheet of the present invention is that B << A (or D << C). With B / A (or D / C) being less than 0.25, gas diffusion within the adsorption sheet can be carried out with high efficiency.

[0379] In the adsorption sheet of the present invention, the range of A (or C) is preferably 1.5 to 3, more preferably 1.5 to 2.8.

[0380] In the adsorption sheet of the present invention, the range of B (or D) is preferably 0.1 to 0.4, more preferably 0.1 to 0.38.

[0381] By applying the adsorption sheet (roughened sheet, roughened laminate and adsorption element) of the present invention to a dehumidifier, the gas diffusion within the adsorption sheet can be improved, thereby enhancing the dehumidification performance.

Claims

1. An adsorption sheet, wherein As a porous material, it contains silica gel and / or porous metal complexes. The pore volume obtained by mercury intrusion porosimetry is taken as Ac cc / g. Based on the N2 adsorption isotherm, when the pore capacity is B cc / g at a relative pressure p / p0 = 0.4, The B / A ratio, obtained by dividing B by A, is less than 0.

25.

2. An adsorption sheet, wherein As a porous material, it contains silica gel and / or porous metal complexes. The pore capacity in the range of pore diameter from 3 nm to 500 μm is defined as Ccc / g. When the pore capacity at a relative pressure p / p0 = 0.4, where the pore diameter is less than 3 nm, is taken as Dcc / g, The D / C ratio obtained by dividing D by C is less than 0.

25.

3. The adsorption sheet according to claim 1 or 2, wherein, Containing 40% to 85% by mass of the aforementioned silica gel and / or porous metal complex.

4. A corrugated sheet having a plurality of units, wherein the plurality of units are formed by bonding the absorbent sheets of claim 1 or 2 together, and wherein the planar absorbent sheets are bonded together with the corrugated absorbent sheets to form an air passage.

5. A corrugated laminate, wherein the corrugated sheets of claim 4 are stacked together.

6. The corrugated laminate according to claim 5, wherein, The number of units per unit area of ​​the air-permeable surface is 80 / cm². 2 Above and 135 / cm 2 the following.

7. A corrugated laminate comprising an absorbent sheet, wherein the absorbent sheet is, As a porous material, it contains silica gel and / or porous metal complexes. The pore volume obtained by mercury intrusion porosimetry is taken as Ac cc / g. Based on the N2 adsorption isotherm, when the pore capacity is B cc / g at a relative pressure p / p0 = 0.4, The B / A ratio, obtained by dividing B by A, is less than 0.

25.

8. A laminated body with a raised texture, wherein, As a porous material, it contains silica gel and / or porous metal complexes. The pore capacity in the range of pore diameter from 3 nm to 500 μm is defined as Ccc / g. When the pore capacity at a relative pressure p / p0 = 0.4, where the pore diameter is less than 3 nm, is taken as Dcc / g, The D / C ratio obtained by dividing D by C is less than 0.

25.

9. An adsorption element formed from a corrugated laminate as described in claim 5, 7 or 8.

10. A dehumidifier comprising a rotating body, an air inlet passage for an adsorption zone, and an air inlet passage for a regeneration zone. The rotating body is a rotating body centered on a rotation axis, which rotates the adsorption element according to claim 9. It is a rotating body having an adsorption zone and a regeneration zone along its rotation direction, i.e., circumferentially. The air inlet passage of the adsorption zone is a passage that supplies the air to be treated to the adsorption zone, and the adsorption element adsorbs moisture from the air. The regeneration zone air intake passage is a regeneration zone air intake passage for supplying regeneration air to the regeneration zone in order to remove moisture from the adsorption element that has adsorbed moisture.

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