WO2013115033A1 - Adsorption sheet and adsorption element used for same - Google Patents

Abstract

The purpose of the present invention is to provide an adsorption sheet, and an adsorption element using the same, that can provide sufficient adsorption and desorption performance originating in a porous metal complex even in a case where the structure of the porous metal complex changes as a result of adsorption and desorption of gases, and that is heat resistant, has excellent porous metal complex supporting properties and sheet flexibility in addition to sufficient adsorption performance. This adsorption sheet includes a porous metal complex (A) that comprises a porous structure resulting from the bonding of metal ions and organic ligands that can bond with the metal ions, and organic fibers (B), or includes the porous metal complex (A) and heat resistant fibers (D).

Description

Adsorption sheet and adsorption element using the same

The present invention relates to an adsorbent sheet that can be used as an adsorbent, an occlusion material, and a separation material. It is related with the form provision at the time of using. The present invention also relates to an adsorption sheet for efficiently separating / collecting or adsorbing / removing moisture, organic solvents, and malodorous components in the air, and an adsorption element using the same.

Porous materials such as activated carbon, silica gel, and zeolite are used for deodorization, air and water purification, and gas separation and purification. In recent years, a porous material obtained by self-assembly by combining a metal ion capable of various coordination forms and a bridging ligand having two or more coordination sites, that is, a porous metal complex (MOF) ) Or a new porous material called a porous coordination polymer (PCP) has been found, and these porous metal complexes have characteristics not found in conventional porous materials such as activated carbon, silica gel, zeolite, That is, it has features such as a high specific surface area, a sharp pore distribution, and a high structural design, and has attracted attention.

For example, as a porous metal complex that seems to be useful for separating a specific gas from a mixed gas, Patent Document 1 discloses a gate-type polymer complex that exhibits gas adsorption as a gate and a gas that is I-type. Porous metal complexes have been reported in which the properties of both type I complexes vary with the switching material. Patent Documents 2 and 3 report a porous metal complex that selectively adsorbs only a specific gas with a change in pore structure and size. Furthermore, in Patent Document 3 and Non-Patent Document 1, a flexible porous metal complex whose structure is changed depending on the type of gas in contact with it and a gas separation method using the same are also reported.

However, these documents do not specifically describe the form of the porous metal complex when used in an actual separation process.

Further, Patent Document 4 discloses a specific dicarboxylic acid metal complex as a porous metal complex, and discloses that this is suitable as a gas storage material, particularly a gas storage material mainly composed of methane. Yes. Patent Document 5 discloses a porous complex synthesized from copper ions and trimesic acids, and an adsorbent is disclosed as an example of its use. Furthermore, Patent Document 6 discloses that a porous coordination polymer obtained from metal chromium or a chromium salt and trimesic acid is particularly excellent as a water vapor adsorbent, and has a high porous coordination polymer. It is disclosed that in order to use molecules as adsorbents for various substances, it is preferable to remove the solvent by heating under reduced pressure.
However, Patent Documents 4 to 6 do not specifically describe an adsorbing sheet composed of these porous metal complexes and a manufacturing method for an adsorbing element using the adsorbing sheet.

On the other hand, as an adsorbing sheet used for a filter for the purpose of separation and recovery of an organic solvent in the air, a sheet made by mixing and making a porous material such as powdered activated carbon or zeolite and a fiber component is conventionally known. For example, Patent Document 7 discloses a corrugated sheet containing powdered activated carbon and a self-consolidating fibrous clay mineral and heat-resistant artificial fibers as main components as a sheet made by mixing powdered activated carbon. A processable adsorbent sheet is disclosed. However, since powdered activated carbon is used as an adsorbent, there is a problem that the adsorption performance is not sufficient.

Further, as a sheet made by mixing and making zeolite, for example, Patent Document 8 discloses an adsorption sheet containing zeolite and moisture minerals, clay mineral fibers having self-consolidating properties, glass fibers, and an organic binder. Yes. Since this adsorbing sheet contains clay mineral fibers and glass fibers, it has excellent heat resistance, and since it contains an organic binder, it exhibits excellent adsorbent supportability and sheet flexibility. .

JP 2010-58034 A JP 2009-208028 A JP 2010-158617 A JP 2001-348361 A JP 2000-327628 A JP 2007-51112 A Japanese Patent Laid-Open No. 2-191547 Japanese Patent Laid-Open No. 2007-14880

When using a porous material in an actual process, for example, when using zeolite or molecular sieve charcoal as an adsorbent for pressure swing adsorption, the adsorbent is compressed into a pellet using a tablet molding machine or the like. Is common. However, when a porous metal complex having a flexible structure that changes its structure with gas adsorption like the porous metal complex described above is pelletized by general tableting molding, If it is molded to have sufficient strength, there is a problem that the adsorption performance decreases. On the other hand, if the molding conditions are adjusted to such an extent that the adsorption performance is not lowered, the crushing strength will be insufficient, or the molded body will not follow the structural changes accompanying adsorption and desorption, and the molded body will collapse and become powdered. There is a problem that it ends up.

In addition, when adsorbents such as zeolite and organic binders are mixed to form an adsorbent sheet, the side chains of the organic binder are adsorbed in the pores of the adsorbent zeolite, resulting in sufficient adsorption performance. The same problem is expected when a porous metal complex is used as an adsorbent.
The organic binder adsorbed in the pores of the adsorbent (zeolite) can be removed by calcination at a temperature of 400 ° C. to 800 ° C. for 30 minutes or more. However, even if the organic binder is removed, the adsorbent is zeolite. Therefore, the adsorption performance is not sufficient. In addition, when a porous metal complex is used as an adsorbent instead of zeolite, firing under the above conditions destroys the pore structure of the porous metal complex, resulting in insufficient adsorption performance. It was.

Therefore, it is excellent in heat resistance, adsorbent (porous metal complex) supportability, and sheet flexibility, and there is no adsorbing sheet with sufficient adsorbing performance, and no adsorbing element using it. Is the current situation. The term “heat resistance” as used herein means that the strength is not significantly reduced in the adsorption sheet and the adsorption element using the same under a temperature condition of 80 ° C. or higher.

The present invention has been made by paying attention to such circumstances, and its purpose is to absorb absorption derived from the porous metal complex even when the structure of the porous metal complex changes due to gas adsorption / desorption. It is an object of the present invention to provide an adsorption sheet that can sufficiently exhibit the desorption performance.

Another object of the present invention is an adsorbent sheet that is excellent in heat resistance, porous metal complex support, and sheet flexibility and has sufficient adsorbing performance, and adsorbing using the same To provide an element.

The adsorbing sheet of the present invention includes a porous metal complex (A) and an organic fiber (B) that form a porous structure with metal ions and organic ligands that can bind to the metal ions. Has characteristics.

As a result of intensive studies, the inventors of the present invention have made a porous metal by gas adsorption / desorption by forming a sheet-like molded body in which a porous metal complex (A) is supported on an organic fiber (B). Discovered that a molded article containing a porous metal complex (A) capable of following the structural change of the complex and sufficiently exhibiting the excellent adsorption / desorption performance possessed by the porous metal complex (A) can be obtained, and the present invention has been completed. did.

The adsorbing sheet of the present invention preferably contains 50% to 90% by mass of the porous metal complex (A).

The porous metal complex (A) has hysteresis in the adsorption / desorption isotherm for at least one gas selected from the group consisting of hydrogen, oxygen, nitrogen, carbon monoxide, carbon dioxide and hydrocarbons having 1 to 4 carbon atoms. It preferably represents a loop.

The organic ligand is preferably at least one organic compound selected from the group consisting of the following (1) to (3).
(1) Organic compound having two or more carboxyl groups and / or hydroxyl groups in the molecule, having no heterocyclic ring, and capable of bidentate coordination with metal ions (2) In the molecule, N, O or S A monocyclic or polycyclic saturated or unsaturated heterocyclic ring having one heteroatom selected from the following: an organic compound having a carboxyl group or a hydroxyl group and capable of bidentate coordination to a metal ion (3) Intramolecular And a bidentate organic compound having a monocyclic or polycyclic saturated or unsaturated heterocycle having 2 or more heteroatoms selected from the group consisting of N, O and S

More specifically, the organic ligand includes an alkylene dicarboxylic acid compound having 4 to 20 carbon atoms, an alkenylene dicarboxylic acid compound having 4 to 20 carbon atoms, and a dicarboxylic acid represented by the following general formulas (I) to (III). Acid compounds;

(Wherein R ^{1 s} are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a formyl group, carbon An acyloxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, a nitro group, a cyano group, a carboxyl group, an amino group, a monoalkylamino group having 1 to 4 carbon atoms, and a dialkylamino group having 1 to 4 carbon atoms Or an acylamino group having 1 to 4 carbon atoms, and two or more R ¹ groups may be cyclic, or two or more R ¹ groups may be condensed cyclically.) In the following general formula (IV) Dicarboxylic acid compounds represented;

(Wherein R ^{2 s} are the same or different and each represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent, and X represents a hydrogen atom or a substituent. Or an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, or an amino group. An organic compound represented by the following general formula (V);

(Wherein R ³ are the same or different and each represents a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms) Or an alkoxy group having 1 to 4 carbon atoms), organic compounds represented by the following general formulas (VI) to (VIII);

(Wherein R ³ are the same or different and each represents a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms) Or an alkoxy group having 1 to 4 carbon atoms), and organic compounds represented by the following general formulas (IX) to (XII);

Wherein Y is the same or different and represents an oxygen atom, a sulfur atom, —CH ₂ —, —CH (OH) —, —CO—, —NH—, —C ₂ N ₄ —, —C≡C—, —C ₂ H ₂ — or —C ₆ H ₄ —, wherein R ^{4 s} are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, carbon An alkoxy group having 1 to 4 carbon atoms, a formyl group, an acyloxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having an alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyano group, a carboxyl group, an amino group, 1 to carbon atoms 4 monoalkylamino groups, dialkylamino groups having 1 to 4 carbon atoms or acylamino groups having 1 to 4 carbon atoms, and n is an integer of 0 to 3). Desirably one or more organic compounds.

The organic fiber (B) is preferably cellulose. The adsorbing sheet of the present invention is preferably produced by a wet papermaking method.

The present invention also includes an adsorption sheet characterized by containing a porous metal complex (A) and a heat-resistant fiber (D).
The adsorbing sheet preferably contains clay mineral fibers having self-consolidating properties. Moreover, it is preferable that the said adsorption sheet contains an organic binder. The adsorption element using the adsorption sheet of the present invention is a preferred embodiment of the present invention.

According to the adsorption sheet of the present invention, it can be reproduced without impairing the adsorption performance of the porous metal complex (A). Moreover, the adsorption | suction sheet | seat of this invention can reproduce | regenerate adsorption | suction performance easily by putting it in a pressure-reduced environment.
Furthermore, when the adsorbing sheet of the present invention and the adsorbing element using the same contain the porous metal complex (A) and the heat-resistant fiber (A), and if necessary, self-consolidating In the case of containing a clay mineral fiber having an organic binder and an organic binder, it has the advantages of excellent heat resistance, porous metal complex support, sheet flexibility, and adsorption performance.
Therefore, the adsorbing sheet of the present invention can be used for applications of adsorbents, occlusion materials, and separating materials depending on the purpose.

In addition, the organic solvent as used in this specification refers to the organic compound which has the property to melt | dissolve a substance, specifically, aromatic hydrocarbons, such as toluene, xylene, and styrene; Chlorinated aromatics, such as chlorobenzene Hydrocarbons; chlorinated aliphatic hydrocarbons such as dichloromethane and chloroethylene; alcohols such as methanol, ethanol and isopropanol; esters such as ethyl acetate; ethers such as 1,4-dioxane; ketones such as methyl ethyl ketone; Glycol ethers such as methyl cellosolve; alicyclic hydrocarbons such as cyclohexanone; aliphatic hydrocarbons such as normal hexane; trimethylsilanol, hexamethyldisilazane, cyclic siloxane (octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane Silicon-containing compounds such as Other, cresol, carbon disulfide, N, N- dimethylformamide, N- methylpyrrolidone and the like; and the like.

Further, as the malodorous component referred to in the present specification, specifically, aldehydes such as formaldehyde and acetaldehyde; carboxylic acids such as acetic acid and isovaleric acid; nitrogen-containing compounds such as ammonia; hydrogen sulfide, methyl disulfide, methyl And sulfur-containing compounds such as mercaptans.

FIG. 3 is a graph showing an adsorption / desorption isotherm of carbon dioxide at 298 K of the blue powder obtained in Experimental Example 1-1. FIG. 4 is a graph showing an adsorption and desorption isotherm of carbon dioxide at 298 K of the adsorption sheet obtained in Experimental Example 1-1. FIG. 3 is a graph showing ethylene adsorption / desorption isotherms at 273 K of the blue powder obtained in Experimental Example 1-1. FIG. 3 is a graph showing an adsorption / desorption isotherm of ethylene at 273 K of the adsorption sheet obtained in Experimental Example 1-1. FIG. 3 is a graph showing an adsorption / desorption isotherm of carbon dioxide at 298 K of the white powder obtained in Experimental Example 1-2. It is a figure which shows the adsorption-and-desorption isotherm of a carbon dioxide in 298K of the adsorption sheet obtained in Experimental example 1-2. FIG. 3 is a graph showing the adsorption and desorption isotherm of carbon dioxide at 298 K of the blue powder obtained in Experimental Example 1-3. It is a figure which shows the adsorption-desorption isotherm of a carbon dioxide in 298K of the adsorption sheet obtained in Experimental example 1-3. FIG. 3 is a graph showing adsorption / desorption isotherms of carbon dioxide at 298 K of the pellets obtained in Experimental Example 1-4. FIG. 4 is a graph showing ethylene adsorption / desorption isotherms at 273 K of the pellets obtained in Experimental Example 1-4. FIG. 7 is a graph showing adsorption / desorption isotherms of carbon dioxide at 298 K of the pellets obtained in Experimental Example 1-5. It is a model figure in case the adsorption-desorption isotherm of a porous metal complex shows a hysteresis loop. It is a figure which shows the X-ray-diffraction pattern of a porous metal complex (A1-1). It is a figure which shows the X-ray-diffraction pattern of a porous metal complex (A1-2).

1. Adsorption sheet The adsorption sheet of the present invention comprises (i) a porous metal complex (A) having a porous structure composed of a metal ion and an organic ligand capable of binding to the metal ion, and an organic fiber (B). (Hereinafter sometimes referred to as “first adsorbing sheet”) or (ii) a porous metal complex (A) and a heat-resistant fiber (D) (hereinafter referred to as “second”). However, the first and second suction sheets may be collectively referred to as “the suction sheet of the present invention”). First, the first suction sheet will be described.

1-1. 1st adsorption sheet The 1st adsorption sheet of this invention is a porous metal complex (A) which comprises a porous structure by the metal ligand and the organic ligand which can be couple | bonded with the said metal ion, and organic It is characterized by including the fiber (B).

The thickness of the first adsorption sheet of the present invention is preferably 0.01 mm to 2 mm. More preferably, it is 0.1 mm to 0.5 mm, and further preferably 0.1 mm to 0.3 mm. If the thickness of the adsorbing sheet is too thin, it is difficult to increase the amount of the porous metal complex (A) supported. On the other hand, if the adsorbing sheet is too thick, the workability of the adsorbing element such as a gas separation device may be reduced.
The basis weight of the first adsorbing sheet of the present invention is preferably 50 g / m ² to 200 g / m ² . More preferably, it is 130 g / m ² to 170 g / m ² . If the basis weight is too small, the structure of the adsorption sheet becomes sparse, and the amount of the porous metal complex (A) supported becomes small, so that sufficient adsorption performance may not be exhibited, while the basis weight is large. If it is too large, the adsorbing sheet becomes thick, and there is a possibility that problems such as cracking are likely to occur when the adsorbing element is processed.

1-1-1. Porous metal complex (A)
The porous metal complex (A) contained in the first adsorbing sheet of the present invention has a porous structure formed by metal ions and organic ligands that can bind to the metal ions. Therefore, the porous metal complex (A) has pores, and gas molecules can be accommodated in the pores.

It is preferable that the pores have a flexible structure capable of selectively adsorbing only a specific kind of gas with a change in structure or size by an external stimulus (pressure or the like). With such pores, a specific type of gas can be selectively adsorbed in the pores. Therefore, the porous metal complex (A) according to the present invention can be used as an adsorbent that adsorbs a specific gas in accordance with the purpose of adsorption, occlusion, and separation. Therefore, the size of the pores of the porous metal complex (A) according to the present invention is not particularly limited, but is preferably 2 to 50 mm, more preferably 2 to 30 mm, and still more preferably 2 to 20 mm. It is.

Specific examples of the specific gas include at least one gas selected from the group consisting of hydrogen, nitrogen, oxygen, carbon monoxide, carbon dioxide, and hydrocarbons having 1 to 4 carbon atoms. Examples of the hydrocarbon having 1 to 4 carbon atoms include methane, ethane, propane and butane.

In the porous metal complex (A) according to the present invention, the adsorption / desorption isotherm with respect to the above-mentioned specific gas preferably exhibits a hysteresis loop. Here, “the adsorption / desorption isotherm shows a hysteresis loop” means that when the adsorption / desorption isotherm for a specific gas is created for the porous metal complex (A), as shown in FIG. It means that the adsorption / desorption isotherm at the time and the desorption isotherm at the time of gas desorption take different trajectories.

FIG. 12 is a model example when the adsorption / desorption isotherm of the porous metal complex (A) shows a hysteresis loop. Usually, when the adsorption / desorption isotherm does not show a hysteresis loop, the locus of the adsorption / desorption isotherm during adsorption coincides with the locus of the desorption isotherm during desorption. On the other hand, when the adsorption isotherm shows a hysteresis loop, the adsorption amount A1 at the pressure P1 at which the adsorption amount at the time of gas adsorption starts to increase greatly, the adsorption amount A2 at the pressure P1 at the time of desorption, and at the time of gas desorption. Since the adsorption amount A3 at the pressure P2 at which the adsorption amount starts to decrease greatly and the adsorption amount A4 at the pressure P2 at the time of adsorption are different from each other, the adsorption and desorption isotherms at the time of adsorption and desorption become different trajectories. Therefore, the porous metal complex (A) in which the adsorption / desorption isotherm shows a hysteresis loop as shown in FIG. 12 can arbitrarily perform gas adsorption / desorption by controlling the pressure. It is useful because it can also be used in a gas separator utilizing this characteristic.

The metal ion constituting the porous metal complex (A) of the present invention is not particularly limited as long as it can form pores capable of accommodating a specific molecule by organization with an organic ligand. Elements and transition metal elements can be used, but preferably at least one metal selected from the group consisting of magnesium, calcium, aluminum, vanadium, manganese, iron, cobalt, nickel, copper, zinc, cadmium, lead and palladium. Cations. More preferably, it is at least one metal ion selected from magnesium, aluminum, copper and zinc.

The organic ligand constituting the porous metal complex (A) according to the present invention has two or more sites capable of coordinate bonding with a metal ion in the molecule, and a specific molecule is formed by organization with the metal ion. The organic compound is not particularly limited as long as it can form a porous structure having a plurality of pores that can be accommodated, but at least one of the organic compounds is selected from the following groups (1) to (3): preferable.

(1) Organic compound having two or more carboxyl groups and / or hydroxyl groups in the molecule, having no heterocyclic ring, and capable of bidentate coordination with metal ions (2) N, O or S in the molecule A monocyclic or polycyclic saturated or unsaturated heterocycle having one heteroatom selected from the following, an organic compound having a carboxyl group or a hydroxyl group and capable of bidentate coordination to a metal ion (3) Intramolecular And a bidentate organic compound having a monocyclic or polycyclic saturated or unsaturated heterocycle having 2 or more heteroatoms selected from the group consisting of N, O and S

(1) As an organic compound having two or more carboxyl groups and / or hydroxyl groups in the molecule, having no heterocyclic ring and capable of bidentate coordination with a metal ion (hereinafter referred to as organic compound (1)) Is an alkylene dicarboxylic acid compound having 4 to 20 carbon atoms (the carbon number includes carbon constituting a carboxy group), an alkenylene dicarboxylic acid compound having 4 to 20 carbon atoms (the carbon number is a carboxy group). And carbon atoms constituting), dicarboxylic acid compounds represented by the following general formulas (I) to (III), dicarboxylic acid compounds represented by the following general formula (IV), and the following general formula (V) An organic compound is mentioned.

In formulas (I) to (III), each R ¹ is the same or different and is a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an alkoxy having 1 to 4 carbon atoms. Group, formyl group, acyloxy group having 1 to 4 carbon atoms, alkoxycarbonyl group having an alkoxy group having 1 to 4 carbon atoms, nitro group, cyano group, carboxyl group, amino group, monoalkylamino group having 1 to 4 carbon atoms A dialkylamino group having an alkyl group having 1 to 4 carbon atoms or an acylamino group having 1 to 4 carbon atoms, wherein two or more R ¹ may be cyclic, and two or more R ¹ may be cyclic May be condensed. In the dialkylamino group, the two alkyl groups may be the same or different (the same applies hereinafter).

The alkyl group may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. The alkoxy group includes a methoxy group. , An ethoxy group, a propoxy group, and a butoxy group. Examples of the acyloxy group include those substituted with a linear or branched alkyl group having 1 to 4 carbon atoms (for example, an acetoxy group, a propionyloxy group). Group, isopropionyloxy group, etc.) and alkoxycarbonyl group include those substituted with a linear or branched alkyl group having 1 to 4 carbon atoms (eg, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group). Group, isopropoxycarbonyl group, butoxycarbonyl group, etc.) and monoalkylamino group include straight-chain Examples include those substituted with a branched alkyl group (for example, methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, etc.). Examples thereof include those having 1 to 4 linear or branched alkyl groups substituted (for example, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, s-butylamino group, etc.), and acylamino group Includes those substituted with a linear or branched alkyl group having 1 to 4 carbon atoms (for example, acetylamino group, propionylamino group, etc.). Among these, R ¹ is preferably a hydrogen atom.

In formula (IV), R ^{2 s} are the same or different and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms which may have a substituent, and X represents a hydrogen atom or a substituent. An alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group or an amino group. It is. Among these, R ² is preferably a hydrogen atom.

In formula (V), each R ³ is the same or different and is a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkyl group having 2 to 4 carbon atoms. An alkynyl group or an alkoxy group having 1 to 4 carbon atoms. Among these, R ³ is preferably a hydrogen atom.

(2) Two or more metal ions having a monocyclic or polycyclic saturated or unsaturated heterocycle having one heteroatom selected from N, O or S and a carboxyl group or a hydroxyl group in the molecule. Examples of the organic compound capable of conformation (hereinafter referred to as organic compound (2)) include organic compounds represented by the following general formulas (VI) to (VIII)).

In formulas (VI) to (VIII), R ^{3 s} are the same or different and each represents a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, carbon An alkynyl group having 2 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. Among these, R ³ is preferably a hydrogen atom.

(3) bidentate coordination to a metal ion having a monocyclic or polycyclic saturated or unsaturated heterocycle having two or more heteroatoms selected from the group consisting of N, O and S in the molecule Examples of possible organic compounds (hereinafter referred to as organic compounds (3)) include organic compounds represented by the following general formulas (IX) to (XII).

In formulas (IX) to (XII), Y is the same or different and represents an oxygen atom, a sulfur atom, —CH ₂ —, —CH (OH) —, —CO—, —NH—, —C ₂ N ₄ — ( 1,2,4,5-tetrazine-3,6-diyl group), —C≡C—, —C ₂ H ₂ — or —C ₆ H ₄ —, preferably —C ₂ H ₂ — or — C ₆ H ₄ —. R ^{4 s} are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a formyl group, or 1 to 4 carbon atoms. An acyloxy group, an alkoxycarbonyl group having an alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyano group, a carboxyl group, an amino group, a monoalkylamino group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. Or a dialkylamino group having 1 to 4 carbon atoms. Specific examples of the acyloxy group, alkoxycarbonyl group, mono- or di-alkylamino group, and acylamino group are the same as those for R ¹ of the organic compound (1). Among these, R ⁴ is preferably a hydrogen atom. Note that n is an integer of 0 to 3, preferably 0 or 1.

The above organic ligands may be used alone or in combination of two or more, and may be appropriately selected according to the type of gas to be adsorbed. Among the organic compounds, alkylene dicarboxylic acid compounds having 4 to 20 carbon atoms, organic compound (I), organic compound (IV), organic compound (IX), and organic compound (X) are preferable, and fumaric acid, Terephthalic acid and its derivatives, isophthalic acid and its derivatives, pyrazine and its derivatives, 4,4′-bipyridine, 1,2-bis (4-pyridyl) ethane, 1,2-bis (4-pyridyl) ethylene, 1, 2-bis (4-pyridyl) acetylene, more preferably 1,3,5-benzenetricarboxylic acid, 5-nitroisophthalic acid, pyrazine, 2,3-pyrazinecarboxylic acid, 1,2-bis (4- Pyridyl) ethylene.

Moreover, there is no restriction | limiting in particular also in the combination of the organic ligand in the case of using 2 or more types of organic ligands, For example, it specifies with the organic compound group specified by said (1), and (3). A combination of organic ligands selected from each of the organic compound groups; a combination of two or more organic ligands selected from the organic compound group specified in (3) above is preferred, more preferably an organic compound ( I) and a combination of organic compound (IX), a combination of organic compound (IV) and organic compound (IX), a combination of organic compound (X) and organic compound (IX), represented by organic compound (X) A combination of two or more compounds, more preferably a combination of 5-nitroisophthalic acid and 1,2-bis (4-pyridyl) ethylene, 2,3-pyrazinecarboxylic acid and pyrazi It includes the combination of a.

The porous metal complex (A) is a salt of the above metal (for example, nitrate, sulfate, formate, acetate, carbonate, hydrochloride, hydrobromide, tetrafluoroborate, phosphorus hexafluoride). Acid salt) and the above-mentioned organic ligand are dissolved in water or an organic solvent and reacted for several hours to several days. The organic solvent only needs to dissolve the metal salt and the organic ligand. For example, methanol, ethanol, propanol, diethyl ether, tetrahydrofuran, hexane, cyclohexane, benzene, toluene, methylene chloride, chloroform, acetone, Ethyl acetate, acetonitrile, dimethyl sulfoxide, dimethylformamide (DMF), water, or a mixed solvent of two or more of these can be used. The reaction conditions are not particularly limited, and may be appropriately adjusted according to the progress of the reaction. For example, the reaction temperature is preferably room temperature (25 ° C.) to 150 ° C. Moreover, you may perform the said reaction under pressure.

Examples of the form of the porous metal complex (A) according to the present invention include various forms such as granular, powdery, fibrous, film-like, and plate-like, preferably powdery or granular, preferably powdery. Is more preferable. The average particle size of the porous metal complex (A) is preferably 0.1 μm or more, more preferably 1 μm or more, further preferably 5 μm or more, preferably 500 μm or less, more preferably 200 μm or less. More preferably, those having a thickness of 100 μm or less can be preferably used. If the average particle size is too small, it is difficult to handle, and if the average particle size is too large, it may be difficult to sufficiently support the porous metal complex on the adsorption sheet, and the porous metal complex may drop off frequently. is there. In the present invention, the “average particle diameter” is a 50% diameter (median diameter), and can be measured by, for example, a laser diffraction / scattering particle size distribution measuring apparatus.

The BET specific surface area of the porous metal complex by the 77K nitrogen adsorption method is not particularly limited, but is preferably 500 m ² / g or more, for example. If the BET specific surface area is smaller than 500 m ² / g, it may be difficult to obtain sufficient adsorption performance. The BET specific surface area is more preferably 1000 m ² / g or more. The upper limit of the BET specific surface area is not particularly limited, but is preferably 6000 m ² / g or less. If this range is exceeded, the production of the porous metal complex becomes very difficult.
In addition, an average particle diameter and a BET specific surface area can be measured by the method as described in an Example.

The amount of the porous metal complex (A) contained in the first adsorption sheet of the present invention is preferably 50% by mass to 90% by mass. Considering the adsorption performance, the productivity of the adsorption sheet, the dropping of the porous metal complex (A), etc., the content of the porous metal complex (A) is more preferably 60% by mass to 80% by mass. When the content of the porous metal complex (A) is less than 50% by mass, the gas adsorption efficiency per unit mass is deteriorated. On the other hand, when the content exceeds 90% by mass, the productivity of the adsorbing sheet is lowered or the porous metal complex ( There is a tendency for dropout of A) to increase.

1-1-2. Organic fiber (B)
The organic fiber (B) in the 1st adsorption sheet of this invention is a component which functions as a support | carrier which carries a porous metal complex (A), and a pulp-like fiber is preferable. From the viewpoint of highly supporting the porous metal complex (A) on the first adsorbing sheet, the organic fiber (B) is desirably fibrillated. The pulp form means a state separated and processed for use in papermaking.

Examples of the organic fiber (B) include cellulose fiber, polyester, vinylon, polypropylene, polyamide, rayon, acrylic fiber, polylactic acid fiber, polybenzimidazole, polybenzoxazole, polyimide, polyamideimide, and polyether ketone. When heat resistance is required for the adsorption sheet, more preferably, fibers made from wholly aromatic polyamides such as aramid and meta-aramid, polybenzimidazole, polybenzoxazole, polyimide, polyamideimide or polyether ketone are used. It is done. The said organic fiber (B) may be used independently, and 2 or more types may be mixed and used for it.

The amount of the organic fiber (B) contained in the first adsorption sheet of the present invention is preferably 5% by mass to 20% by mass. When the content of the organic fiber (B) is less than 5% by mass, the supporting ability of the porous metal complex tends to be insufficient. On the other hand, when the content exceeds 20% by mass, the porous metal complex (A) contained in the adsorption sheet Since the amount is relatively small, it may be difficult to obtain a sufficient adsorption effect. More preferably, it is 10% by mass to 20% by mass, and further preferably 15% by mass to 20% by mass.

1-1-3. Other components In the 1st adsorption sheet of this invention, even if it uses an organic binder (C) as a binder for carrying | supporting a porous metal complex (A) on an organic fiber (B) as needed. Good. The organic binder (C) is not particularly limited as long as the porous metal complex (A) can be supported on the adsorption sheet at a high ratio during the production of the adsorption sheet. For example, as the organic binder (C), a polyvinyl alcohol polymer, a polyacrylonitrile polymer, a polyethylene polymer, a polyester polymer, a starch binder, a cellulose polymer, or the like can be used. Specific examples include polyvinyl alcohol (PVA), starch, polyacrylonitrile, methyl cellulose, carboxymethyl cellulose, and the like.

The amount of the organic binder (C) is preferably 5% by mass to 30% by mass with respect to a total of 100% by mass of the constituent components of the adsorption sheet (more preferably 5% by mass to 10% by mass, and even more preferably 5% by mass). Mass% to 7 mass%). When the amount of the organic binder (C) is less than 5% by mass, the fixability of the porous metal complex (A) to the fiber component such as the organic fiber (B) and the bonding property between the fiber components tend to be poor. If it exceeds 30% by mass, the amount of the porous metal complex (A) in the adsorbing sheet is relatively small, so that it may be difficult to obtain a sufficient adsorbing effect.

In a preferred embodiment, the first adsorption sheet of the present invention may contain additives other than the porous metal complex (A), the organic fiber (B), and the organic binder (C) as necessary. Examples of the additive include glass fiber, polymer flocculant, and pigment for the purpose of improving the mechanical strength of the adsorption sheet. The amount of these components to be used is preferably 0% by mass to 10% by mass (more preferably 3% by mass to 7% by mass) with respect to a total of 100% by mass of the constituent components of the adsorption sheet.

The first adsorbing sheet of the present invention can selectively adsorb only a specific kind of gas while the porous metal complex (A) changes its structure and size, and adsorbs and desorbs the specific gas by changing the pressure. Since it has a porous metal complex (A) that can be used, it has excellent separation performance for separating a specific gas from a mixed gas. Moreover, since the component which comprises a 1st adsorption sheet is comparatively flexible and can follow the structural change of a porous metal complex (A), a porous metal complex (A) has also in an adsorption sheet. Excellent performance can be demonstrated. Therefore, the 1st adsorption sheet of this invention is preferably used as an adsorption sheet which comprises the adsorption element in a pressure swing adsorption method gas separation apparatus, for example.

1-2. Second Adsorption Sheet Next, the second adsorption sheet will be described.
The 2nd adsorption sheet of the present invention contains a porous metal complex (A) and a heat resistant fiber (D). By containing the porous metal complex, sufficient adsorption performance can be obtained, and by containing the heat resistant fiber (D), it is difficult to cause a significant decrease in strength even under a temperature condition of 80 ° C. or higher. This is because excellent heat resistance can be obtained. When the adsorption sheet does not contain the porous metal complex (A), the adsorption performance becomes insufficient. Moreover, if the adsorbing sheet does not contain the heat resistant fiber (D), sufficient heat resistance cannot be obtained, and the strength of the adsorbing sheet is significantly reduced under a temperature condition of 80 ° C. or higher.

The thickness of the second suction sheet of the present invention is preferably 0.1 mm to 0.6 mm, more preferably 0.1 mm to 0.5 mm. If the thickness is less than 0.1 mm, the sheet strength is remarkably reduced, and it may be difficult to process the honeycomb-shaped adsorption element in post-processing. Further, if the thickness is larger than 0.6 mm, the pressure loss of the adsorbing element tends to increase when the adsorbing sheet is processed into a honeycomb shape or the like.

The basis weight of the second adsorbing sheet of the present invention is preferably 25 g / m ² to 200 g / m ² . More preferably, it is 40 g / m ² to 150 g / m ² . If the basis weight is less than 25 g / m ² , the thickness of the sheet may be reduced, and the sheet strength may be significantly reduced, which may make it difficult to process the honeycomb-shaped adsorption element in post-processing. On the other hand, if the basis weight exceeds 200 g / m ² , the thickness of the sheet becomes too large, and the pressure loss of the adsorption element when processed into a honeycomb or the like may increase.

1-2-1. Porous metal complex (A)
The porous metal complex (A) according to the present invention is a porous material composed of a metal ion and a compound having a ligand. As a porous metal complex (A), the same thing as the thing used with a 1st adsorption sheet can be used.

Although it does not specifically limit as a preferable metal ion which comprises the porous metal complex (A) which concerns on a 2nd adsorption sheet, For example, transition metal, such as typical metal elements, such as aluminum ion, iron ion, copper ion, and zinc ion Elements. On the other hand, preferred compounds having a ligand include, for example, 2-methylimidazole, terephthalic acid and trimesic acid. As a specific porous metal complex (A) constituting the second adsorbing sheet, for example, a porous metal complex composed of zinc ions and 2-methylimidazole (manufactured by BASF, Basolite (registered trademark, the same applies hereinafter) Z1200), porous metal complex composed of aluminum ion and terephthalic acid (BASF, Basolite A100), porous metal complex composed of copper ion and trimesic acid (BASF, Basolite C300), iron ion And a porous metal complex composed of trimesic acid (BASF Corp., Basolite F300) is preferred.
If the purpose of using the adsorbent sheet is to efficiently separate / recover, or adsorb / remove organic solvents and malodorous components from moisture-containing gases, a highly hydrophobic porous metal complex should be used. preferable. A highly hydrophobic porous metal complex is a porous metal complex that has been subjected to a vacuum heat treatment at a temperature of 200 ° C. for 48 hours or more under vacuum conditions in a nitrogen atmosphere at 30 ° C. and a relative humidity of 60% RH. It refers to a porous metal complex having a mass increase rate of less than 10% by mass obtained by dividing the mass increase when left standing for 3 days or more by the mass of the porous metal complex immediately after the vacuum heat treatment. Specific examples of the highly hydrophobic porous metal complex (A) include a porous metal complex composed of zinc ions and 2-methylimidazole (Basolite Z1200, manufactured by BASF).

In the second adsorption sheet of the present invention, the content of the porous metal complex (A) is preferably 50% by mass to 85% by mass, more preferably 60% by mass to 80% by mass. If the content is less than 50% by mass, it may be difficult to obtain sufficient adsorption performance. On the other hand, when the content exceeds 85% by mass, it becomes difficult to sufficiently support the porous metal complex on the adsorption sheet, and the amount of dropping off increases. In addition, the sheet strength may be significantly reduced.

1-2-2. Heat resistant fiber (D)
The heat resistant fiber (D) contained in the second adsorbing sheet of the present invention is a component that ensures the heat resistance of the adsorbing sheet. Here, the heat-resistant fiber (D) is a calorimeter measuring device (Q50, manufactured by TA Instruments Japan Co., Ltd.) using 30 mg of a sample dried in advance at 150 ° C. under vacuum for 12 hours. It means a fiber having a weight loss rate of 5% or less when the temperature is raised from room temperature to 300 ° C. at an air flow rate of 60 mL / min and a temperature increase rate of 20 ° C./min. Such a heat-resistant fiber (D) is less likely to cause a significant decrease in strength under a temperature condition of 80 ° C. or higher, and is preferable as a component that imparts heat resistance to the adsorption sheet. Note that the significant decrease in strength means that when the second adsorbing sheet of the present invention is bent at 90 degrees in a heated atmosphere of 80 ° C. or higher, the adsorbing sheet is not easily cracked or cracked.

Specific examples of the heat resistant fiber (D) include inorganic fibers such as glass fiber, ceramic fiber, rock wool fiber, etc .; among the organic fibers (B) exemplified in the first adsorption sheet, those having heat resistance, specifically Include organic fibers such as aramid fiber, meta-aramid fiber, polybenzimidazole fiber, polybenzoxazole fiber, polyimide fiber, polyamide fiber, polyamideimide fiber, polyetherketone fiber; and fibers obtained by fibrillating them; Of these, it is preferable to use one or more of them. The fiber diameter of the heat resistant fiber (D) is preferably 1 μm to 15 μm, and more preferably 1 μm to 10 μm. The fiber length is preferably 1 mm to 10 mm, more preferably 2 mm to 5 mm. From the viewpoint of improving both the strength and flexibility of the second adsorbing sheet, the heat resistant fiber (D) contains glass fibers having a fiber diameter of 1 μm to 10 μm and a fiber length of 2 mm to 5 mm. Is preferred.

The content of the heat resistant fiber (D) in the second adsorption sheet is preferably 5% by mass to 30% by mass, more preferably 10% by mass to 25% by mass, and further preferably 10% by mass to 20% by mass. It is. If the amount of the heat-resistant fiber (D) is too large, the amount of the porous metal complex (A) contained in the adsorption sheet is relatively small, so that it may be difficult to obtain a sufficient adsorption effect. If the amount of the conductive fiber (D) is too small, it may be difficult to obtain sufficient heat resistance.

1-2-3. Clay mineral fiber (E)
It is preferable that the 2nd adsorption sheet in this invention contains the clay mineral fiber (E) which has self-consolidating property. Here, the self-consolidating property represents a property of consolidating only by itself. Therefore, by using the clay mineral fiber (E) having self-consolidating properties, the heat resistance of the adsorption sheet and the supportability of the porous metal complex (A) can be improved. The adsorption sheet strength can be further improved by the self-consolidating property of (E). Although it does not specifically limit about the kind of said clay mineral fiber (E), Since it is easy to acquire, a magnesium silicate fiber or a calcium silicate fiber is preferable.
The fiber diameter and fiber length of the clay mineral fiber (E) are not particularly limited, but the fiber diameter is preferably 0.1 μm to 0.5 μm, more preferably 0.1 μm to 0.2 μm. The length is preferably 1 μm to 50 μm, more preferably 1 μm to 30 μm. When the fiber diameter is less than 0.1 μm and the fiber length is less than 1 μm, the fiber is too fine, so that not only the support property of the porous metal complex (A) tends to be lowered, but also the strength of the adsorption sheet is lowered. Furthermore, it may be difficult to handle the clay mineral fiber (E) during sheet production. On the other hand, when the fiber diameter is larger than 0.5 μm and the fiber length is longer than 50 μm, heating at a high temperature for a long time is required to develop sufficient self-consolidation properties, and the porous metal complex (A) The pore structure may be broken.

The content of the clay mineral fiber (E) in the second adsorption sheet is preferably 5% by mass to 35% by mass, more preferably 5% by mass to 25% by mass. When the content of the clay mineral fiber (E) is less than 5% by mass, the supportability of the porous metal complex (A) is insufficient. On the other hand, when the content exceeds 35% by mass, the porous metal complex (A) becomes the clay mineral fiber. It may be covered with (E) and it may be difficult to obtain sufficient adsorption performance.

1-2-4. Organic binder (C)
It is preferable that the 2nd adsorption sheet in this invention contains an organic binder (C). This is because the flexibility and strength of the adsorption sheet can be improved. The organic binder (C) is not particularly limited as long as it can join the porous metal complex (A) (adsorbent) and the heat-resistant fiber (D). For example, the same organic binder as that of the first adsorption sheet, such as a polyvinyl alcohol polymer, a polyacrylonitrile polymer, a polyethylene polymer, and a polyester polymer, can be used. From the viewpoint of handleability, polyvinyl alcohol polymers are preferred.
Although the usage mode of an organic binder (C) is not specifically limited, Since a fibrous thing is used, since an adsorption sheet can be produced simply, it is preferable. The content (C) of the organic binder in the second adsorption sheet is preferably 5% by mass to 15% by mass, and more preferably 5% by mass to 10% by mass. If it is less than 5% by mass, the supportability of the porous metal complex (A) is insufficient, and if it exceeds 15% by mass, the porous metal complex (A) is coated with the organic binder (C), and sufficient adsorption performance is obtained. There is a tendency to become difficult to get.

1-2-5. Other Components The second adsorbing sheet of the present invention may contain a porous material other than the porous metal complex (A), and the porous material contained in the adsorbing sheet of the present invention is not particularly limited. However, organic polymer porous materials such as activated carbon, zeolite, silica gel, activated alumina, clay mineral (excluding the clay mineral fiber (E) described above), aluminophosphate, silicoaluminophosphoric acid, styrene-divinylbenzene copolymer, etc. Examples include masses. Preferred are activated carbon, zeolite, silica gel and activated alumina, which can be obtained at low cost. The content of other components in the second adsorption sheet is preferably 20% by mass or less.

The second adsorbing sheet of the present invention is an indoor, vehicle, wallpaper, furniture, interior material, resin molded body, electrical device, etc., for the purpose of reducing malodorous components, etc., or in the air discharged from factories, etc. It can be widely used for the purpose of solvent separation / recovery or adsorption / removal.

2. Manufacturing method of adsorption sheet The method in particular of manufacturing the adsorption sheet of this invention is not restrict | limited, A conventionally well-known processing method can be used. Preferably, sheet constituent materials such as porous metal complex (A), organic fiber (B) and / or heat resistant fiber (D), and organic binder (C) and clay mineral fiber (E) used as necessary. There is a wet sheeting method in which a sheet-like material is obtained by dispersing in water, an organic solvent or a mixture thereof, molding, dehydrating and drying.

For example, when producing a sheet-like material by a wet papermaking method, first, a porous metal complex (A), an organic fiber (B) or a heat-resistant fiber (D), and an optionally used organic binder (C) and viscosity Other components such as mineral fiber (E) are dispersed in water at a predetermined blending ratio (preparation of dispersion slurry). At this time, the concentration of each component in the dispersed slurry may be appropriately adjusted so that the content in the adsorption sheet is within the above-described range.

Next, the obtained dispersion slurry is paper-made with a paper machine to obtain a sheet-like material, which is then dehydrated and dried to obtain an adsorption sheet. The method of dehydration and drying is not particularly limited, for example, a dehydration method such as a method of dehydrating under pressure by passing a sheet-like material between a pair of rolls; hot air is blown on the sheet-like material after sun-drying and dehydration Any conventionally known method such as a method; etc. can be used.

In addition, it is preferable that the porous metal complex (A) is mixed with the sheet constituent material in a state having solvent molecules in the pores and subjected to a sheet forming step. When the porous metal complex (A) does not have solvent molecules in the pores, the organic binder (C) constituting the adsorption sheet may be adsorbed in the pores. In this case, it is difficult to remove the organic binder (C) trapped in the pores of the porous metal complex (A) even if the solvent removal treatment described later is performed after forming the sheet, and the adsorption performance of the adsorption sheet is The result is inferior. That is, by adsorbing solvent molecules to the pores of the porous metal complex (A), adsorption to the pores of the organic binder (C) and the like in the sheeting step is prevented, and will be described later after the sheeting step. By removing the solvent molecules from the pores by the solvent removal treatment, the adsorption performance of the adsorption sheet can be secured. Usually, at the stage of synthesizing the porous metal complex (A), solvent molecules are adsorbed in the pores of the porous metal complex (A), but the porous metal complex (A) is solvent molecules in the pores. In the case where the organic solvent is not present or the amount of adsorption of the solvent molecules is insufficient, the organic solvent can be adsorbed in the pores by the method described in the examples described later. In addition, the solvent molecule | numerator here refers to water and a general organic solvent molecule.

In the production of the adsorbing sheet of the present invention, it is preferable to carry out a desolvation treatment process for removing the solvent contained in the adsorbing sheet after the sheeting process. As described above, when the porous metal complex (A) is formed into a sheet with solvent molecules in the pores, the porous metal complex (A) is solvent molecules in the pores. In this state, it is difficult to obtain sufficient adsorption performance. Therefore, in order to develop the adsorption performance, it is preferable to perform a solvent removal treatment after the sheet forming step. In addition, if the implementation time of a solvent removal process is after the sheet forming process, it will not be specifically limited.

The conditions for the solvent removal treatment are not particularly limited, but the temperature is preferably 80 ° C. to 300 ° C. If it is less than 80 degreeC, there exists a possibility that the removal of a solvent may become incomplete and sufficient adsorption | suction performance may be difficult to be obtained. On the other hand, when it exceeds 300 ° C., the pore structure of the porous metal complex (A) may be broken, and in this case, it is difficult to obtain sufficient adsorption performance. More preferably, it is 100 ° C to 200 ° C. Moreover, the solvent removal can be more efficiently removed by carrying out the solvent removal treatment under reduced pressure. At this time, the degree of reduced pressure is not particularly limited, and may be appropriately adjusted according to the physical properties and blending amount of the porous metal complex (A). For example, 10 ³ Pa to 10 ⁻⁵ Pa is preferable, and 10 ⁻¹ Pa. More preferably, it is ^{˜10 −5} Pa. Although the solvent removal treatment time is not particularly limited, it is preferably, for example, 1 hour to 100 hours, more preferably 3 hours to 48 hours, and further preferably 3 hours to 24 hours. The most preferable solvent removal treatment conditions are 100 to 200 ° C. and 3 to 24 hours under vacuum.

The adsorption sheet of the present invention may be used in a planar shape, or may be used in a desired shape by appropriately performing pleating processing, honeycomb processing, corrugating processing, or the like.

3. Adsorption element The adsorption element of the present invention is characterized by being provided with the adsorption sheet of the present invention. The type of the adsorbing element according to the present invention is not particularly limited, and any conventionally known type can be adopted and may be appropriately selected according to the application and purpose. Further, the shape of the suction sheet provided in the suction element of the present invention is not particularly limited, but for example, a suction sheet processed into a flat shape, a pleat shape, a honeycomb shape, or the like can be used. For example, when the adsorption sheet processed into a pleat is used as a cross-flow type adsorption element, and when the adsorption sheet processed into a honeycomb is used as a parallel flow type adsorption element, contact with the gas to be treated respectively. By increasing the area, it is possible to improve the removal efficiency and reduce the pressure loss of the adsorption element at the same time. The parallel flow type adsorption element is superior to the cross flow type adsorption element in terms of prevention of clogging due to mist and dust, low pressure loss, and weight reduction. Therefore, the adsorption sheet provided in the adsorption element is a honeycomb. It is preferable that it is a shape.

The adsorbing element using the adsorbing sheet of the present invention is used in indoors, in vehicles, for wallpaper, furniture, interior materials, resin moldings, electrical equipment, etc., for reducing malodorous components, etc. It can be widely used for the purpose of separation / recovery or adsorption / removal of organic solvents.

This application is based on Japanese patent application No. 2012-17192 filed on January 30, 2012 and Japanese patent application No. 2012-17193 filed on January 30, 2012. It is what I insist. The entire contents of the specifications of Japanese Patent Application No. 2012-17192 filed on January 30, 2012 and Japanese Patent Application No. 2012-17193 filed on January 30, 2012 are hereby incorporated by reference. Incorporated for.

Hereinafter, the present invention will be described more specifically with reference to experimental examples.However, the present invention is not limited by the following experimental examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.
Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.

Experimental example 1
[Creation of adsorption / desorption isotherm]
The porous metal complex, adsorbent sheet or pellet obtained in the following experimental example was dried under reduced pressure at 423 K and 50 Pa for 6 hours or more to remove adsorbed water and the like, and then a gas adsorption amount measuring device (“BELSORP-” manufactured by Bell Japan Co., Ltd.). HP ”) was used to measure by the volume method (equilibrium waiting time: 500 seconds), and an adsorption / desorption isotherm was created. In any sample, the measurement was performed such that the amount of the porous metal complex in the sample was 0.3 g to 0.5 g.

(Experimental example 1-1)
Porous metal complex (A1-1): Synthesis of [Cu ₂ (pzdc) ₂ (prz)] Copper nitrate trihydrate (1.23 g, 5.0 mmol, 1.0 eq.) Was added to an eggplant flask (500 ml), Pyrazine (4.05 g, 50.0 mmol, 10.0 eq.) And pure water (100 ml) were added and mixed. To the obtained blue transparent solution, a mixed solution of an aqueous solution (80 ml) of 2,3-pyrazinedicarboxylic acid (0.84 g, 5.0 mmol, 1.0 eq.) And an aqueous 1N NaOH solution (20 ml) was added dropwise. . After stirring the mixed solution at room temperature (25 ° C.) for 2 hours, the obtained blue solid was filtered with Kiriyama funnel (registered trademark), washed with pure water and methanol in this order, dried, and blue powder (porous) Metal complex (A1-1)) was obtained (yield: 1.32 g). When measured using a laser diffraction / scattering particle size distribution measuring apparatus (“Partica (registered trademark) LA-950V2” manufactured by Horiba, Ltd.), the average particle size of the porous metal complex (A1-1) was 23 μm. Met. In the above formula, “prz” means pyrazine, and “pzdc” means 2,3-pyrazinedicarboxylic acid.

The powder X-ray diffraction pattern of the obtained porous metal complex (A1-1) was measured. The measurement was performed by a symmetric reflection method using an X-ray diffractometer (“Multiflex” manufactured by Rigaku Corporation), scanning a range of diffraction angle (2θ) = 3 to 50 ° at a scanning speed of 3 ° / min. The measurement results are shown in FIG.

Production of Adsorbent Sheet The composition of the adsorbent sheet is 70% by mass of the porous metal complex (A1-1), 20% by mass of pulp-like cellulose as the organic fiber (B), 5% by mass of PVA as the organic binder (C), inorganic fiber The adsorbent sheet (1), which is a sheet-like molded body having a thickness of about 0.26 mm and a basis weight of about 150 g / m ² , was manufactured using a wet papermaking apparatus so that the glass fiber was 5% by mass. In Experimental Example 1, the reduced-pressure drying process at the time of creating the adsorption / desorption isotherm corresponds to the desolvation step.

(Adsorption characteristics evaluation)
For the porous metal complex (A1-1) and the adsorption sheet (1) obtained in Experimental Example 1-1, the adsorption / desorption isotherm of carbon dioxide at 298K and the adsorption / desorption isotherm of ethylene at 273K were measured, respectively. The results are shown in FIGS. In either case, the vertical axis represents the amount of adsorption of the target gas (CO ₂ or C ₂ H ₄ ) per unit mass of the porous metal complex (A1-1) (the same applies hereinafter).

1 and FIG. 2, CO 2 per unit mass of the porous metal complex (A1-1) in the case of the porous metal complex (A1-1) (FIG. 1) and the case of the adsorption sheet (FIG. 2) are compared. _{2 There} is almost no difference in the adsorption amount, and it can be seen that the adsorption sheet (1) has a CO ₂ adsorption amount corresponding to the mass of the porous metal complex (A1-1) to be supported.

3 and 4, when ethylene gas is to be adsorbed, the porous metal complex (A1-1) (FIG. 3) and the adsorption sheet (1) (FIG. 4) There is almost no difference in the adsorption amount of ethylene gas per unit mass of the porous metal complex (A1-1), and the adsorption sheet (1) has an ethylene adsorption amount corresponding to the mass of the porous metal complex (A1-1) supported. Was showing. In addition, in FIG. 4, as in FIG. 3, it is possible to confirm a hysteresis loop in which the gas adsorption amount increases rapidly at about 200 kPa, whereas the gas release amount increases rapidly at about 230 kPa. In the adsorption sheet (1), the gate-type adsorption behavior was also reproduced. From this result, it is clear that the adsorption sheet of the present invention is excellent as an adsorbent without impairing the adsorption performance of the porous metal complex powder.

(Experimental example 1-2)
Synthesis of Porous Metal Complex (A1-2): [Zn (NO ₂ -ip) (bpe)] Zinc nitrate hexahydrate (1.50 g, 5.04 mmol, 1.0 eq.) Was added to an eggplant flask (300 ml). , 5-nitroisophthalic acid (1.07 g, 5.07 mmol, 1.0 eq.), 1,2-bis (4-pyridyl) ethylene (0.91 g, 5.01 mmol, 1.0 eq.), DMF (100 ml ) And heated at 120 ° C. for 16 hours (under N ₂ gas atmosphere). The obtained white solid was filtered through Kiriyama funnel (registered trademark), washed in turn with DMF and methanol, and then dried to obtain a white powder (porous metal complex (A1-2)) (yield: 2). .3 g, average particle size 63 μm). In the above formula, “NO ₂ -ip” means 5-nitroisophthalic acid, and “bpe” means 1,2-bis (4-pyridyl) ethylene.

For the obtained porous metal complex (A1-2), a powder X-ray diffraction pattern was measured in the same manner as in Experimental Example 1-1. The results are shown in FIG.

Production of Adsorbent Sheet The composition of the adsorbent sheet is 70% by mass of the porous metal complex (A1-2), 20% by mass of the pulp-like cellulose as the organic fiber (B), 5% by mass of PVA as the organic binder (C), and glass as the inorganic fiber. An adsorption sheet (2) having a thickness of about 0.25 mm and a basis weight of about 150 g / m ² was produced using a wet papermaking machine so that the fiber content was 5% by mass.

(Adsorption characteristics evaluation)
For each of the porous metal complex (A1-2) and the adsorption sheet (2) obtained in Experimental Example 1-2, the adsorption / desorption isotherm of carbon dioxide at 298 K was measured. The results are shown in FIGS.

5 and FIG. 6, the unit mass of the porous metal complex (A1-2) in the case of the porous metal complex (A1-2) (FIG. 5) and the case of the adsorption sheet (2) (FIG. 6) is shown. almost no difference in the CO ₂ adsorption amount per adsorption sheet (2) is found to have a CO ₂ adsorption amount corresponding to the mass of the porous metal complex (A1-2) carrying. From this result, it is clear that the adsorbing sheet of the present invention is excellent as an adsorbing material without impairing the adsorption performance of the porous metal complex.

(Experimental Example 1-3)
Production of Adsorption Sheet Using blue powder of “Basolite (registered trademark) C300” (obtained from Sigma Aldrich Japan Co., Ltd., average particle size 35 μm) as the porous metal complex (A1-3), the composition in the adsorption sheet is 60% by mass of the porous metal complex (A1-3), 20% by mass of the pulp-like cellulose as the organic fiber (B), 5% by mass of PVA as the organic binder (C), and 5% by mass of glass fiber as the inorganic fiber. Then, using a wet papermaking apparatus, an adsorption sheet (3) having a thickness of about 0.28 mm and a basis weight of about 156 g / m ² was produced.

(Adsorption characteristics evaluation)
For each of the porous metal complex (A1-3) and the adsorption sheet (3), the adsorption / desorption isotherm of carbon dioxide at 298 K was measured. The results are shown in FIGS.

7 and FIG. 8, the unit mass of the porous metal complex (A1-3) in the case of the porous metal complex (A1-3) (FIG. 7) and the case of the adsorption sheet (3) (FIG. 8) CO ₂ difference in adsorption amount is little per adsorption sheet (3) is found to have a CO ₂ adsorption amount corresponding to the mass of the porous metal complex (A1-3) carrying. From this result, it is clear that the adsorbing sheet of the present invention is excellent as an adsorbing material without impairing the adsorption performance of the porous metal complex.

(Experimental Example 1-4)
The porous metal complex (A1-1) obtained in Experimental Example 1-1 was used as the porous metal complex, and the composition in the pellet was 94% by mass of the porous metal complex (A1-1), the organic binder (C) Pellets (1) having a thickness of about 4 mm and a diameter of 3 mm were molded by a tablet molding apparatus so that 3% by mass of PVA and 3% by mass of graphite as a lubricant were obtained.

(Adsorption characteristics evaluation)
Carbon dioxide adsorption / desorption isotherm at 298K and ethylene adsorption / desorption isotherm at 273K of the obtained pellet (1) were measured. The results are shown in FIGS.

From comparison between FIGS. 1 and 3 and FIGS. 9 and 10, the CO ₂ adsorption amount and ethylene adsorption amount of the pellet (1) were in each case per unit mass of the porous metal complex (A1-1) used. It was only 90% of the adsorption amount. Further, in the adsorption / desorption isotherm (ethylene) of the porous metal complex (A1-1), a sudden rise in the adsorption amount was observed at around 200 kPa (FIG. 3). In FIG. 10, the adsorption amount at the adsorption start pressure was observed. The rise of was unclear. In the pellet (1) produced by compression molding, the porous metal complex (A1-1) and other components are firmly solidified, and the porous metal complex (A1-1) has its structure. It is considered that the original adsorption performance could not be exhibited because it was difficult to change, and the rise of the adsorption amount became unclear. From this result, it is clear that the adsorption performance of the porous metal complex (A1-1) is impaired by molding into pellets.

(Experimental Example 1-5)
The porous metal complex (A1-3) used in Experimental Example 1-3 was used as the porous metal complex, the composition in the pellet was 94% by mass of the porous metal complex (A1-3), and 3% of PVA was used as the organic binder component. %, Pellets (2) having a thickness of about 4 mm and a diameter of 3 mm were molded by a tablet molding apparatus so that the lubricant was 3% by mass of graphite.

(Adsorption characteristics evaluation)
With respect to the obtained pellet (2), an adsorption and desorption isotherm of carbon dioxide at 298K was measured. The results are shown in FIG.

From the comparison between FIG. 7 and FIG. 11, the CO ₂ adsorption amount of the pellet (2) was only about 18% of the adsorption amount per unit mass of the porous metal complex (A1-3) used. From this result, it is clear that the adsorption performance of the porous metal complex is impaired by molding into pellets.

Experimental example 2
[Measurement method of BET specific surface area]
About 100 mg of a porous metal complex sample (before treatment with an organic solvent) used in the following experimental examples was collected, vacuum-dried at 120 ° C. for 12 hours, and weighed. Using an automatic specific surface area measuring device (Gemini 2375, manufactured by Micromeritics), the amount of nitrogen gas adsorbed at the boiling point of liquid nitrogen (-195.8 ° C.) was set to a relative pressure of 0.02 to 0.95. 40 points were measured while gradually increasing in the range, and an adsorption isotherm of the sample was created. With the analysis software (GEMINI-PCW version 1.01) attached to the automatic specific surface area measurement device, set the surface area analysis range to 0.01 to 0.15 under the BET conditions, and the BET specific surface area [m ² / g] Asked.

[Measurement method of average particle size]
Using a scanning electron microscope (manufactured by Hitachi, Ltd., S-3500), the diameter of the porous metal complex used in the following experimental examples was measured at 100 points, and this was averaged to obtain a porous metal complex. The average particle diameter [μm] was determined.

[Measurement method of fiber diameter and fiber length]
Using a scanning electron microscope (manufactured by Hitachi, Ltd., S-3500), the fiber diameter [μm] and fiber length [mm] of 100 points of heat resistant fiber, clay mineral fiber, and organic binder used in the following experimental examples were measured. It was measured. The fiber diameter [μm] of the sample was obtained by arithmetically averaging the fiber diameters of 100 points. Moreover, the fiber length [mm] of the sample was calculated by averaging the fiber lengths of 100 points.

[Measurement method of heat resistance]
A test piece of 10 cm × 10 cm cut out from the adsorbent sheet produced in the following experimental example was treated at 250 ° C. for 10 hours in an air atmosphere, and then both ends of the treated test piece were held and bent at 90 degrees. At this time, the case where the sheet was not broken was evaluated as ◯, the case where the crack was generated was evaluated as Δ, and the case where the sheet was broken was evaluated as ×.

[Measurement method of supportability]
A 10 cm × 10 cm test piece cut out from the adsorbent sheet produced in the following experimental example was impacted with a sphere (material: aluminum) having a diameter of 2.4 cm and a mass of 20 g 10 times at a speed of 10 cm / s and dropped. The case where the amount of the metal complex was less than 0.1 mg was marked as ◯, the case where it was larger than 10 mg was marked as x, and the case where the amount was from 0.1 mg to 10 mg was marked as Δ.

[Measurement method of flexibility]
A 10 cm × 10 cm test piece cut out from the adsorption sheet manufactured in the following experimental example was held and bent at 90 degrees. At this time, the case where the sheet was not broken was evaluated as ◯, the case where the crack was generated was evaluated as Δ, and the case where the sheet was broken was evaluated as ×.

[Measurement method of adsorption performance]
An inorganic adhesive (water glass) is used as a binder, the adsorbing sheet is corrugated by a regular method, and the obtained corrugated board is laminated by using an inorganic adhesive (water glass) to form a honeycomb, 300 A cell / inch ² honeycomb sample was prepared. A honeycomb sample (60 mmφ, thickness 20 mm) was set in a 60 mmφ glass column, and dry air containing 5 ppm of toluene at a temperature of 25 ° C. was passed through the column at a speed of 2 m / s. Using a gas chromatograph with FID (manufactured by Shimadzu Corporation, GC-2014), the toluene concentration before and after passing through the honeycomb sample was measured every minute, and the toluene removal rate was calculated from the change in concentration before and after the passage. The measurement is continued until the removal rate reaches 20%, and the total removal mass [g] of toluene is calculated from the elapsed time and the removal rate, and the toluene removal amount [g / L] is calculated by dividing it by the volume of the honeycomb sample. Calculated.

(Experimental example 2-1)
As the porous metal complex (A), Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-1) in which solvent molecules were adsorbed in the pores. 70% by mass of the porous metal complex sample (A2-1) (excluding solvent molecules), 15% by mass of glass fiber (fiber diameter 6 μm, fiber length 3 mm) as heat-resistant fiber (D), clay mineral fiber ( E), magnesium silicate fiber (fiber diameter 0.1 μm, fiber length 1 μm) 5 mass%, organic binder (C), polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) was mixed at a ratio of 10% by mass, and an adsorbing sheet was prepared using a wet papermaking machine (manufactured by Toyobo Engineering Co., Ltd., the same applies hereinafter) at a mass of basis weight 70 g / m ² . Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained sample was measured for heat resistance, supportability, flexibility, and adsorption performance.

(Experimental example 2-2)
As the porous metal complex (A), Basolite A100 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-2) in which solvent molecules were adsorbed in the pores. 70% by mass of the porous metal complex sample (A2-2), heat-resistant fiber (D), 15% by mass of glass fiber (fiber diameter 6 μm, fiber length 3 mm), and clay mineral fiber (E), magnesium silicate Fiber (fiber diameter 0.1 μm, fiber length 1 μm) 5 mass%, organic binder (C), polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) 10 mass% The adsorbent sheet was prepared using a wet papermaking machine with a mass of basis weight 70 g / m ² . Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.

(Experimental Example 2-3)
As a porous metal complex (A), Basolite C300 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in ethanol for 24 hours and then filtered to obtain a porous metal complex sample (A2-3) in which solvent molecules were adsorbed in the pores. 70% by mass of the porous metal complex sample (A2-3), heat-resistant fiber (D), 15% by mass of glass fiber (fiber diameter 6 μm, fiber length 3 mm), and clay mineral fiber (E), magnesium silicate Fiber (fiber diameter 0.1 μm, fiber length 1 μm) 5 mass%, organic binder (C), polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) 10 mass% The adsorbent sheet was prepared using a wet papermaking machine with a mass of basis weight 70 g / m ² . Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.

(Experimental example 2-4)
As a porous metal complex (A), Basolite F300 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-4) in which solvent molecules were adsorbed in the pores. 70% by mass of the porous metal complex sample (A2-4), heat-resistant fiber (D), 15% by mass of glass fiber (fiber diameter 6 μm, fiber length 3 mm), and magnesium mineral silicate as clay mineral fiber (E) Fiber (fiber diameter 0.1 μm, fiber length 1 μm) 5 mass%, organic binder (C), polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) 10 mass% The adsorbent sheet was prepared using a wet papermaking machine with a mass of basis weight 70 g / m ² . Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.

(Experimental Example 2-5)
As the porous metal complex (A), Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-5) in which solvent molecules were adsorbed in the pores. The porous metal complex sample (A2-5) is 60% by mass, heat-resistant fiber (D), glass fiber (fiber diameter 6 μm, fiber length 3 mm) is 15% by mass, and clay mineral fiber (E) is magnesium silicate. Fiber (fiber diameter 0.2 μm, fiber length 30 μm) 15 mass%, organic binder (C), polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) 10 mass% The adsorbent sheet was prepared using a wet papermaking machine with a mass of basis weight 70 g / m ² . Further, the solvent removal treatment was performed at 150 ° C. and 1 atm for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.

(Experimental Example 2-6)
As the porous metal complex (A), Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-6) in which solvent molecules were adsorbed in the pores. 60% by mass of the porous metal complex sample (A2-6), heat-resistant fiber (D), and fibrillated aramid fiber (Teijin, Twaron (registered trademark), fiber diameter 12 μm, fiber length 3 mm) 15 15% by mass of magnesium silicate fiber (fiber diameter: 0.1 μm, fiber length: 1 μm) as clay mineral fiber (E), polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105) as organic binder (C) , Fiber diameter 11 μm, fiber length 3 mm) were mixed at a ratio of 10% by mass, and an adsorbent sheet was prepared using a wet papermaking apparatus at a mass of basis weight 70 g / m ² . Furthermore, the solvent removal treatment was performed at 150 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.

(Experimental example 2-7)
As the porous metal complex (A), Basolite Z1200 (manufactured by BASF) was sieved to prepare an average particle size of 10 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-7) in which solvent molecules were adsorbed in the pores. Magnesium silicate containing 60% by mass of the porous metal complex sample (A2-7), heat-resistant fiber (D), 15% by mass of glass fiber (fiber diameter 6 μm, fiber length 3 mm), and clay mineral fiber (E) Fiber (fiber diameter 0.1 μm, fiber length 1 μm) 15 mass%, organic binder (C), polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) 10 mass% The adsorbent sheet was prepared using a wet papermaking machine with a mass of basis weight 70 g / m ² . Furthermore, the solvent removal treatment was performed at 150 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.

(Experimental Example 2-8)
As the porous metal complex (A), Basolite Z1200 (manufactured by BASF) was lightly pressed and hardened at a pressure of 10 kgf / cm ² and sieved to prepare an average particle size of 150 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-8) in which solvent molecules were adsorbed in the pores. The porous metal complex sample (A2-8) is 60% by mass, heat-resistant fiber (D), glass fiber (fiber diameter 6 μm, fiber length 3 mm) is 15% by mass, and clay mineral fiber (E) is magnesium silicate. Fiber (fiber diameter 0.1 μm, fiber length 1 μm) 15 mass%, organic binder (C), polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) 10 mass% The adsorbent sheet was prepared using a wet papermaking machine with a mass of basis weight 70 g / m ² . Furthermore, the solvent removal treatment was performed at 150 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.

(Experimental example 2-9)
As the porous metal complex (A), Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-9) in which solvent molecules were adsorbed in the pores. 80% by mass of the porous metal complex sample (A2-9), heat-resistant fiber (D), 10% by mass of glass fiber (fiber diameter 6 μm, fiber length 3 mm), and clay mineral fiber (E), magnesium silicate 5% by mass of fibers (fiber diameter 0.1 μm, fiber length 1 μm) and 5% by mass of polyvinyl alcohol (PVA) fibers (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) as organic binder (C) The adsorbent sheet was prepared using a wet papermaking machine with a mass of basis weight 70 g / m ² . Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample, and the obtained sample was measured for heat resistance, supportability, flexibility, and adsorption performance.

(Experimental example 2-10)
As the porous metal complex (A), Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-10) in which solvent molecules were adsorbed in the pores. 70% by mass of the porous metal complex sample (A2-10), heat-resistant fiber (D), 20% by mass of glass fiber (fiber diameter 6 μm, fiber length 3 mm), polyvinyl alcohol (C) as polyvinyl alcohol (C) PVA) fibers (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) were mixed at a ratio of 10% by mass, and an adsorbent sheet was prepared using a wet papermaking machine at a mass of basis weight 70 g / m ² . . Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.

(Experimental example 2-11)
As the porous metal complex (A), Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-11) in which solvent molecules were adsorbed in the pores. 70% by mass of the porous metal complex sample (A2-11), heat-resistant fiber (D), 20% by mass of glass fiber (fiber diameter 6 μm, fiber length 3 mm), and clay mineral fiber (E), magnesium silicate Fibers (fiber diameter: 0.1 μm, fiber length: 1 μm) were mixed at a ratio of 10% by mass, and an adsorbing sheet was prepared using a wet papermaking machine at a mass of basis weight 70 g / m ² . Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.

(Experimental example 2-12)
HSZ-390HUA (Y-type zeolite manufactured by Tosoh Corporation) was pulverized in a mortar and sieved to prepare an average particle size of 1 μm. The obtained zeolite sample was 70% by mass, heat-resistant fiber (D), glass fiber (fiber diameter 6 μm, fiber length 3 mm) 15% by mass, clay mineral fiber (E), magnesium silicate fiber (fiber diameter 0. 1 μm, fiber length of 1 μm) as an organic binder (C), polyvinyl alcohol (PVA) fibers (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter of 11 μm, fiber length of 3 mm) are mixed at a ratio of 10% by mass, An adsorption sheet was prepared using a wet papermaking machine at a mass of basis weight 70 g / m ² . Furthermore, it processed in 200 degreeC and vacuum conditions for 24 hours, and the adsorption sheet sample was obtained. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.

(Experimental Example 2-13)
Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and sieved to prepare an average particle size of 1 μm. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-12) in which solvent molecules were adsorbed in the pores. 70% by mass of the porous metal complex sample (A2-12), 15% by mass of polybutylene terephthalate fiber (fiber diameter 6 μm, fiber length 3 mm) instead of heat resistant fiber (D), and clay mineral fiber (E) , Magnesium silicate fiber (fiber diameter 0.1 μm, fiber length 1 μm) 5 mass%, organic binder (C), polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) An adsorbing sheet was prepared using a wet papermaking apparatus at a mass of 70 g / m ² with a basis weight of 70 g / m ² . Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.

(Experimental Example 2-14)
Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and sieved to prepare an average particle size of 1 μm. Further, the sample was subjected to solvent removal treatment at 200 ° C. under vacuum for 24 hours to obtain a porous metal complex sample (A2-13). The porous metal complex sample (A2-13) was 70% by mass, the polybutylene terephthalate fiber (fiber diameter 6 μm, fiber length 3 mm) was 15% by mass, and the clay mineral fiber (E) was magnesium silicate fiber (fiber diameter 0. 1 μm, fiber length of 1 μm) as an organic binder (C), polyvinyl alcohol (PVA) fibers (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter of 11 μm, fiber length of 3 mm) are mixed at a ratio of 10% by mass, An adsorption sheet was prepared using a wet papermaking machine at a mass of basis weight 70 g / m ² . Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.

(Experimental Example 2-15)
Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and sieved to prepare an average particle size of 1 μm. Further, the sample was subjected to solvent removal treatment at 200 ° C. under vacuum for 24 hours to obtain a porous metal complex sample (A2-14). 70% by mass of the porous metal complex sample (A2-14), 15% by mass of polybutylene terephthalate fiber (fiber diameter 6 μm, fiber length 3 mm) instead of heat resistant fiber (D), clay mineral fiber (E) As magnesium silicate fiber (fiber diameter 0.1 μm, fiber length 1 μm) 5 mass%, organic binder (C), polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 μm, fiber length 3 mm) Were mixed at a ratio of 10% by mass, and an adsorbing sheet was prepared using a wet papermaking apparatus at a mass of 70 g / m ² basis weight. Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.

Table 1 or 2 shows the results of measuring the heat resistance, supportability, flexibility, and adsorption performance of the samples of Experimental Examples 2-1 to 2-15. As is apparent from Tables 1 and 2, in Examples 2-1 to 2-11, which are examples of the present invention, when the adsorbent is not the porous metal complex (A) (Experimental Example 2-12), the heat resistant fiber It can be seen that heat resistance, supportability, flexibility, and adsorption performance are superior to those in the case where (D) is not included (Experimental Examples 2-13, 2-14, and 2-15). Further, when the clay mineral fiber (E) is not included (Experimental Example 2-10), and when the organic binder (C) is not included (Experimental Example 2-11), the heat resistance, A tendency to be slightly inferior in supportability or flexibility was observed.

The first adsorption sheet of the present invention can be reproduced without impairing the adsorption behavior of the porous metal complex (A) in which a hysteresis loop is seen in the adsorption / desorption isotherm depending on the type of gas. Moreover, since the content ratio of a porous metal complex (A) can also be raised by setting it as the shape of an adsorption sheet, the 1st adsorption sheet of this invention has the outstanding adsorption / desorption characteristic. Therefore, the first adsorbing sheet of the present invention can be used in applications such as adsorbents, occlusion materials, and separating materials, and the adsorbent can be desorbed by placing the first adsorbing sheet of the present invention under reduced pressure. Since the regeneration of the adsorption performance is easy, it is extremely meaningful in the industry.

In addition, according to the second adsorbing sheet or adsorbing element of the present invention, it becomes possible to efficiently separate / recover or adsorb / remove moisture, organic solvents, and malodorous components in the air. It can be expected to greatly contribute to the world.

Claims (11)

1. An adsorbent sheet comprising a porous metal complex (A) having a porous structure composed of a metal ion and an organic ligand capable of binding to the metal ion, and an organic fiber (B).
2. The adsorbent sheet according to claim 1, comprising 50% by mass to 90% by mass of the porous metal complex (A).
3. The adsorption and desorption isotherm of the porous metal complex (A) with respect to at least one gas selected from the group consisting of hydrogen, oxygen, nitrogen, carbon monoxide, carbon dioxide, and hydrocarbons having 1 to 4 carbon atoms is a hysteresis loop. The adsorption sheet according to claim 1 or 2 showing.
4. The adsorbing sheet according to any one of claims 1 to 3, wherein the organic ligand is at least one organic compound selected from the group consisting of the following (1) to (3).
   (1) Organic compound having two or more carboxyl groups and / or hydroxyl groups in the molecule, having no heterocyclic ring, and capable of bidentate coordination with metal ions (2) In the molecule, N, O or S A monocyclic or polycyclic saturated or unsaturated heterocyclic ring having one heteroatom selected from the following: an organic compound having a carboxyl group or a hydroxyl group and capable of bidentate coordination to a metal ion (3) Intramolecular And a bidentate organic compound having a monocyclic or polycyclic saturated or unsaturated heterocycle having 2 or more heteroatoms selected from the group consisting of N, O and S
5. The organic ligand is an alkylene dicarboxylic acid compound having 4 to 20 carbon atoms, an alkenylene dicarboxylic acid compound having 4 to 20 carbon atoms, or a dicarboxylic acid compound represented by the following general formulas (I) to (III);
   

   

   
   (Wherein R ^{1 s} are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a formyl group, carbon An acyloxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having an alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyano group, a carboxyl group, an amino group, a monoalkylamino group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms And a dialkylamino group having an alkyl group or an acylamino group having 1 to 4 carbon atoms, and two or more R ¹ may be cyclic, or two or more R ¹ may be condensed cyclically.) ,
   Dicarboxylic acid compound represented by the following general formula (IV);
   

   

   
   (Wherein R ^{2 s} are the same or different and each represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent, and X represents a hydrogen atom or a substituent. Or an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, or an amino group. ),
   An organic compound represented by the following general formula (V);
   

   

   
   (Wherein R ³ are the same or different and each represents a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms) Or an alkoxy group having 1 to 4 carbon atoms).
   Organic compounds represented by the following general formulas (VI) to (VIII);
   

   

   
   (Wherein R ³ are the same or different and each represents a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms) Or an alkoxy group having 1 to 4 carbon atoms), and
   Organic compounds represented by the following general formulas (IX) to (XII);
   

   

   
   Wherein Y is the same or different and represents an oxygen atom, a sulfur atom, —CH ₂ —, —CH (OH) —, —CO—, —NH—, —C ₂ N ₄ —, —C≡C—, —C ₂ H ₂ — or —C ₆ H ₄ —, wherein R ^{4 s} are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, carbon An alkoxy group having 1 to 4 carbon atoms, a formyl group, an acyloxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having an alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyano group, a carboxyl group, an amino group, 1 to carbon atoms 4 monoalkylamino groups, dialkylamino groups having 1 to 4 carbon atoms or acylamino groups having 1 to 4 carbon atoms, and n is an integer of 0 to 3). The organic compound according to any one of claims 1 to 4, which is one or more organic compounds. Adsorption sheet according.
6. The adsorbent sheet according to any one of claims 1 to 5, wherein the organic fiber (B) is cellulose.
7. The adsorbent sheet according to any one of claims 1 to 6, which is produced by a wet papermaking method.
8. An adsorption sheet comprising a porous metal complex (A) and a heat-resistant fiber (D).
9. The adsorbent sheet according to claim 8, wherein the adsorbent sheet contains clay mineral fibers (E) having self-consolidating properties.
10. The adsorption sheet according to claim 8 or 9, wherein the adsorption sheet contains an organic binder (C).
11. A suction element comprising the suction sheet according to any one of claims 8 to 10.

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