WO2021153626A1 - Adsorbent sheet, adsorbent element, and adsorption treatment device using same - Google Patents

Abstract

An adsorbent sheet of the present invention comprises: a porous metal complex comprising a metal and an organic ligand and having a water adsorption ratio of 30% by mass or more at 25°C under a relative pressure of 0.5; and a non-fibrillated fiber and a fibrillated fiber. The adsorbent sheet is excellent in the property of supporting the porous metal complex and the flexibility/processability of the sheet, and can exert sufficient adsorption performance.

Description

Adsorption sheet, adsorption element, and adsorption processing device using it

The present invention relates to an adsorption sheet, an adsorption element, and an adsorption treatment apparatus using the adsorption sheet, which efficiently separates, recovers, or adsorbs and removes substances to be adsorbed such as moisture, organic solvent, and malodorous components.

Porous materials such as activated carbon, silica gel, and zeolite are used for various purposes such as deodorization, purification of air and water, and separation / purification of gas, and are indispensable materials for modern life. In recent years, a porous material in which a metal ion capable of taking various coordination forms and a bridging ligand having two or more coordinations are combined and self-assembled, that is, a porous metal complex (MOF), or a porous metal complex (MOF), or A new porous material called Porous Coordination Polymer (PCP) has been discovered. These porous metal complexes have features such as high specific surface area, sharp pore distribution, and high structural design, which are features not found in conventional porous materials such as activated carbon, silica gel, and zeolite. Attention has been paid.

As such a porous metal complex, for example, Patent Document 1 discloses that a specific dicarboxylic acid metal complex is suitable as a gas occlusion material, particularly a gas occlusion material containing methane as a main component. Further, Patent Document 2 discloses a porous metal complex synthesized from copper ions and trimesic acids, and an adsorbent is disclosed as an example of its use. Further, Patent Document 3 discloses that a metal chromium or a chromium salt and a porous metal complex obtained from trimesic acids are particularly excellent as a water vapor adsorbent.

In this way, the porous metal complex has the potential as an adsorbent for various gases. When used as an adsorbent, it is preferable to mold the porous metal complex existing as powder into an adsorbent element suitable for use so that it can come into contact with the operating fluid with little pressure loss. It becomes important to establish.

Therefore, Patent Document 4 discloses an adsorption sheet containing a porous metal complex, a heat-resistant fiber, a self-consolidating clay mineral fiber, and an organic binder as a sheet containing the porous metal complex. ..

Japanese Patent Publication "Japanese Patent Laid-Open No. 2001-348361" Japanese Patent Publication "Japanese Patent Laid-Open No. 2000-327628" Japanese Patent Publication "Japanese Patent Laid-Open No. 2007-51112" Japanese Patent Publication "Japanese Patent Laid-Open No. 2013-154301"

However, the adsorption sheet disclosed in Patent Document 4 requires clay mineral fibers, and the heat-resistant fiber content ratio is reduced by that amount. Therefore, the sheet itself is not stiff, and for example, a step is formed during honeycomb processing when making a filter. There are problems such as not sticking.

Therefore, the present invention relates to an adsorption sheet, an adsorption element, and an adsorption / desorption treatment apparatus using the adsorption sheet, which is excellent in the supportability of the porous metal complex and the flexibility and processability of the sheet, and has sufficient adsorption performance. Is raised as an issue.

As a result of diligent research in order to solve the above problems, the present inventors have finally completed the present invention. That is, the present invention has the following configuration.
[1] A porous metal complex having a metal and an organic ligand and having a water adsorption rate of 30% by mass or more at 25 ° C. and a relative pressure of 0.5, and non-fibrillated fibers and fibrillated fibers. An adsorption sheet characterized by containing,.
[2] The adsorption sheet according to 1 above, which contains an organic binder having a dissolution temperature in water of 65 ° C. to 100 ° C.
[3] The adsorption sheet of 1 or 2 above, wherein the specific tensile elongation is 5% · m / g or more.
[4] The adsorption sheet according to any one of 1 to 3 above, which contains 60 to 85% by mass of the porous metal complex.
[5] An adsorption element comprising any one of the above 1 to 4 adsorption sheets.
[6] The adsorption target substance is provided with the adsorption element of 5 above, an adsorption means for introducing and adsorbing the adsorption target substance into the adsorption element, and a desorption means for desorbing the adsorption target substance adsorbed by the adsorption element. An adsorption / desorption processing device that continuously performs adsorption / desorption.

According to the above configuration, it is possible to provide an adsorption sheet or the like which is excellent in the supportability of the porous metal complex and the flexibility and processability of the sheet and has sufficient adsorption performance.

It is a figure which shows an example of the single-stage sheet which processed the adsorption sheet of this invention into a corrugated shape. It is a figure which shows an example of the adsorption element of this invention. It is a figure which shows an example of the adsorption / desorption processing apparatus of this invention.

Hereinafter, the present invention will be described in detail.
The adsorption sheet of the present invention contains a porous metal complex having a metal and an organic ligand and having a water adsorption rate of 30% by mass or more at 25 ° C. and a relative pressure of 0.5, and non-fibrillated fibers and fibrils. Containing the carbonized fiber.
Here, the pressure in a state where the progress of adsorption seems to have stopped under a constant pressure (the number of adsorbed molecules = the number of desorbed molecules) is called the adsorption equilibrium pressure, and the relative pressure is the adsorption equilibrium pressure and the saturated vapor pressure. The ratio is called relative pressure.

Since the adsorption sheet of the present invention contains a porous metal complex, high adsorption performance can be obtained. Moreover, since this porous metal complex is characterized in that the water adsorption rate at 25 ° C. and a relative pressure of 0.5 is 30% by mass or more, a large amount of water can be retained by the sheet itself, and the sheet can be processed. High flexibility of time is obtained. Furthermore, since the porous metal complex can sufficiently develop flexibility, it is possible to reduce the amount of organic binder conventionally used for imparting flexibility, and as a result, it is possible to reduce the amount of organic binder in the pores of the adsorbent. The rate of adsorption (porosity) of the side chains of the binder and the like can be reduced, and further sufficient adsorption performance can be obtained. If the water adsorption rate is less than 30% by mass, the flexibility will be lacking.

Further, the adsorption sheet of the present invention contains non-fibrillated fibers and fibrillated fibers. By containing the fibers that are not fibrillated, for example, it is possible to maintain the step shape by itself even when step processing is performed, and the workability is excellent. Further, by containing the fibrillated fiber, the porous metal complex particles can be efficiently retained, and not only the supportability is excellent, but also the organic binder conventionally used for imparting the supportability can be reduced. Is possible. As a result, pore clogging can be reduced, and more sufficient adsorption performance can be obtained.

Further, the adsorption sheet of the present invention may contain an organic binder having a melting point in water of 65 ° C. to 100 ° C. and a high melting point. By using an organic binder having a high melting point of 65 ° C. to 100 ° C. in water, it is possible to further reduce pore clogging and obtain excellent adsorption performance. If the dissolution temperature in water is less than 65 ° C., the adsorption performance will be insufficient due to pore clogging, and if the temperature is higher than 100 ° C., the adhesion will be insufficient and the supportability will be insufficient.

The porous metal complex according to the present invention is a porous material composed of a metal ion and a compound having an organic ligand. The form of the porous metal complex that can be used is not particularly specified, and powder or granular ones can be used. It is preferably a porous metal complex having an average particle size of 0.1 μm to 200 μm, more preferably 1 to 100 μm, and most preferably 1 to 80 μm. If the average particle size is less than 0.1 μm, the yield during the adsorption sheet formation becomes low. On the other hand, if the average particle size exceeds 200 μm, it becomes difficult to sufficiently support the porous metal complex on the adsorption sheet, and the porous metal complex may come off more often. The average particle size can be measured using, for example, a scanning electron microscope.

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. This is because if it exceeds this range, there is a disadvantage that the production of the porous metal complex becomes very difficult. The BET specific surface area can be measured, for example, by the method described in the subsequent examples.

The metal ions constituting the porous metal complex are not particularly limited, and examples thereof include typical metal elements such as aluminum ions and transition metal elements such as titanium ions, zirconium ions, iron ions, and copper ions. On the other hand, examples of the compound having a ligand include fumaric acid, 2-aminoterephthalic acid, 1,4-naphthalenedicarboxylic acid, terephthalic acid, trimesic acid and the like. Specific examples of the porous metal complex include a porous metal complex composed of aluminum ions and terephthalic acid (Basolite A100 manufactured by BASF) and a porous metal complex composed of copper ions and trimesic acid (BASF). , Basolite C300), a porous metal complex composed of iron ions and trimesic acid (BASF, Basolite F300), a porous metal complex composed of titanium ions and terephthalic acid, and composed of zirconium ions and terephthalic acid. Porous metal complex, porous metal complex composed of zirconium ion and fumaric acid, porous metal complex composed of zirconium ion and 2-aminoterephthalic acid, porous metal complex composed of titanium ion and 2-aminoterephthalic acid Examples include a sex metal complex. Even if these porous metal complexes are the same porous metal complex, the BET specific surface area varies depending on the synthesis method and purity, but in order to impart the flexibility of the adsorption sheet, the relative pressure is 0.5 at 25 ° C. The water adsorption rate in the above is preferably 30% by mass or more, more preferably 35% by mass or more, and further preferably 40% by mass or more. If it is less than 30% by mass, it is necessary to increase the content of the organic binder in order to impart sufficient flexibility to the adsorption sheet. If the content of the organic binder is high, the side chains and the like of the organic binder are often adsorbed in the pores of the adsorbent, and as a result, sufficient adsorption performance cannot be exhibited.

The content of the porous metal complex in the adsorption sheet of the present invention is preferably 60% by mass to 85% by mass, more preferably 65% by mass to 80% by mass. If the content is less than 60% by mass, it may be difficult to obtain sufficient adsorption performance. On the other hand, if the content exceeds 85% by mass, it becomes difficult to sufficiently support the porous metal complex on the adsorption sheet, and the amount of shedding increases. In addition, the sheet strength may be significantly reduced.

The fiber diameter of the non-fibrilized fiber is preferably 5 μm or more, and more preferably 5 μm to 30 μm. The fiber length is preferably 1 mm to 10 mm, more preferably 2 mm to 8 mm. If the fiber diameter of the thick fiber is less than 5 μm and the fiber length is less than 1 mm, the strength of the sheet decreases, it is difficult to maintain the step shape by itself after the step processing, and it is processed into a honeycomb-shaped adsorption element in the post processing. This is because it becomes impossible. Further, if the fiber diameter of the non-fibrillated fiber exceeds 30 μm and the fiber length exceeds 10 mm, the fiber is inflexible and difficult to process. Further, fibers having different fiber diameters may be mixed.

Examples of non-fibrillated fibers include inorganic fibers such as glass fibers, ceramic fibers and rock wool fibers; synthetic fibers such as aramid fibers, meta-aramid fibers, polybenzimidazole fibers, polyether ketone fibers, polyethylene terephthalate fibers and nylon fibers;
Examples include semi-synthetic fibers such as acetate fibers and triacetate fibers; rayon fibers; regenerated fibers such as cupra fibers; and plant fibers such as cotton, hemp, and wood-based fibers. One or more of these can be used.

Examples of the fibrillated fiber include pulp and the like in addition to the fibrillated fiber described above. One or more of these can be used. The method of fibrillation is not particularly limited, and a normal beating method can be adopted. A typical example is a method of fibrilizing using a beating machine such as a beater or a refiner. Further, the fibrilized fiber is preferably 50 ml or more and less than 800 ml when the Canadian standard drainage degree (CSF) according to JIS P 811-2 is measured.

The total content of the non-fibrillated fibers and the fibrillated fibers in the adsorption sheet of the present invention is preferably 5% by mass to 25% by mass, more preferably 10% by mass to 25% by mass. If the content is less than 5% by mass, it becomes difficult to sufficiently support the porous metal complex on the adsorption sheet, the amount of falling off may increase, and the strength of the sheet may be significantly reduced. On the other hand, if the content exceeds 25% by mass, it may be difficult to obtain sufficient adsorption performance.

The adsorption sheet in the present invention contains an organic binder. This is because the flexibility and strength of the adsorption sheet are improved. The organic binder is not particularly limited as long as it can bond the porous metal complex and the fiber. For example, polyvinyl alcohol-based polymers, polyacrylonitrile-based polymers, polyethylene-based polymers, polyester-based polymers, polyphenylene ether-based polymers, and the like can be used. From the viewpoint of handleability, a polyvinyl alcohol-based polymer is preferable. The mode of use of the organic binder is not particularly limited, but it is preferable to use a fibrous binder because an adsorption sheet can be easily produced. The content of the organic binder in the adsorption sheet is preferably 3% by mass to 15% by mass, more preferably 4% by mass to 12% by mass. If it is less than 3% by mass, the supportability of the porous metal complex and the flexibility of the sheet are insufficient, and if it exceeds 15% by mass, the porous metal complex is coated with the organic binder, and it tends to be difficult to obtain sufficient adsorption performance. There is.

The dissolution temperature of the organic binder in water is preferably 65 ° C to 100 ° C, more preferably 70 ° C to 100 ° C. If the dissolution temperature in water is less than 65 ° C., the proportion of the binder side chain entering the pores of the porous metal complex increases, and as a result, the adsorption performance may be insufficient. Further, if the temperature is higher than 100 ° C., there is a problem that the supportability is lacking due to insufficient adhesion.

The dissolution temperature of the organic binder in water can be measured by a usual method. For example, 100 ml of pure water is placed in a beaker and stirred, heated in an oil bath until the water temperature reaches 50 ° C., 0.5 g of an organic binder is added thereto, and the water temperature is raised at a heating rate of 2 ° C./min. , There is a method of visually measuring the temperature when the binder begins to melt and becomes translucent.

The adsorption sheet of the present invention exhibits supportability due to the fibrillated fibers even if the content of the organic binder is small, and exhibits the flexibility of the adsorption sheet due to the high water adsorption rate of the porous metal complex. As a result, it is possible to exhibit sufficient adsorption performance due to the small amount of organic binder and the high adsorption performance of the porous metal complex itself.

The adsorption sheet of the present invention preferably has a specific tensile elongation of 5% · m / g or more as an index of flexibility. If it is less than 5% m / g, the sheet lacks flexibility and cracks occur during honeycomb processing (step processing).

The adsorption sheet of the present invention may contain one or more types of porous metal complexes, and may further contain a porous material other than the porous metal complex. The porous material contained in the adsorption sheet of the present invention is not particularly limited, but for example, organic highs such as activated carbon, zeolite, silica gel, activated alumina, aluminophosphate, silicoaluminolic acid, and styrene-divinylbenzene copolymer. Examples include molecular porous materials. Preferred are activated carbon, zeolite, silica gel, and activated alumina, which are inexpensively available.

The thickness of the adsorption sheet of the present invention is preferably 0.1 mm to 0.9 mm, more preferably 0.1 mm to 0.7 mm. If the thickness is less than 0.1 mm, the sheet strength is remarkably lowered, so that it may be difficult to process the adsorption element into a honeycomb shape or the like in the post-processing. Further, if the thickness is larger than 0.9 mm, the pressure loss of the suction element when the suction sheet is processed into a honeycomb shape or the like tends to be high.

The basis weight of the adsorption 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 become thin and the sheet strength may be significantly reduced, which may make it difficult to process the adsorption element such as a honeycomb shape in the post-processing. Further, if the basis weight ^{exceeds 200 g / m 2} , the thickness of the sheet may become too large, and the pressure loss of the suction element when processed into a honeycomb shape or the like may increase.

The method for producing the adsorption sheet of the present invention is not particularly limited, and a conventionally known processing method can be used. Preferably, a wet sheeting method obtained by dispersing the porous metal complex, the fiber, and the organic binder in water, an organic solvent, or a mixture thereof, forming, dehydrating, and drying the mixture can be mentioned.

Here, it is preferable that the porous metal complex is mixed with the above-mentioned sheet constituent material in a state of having solvent molecules in its pores and subjected to the sheet forming step. If the porous metal complex does not have solvent molecules in the pores, the organic binder constituting the adsorption sheet may be adsorbed in the pores. In this case, it is difficult to remove the organic binder trapped in the pores of the porous metal complex even if the solvent removal treatment described later is carried out after the sheet is formed, resulting in inferior adsorption performance of the adsorption sheet. That is, in the present invention, by adsorbing the solvent molecules in the pores of the porous metal complex, the adsorption of the organic binder or the like in the pores in the sheeting step is prevented, and after the sheeting step, the solvent is removed, which will be described later. By removing the solvent molecules from the pores by the treatment, the adsorption performance of the adsorption sheet is ensured. Normally, at the stage of synthesizing a porous metal complex, solvent molecules are adsorbed in the pores of the porous metal complex, but when the porous metal complex does not have solvent molecules in the pores or solvent molecules. When the amount of adsorbed is insufficient, the organic solvent can be adsorbed in the pores by the method described in Examples described later. Here, the solvent molecule refers to water or a general organic solvent molecule.

When producing the adsorption sheet of the present invention, a solvent removal treatment step of removing the solvent contained in the adsorption sheet is carried out after the sheet forming step. As described above, the porous metal complex is preferably sheeted with solvent molecules in its pores, and in this case, sufficient adsorption performance can be obtained by the solvent molecules in the pores of the porous metal complex. It's hard to get rid of. Therefore, in order to develop the adsorption performance, the solvent removal treatment is carried out after the sheeting step. The timing of the desolvation treatment is not particularly limited as long as it is after the sheeting step.

The conditions for the desolvation treatment are not particularly specified, but the temperature is preferably 50 ° C. to 300 ° C. If the temperature is lower than 50 ° C., the removal of the solvent may be incomplete, and it may be difficult to obtain sufficient adsorption performance. On the other hand, if the temperature exceeds 300 ° C., the pore structure of the porous metal complex may be broken, and in this case as well, it becomes difficult to obtain sufficient adsorption performance. More preferably, it is 80 ° C. to 200 ° C. Further, the solvent can be removed more efficiently by carrying out the desolvation treatment under reduced pressure. At this time, the pressure is not particularly limited and may be appropriately adjusted according to the physical properties and the blending amount of the porous metal complex. For example, 10 ³ Pa to 10 ^-5 Pa is preferable, and 10 ^-1 Pa to 10 ^{-5 is preferable.} Pa is more preferable. The desolvation treatment time is also not particularly limited, but is preferably 1 hour to 100 hours, more preferably 3 hours to 48 hours, and further preferably 3 hours to 24 hours. The most preferable desolvation treatment conditions are 80 ° C. to 200 ° C. for 3 hours to 24 hours under vacuum conditions.

The adsorption sheet of the present invention may be used in a flat plate shape, or may be appropriately subjected to pleating, honeycomb processing, corrugated processing, or the like to be used as a desired shape. FIG. 1 shows a single-stage sheet obtained by processing the suction sheet 1 into a corrugated shape as an example of processing the suction sheet of the present invention. In particular, pleating, honeycombing, and corrugating require a step of bending the sheet during processing, and at that time, the flexibility of the sheet is exhibited by sufficiently adsorbing water to the porous metal complex before processing. Will be done. The method for adsorbing water to the porous metal complex is not particularly specified, but a method such as using a humidified room or processing while spraying steam is convenient and preferable.

The adsorption element of the present invention is characterized by including the above-mentioned adsorption sheet of the present invention. The type of the adsorption element of the present invention is not particularly limited, and any conventionally known type can be adopted and may be appropriately selected depending on the intended use and purpose. 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 plate shape, a pleated shape, a honeycomb shape, or the like can be used. For example, the pleated adsorption sheet is used as a orthogonal flow type adsorption element, and the honeycomb-shaped adsorption sheet is used as a parallel flow type adsorption element. It is possible to increase the area to improve the removal efficiency of the substance to be adsorbed and to reduce the low pressure of the adsorption element at the same time. Compared to the orthogonal flow type adsorption element, the parallel flow type adsorption element is superior 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 preferably shaped.

FIG. 2 shows a diagram of a suction rotor 2 in which the suction sheet of the present invention is wound in a rotor shape as an example of the suction element of the present invention. The suction sheet provided in the suction rotor 2 has a honeycomb shape.

The adsorption sheet of the present invention and the adsorption element provided with the adsorption sheet are discharged from factories, etc. for the purpose of reducing malodorous components, etc. in indoors, in vehicles, wallpaper, furniture, interior materials, resin molded products, electrical equipment, etc. It can be widely used for the purpose of separating / recovering organic solvents in the air, or controlling humidity / desiccant.

The present invention also relates to an adsorption / desorption processing apparatus including the adsorption element of the present invention, an adsorption means for introducing an adsorption target substance into the adsorption element and adsorbing the substance, and a desorption means for desorbing the adsorption target substance adsorbed by the adsorption element. Is included in the range of. As the adsorption means, a pipe or the like for introducing air or gas containing a malodorous substance such as an organic solvent or a substance to be adsorbed such as moisture can be considered. As a method for desorbing the substance to be adsorbed, there are a method of heating and a method of lowering the pressure of the system, and as a desorption means, a tube for introducing a heating gas, a heater, a decompressor, or the like can be considered. A means for introducing heated air is desirable from the viewpoint of desorption efficiency and economy.

FIG. 3 shows a desiccant air conditioning system 11 as an example of the suction / desorption processing device of the present invention. The desiccant air conditioning system 11 includes a suction type rotor 2, a motor 3, a heat source 8 such as a heater, a fan 9, and a dehumidifying / humidifying area dividing member 10. In the desiccant air conditioning system 11, when the high-humidity gas 4 containing water as the substance to be adsorbed is introduced, the water is adsorbed by the adsorption rotor 2 and discharged as the gas 5 after dehumidification. When the low-humidity gas 6 heated by the heat source 8 is introduced, the water adsorbed on the adsorption rotor 2 is desorbed and discharged as the gas 7 after humidification. The suction / desorption treatment device of the present invention can be applied to both a desiccant air conditioning system for factories and a desiccant air conditioning system for home use.

Hereinafter, the present invention will be described more specifically by way of examples. It should be noted that the following examples do not have the property of limiting the present invention, and any design change according to the gist of the above and the following is included in the technical scope of the present invention.
First, the measurement method and the evaluation method of the characteristic values obtained in Examples and Comparative Examples are shown below.

[Moisture adsorption rate]
Approximately 100 mg of the porous metal complex (before treatment with water or organic solvent) is collected, vacuum dried at 120 ° C. for 12 hours, and then weighed. Using a high-precision gas / vapor adsorption amount measuring device (BELSORP-max, manufactured by Nippon Bell Co., Ltd.), increase the adsorption amount of water vapor at 25 ° C in the range of 0.02 to 0.95 while gradually increasing 40. Measure points and create an adsorption isotherm. At this time, the target relative pressure is 0.001, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8. , is set to 0.9, further relative pressure adsorption amount decrease allowable amount 0-0.3 in 30 cm ² / g, relative pressure 0.3-0.5 in 50 cm ² / g, a relative pressure of 0.5 at ~ Set to 30 cm ² / g and create an adsorption isotherm. Then, the water adsorption rate [%] is calculated by the following formula (i) from the water adsorption amount [g] per 1 g of the porous metal complex at a relative pressure of 0.5.
Moisture adsorption rate [%] = Moisture adsorption amount per 1 g of adsorbent [g] × 100 ... (i)

[BET specific surface area]
Approximately 100 mg of the porous metal complex (before treatment with water or organic solvent) is collected, vacuum dried at 120 ° C. for 12 hours, and then weighed. Using an automatic specific surface area measuring device (Gemini 2375, manufactured by Micromeritix), the adsorption amount of nitrogen gas at the boiling point (-195.8 ° C.) of liquid nitrogen was adjusted to a relative pressure of 0.02 to 0.95. Measure 40 points while gradually increasing in the range to create an adsorption isotherm. Using the analysis software (GEMINI-PCW version 1.01) attached to the automatic specific surface area measuring device, set the surface area analysis range to 0.01 to 0.15 under BET conditions, and set the BET specific surface area [m ² / g]. Ask for.

[Supportability]
A 10 cm × 10 cm test piece cut out from the adsorption sheet sample was fixed so that the flat portion of 10 cm × 10 cm was perpendicular to the laboratory table, and a sphere (material: aluminum) having a diameter of 2.4 cm and a mass of 20 g was tested therein. It is made to collide vertically with a flat portion of 10 cm × 10 cm 10 times. The sphere rolls at a speed of 10 cm / s. As a result, when the amount of the dropped porous metal complex is less than 0.1 mg, it is evaluated as ◯ (good), when it is more than 10 mg, it is evaluated as × (poor), and when it is 0.1 mg to 10 mg, it is evaluated as Δ (possible).

[Flexibility]
In the examples and the comparative examples, regarding the flexibility, it is observed whether or not the adsorption sheet is cracked during the honeycomb processing (step processing).
A 10 cm × 10 cm test piece cut out from the adsorption sheet sample is dried at 120 ° C. for 1 hour, and then allowed to stand at 22 ° C. for 1 hour in a 40% RH atmosphere. Hold both ends of the test piece whose humidity has been adjusted in this way, and bend it at 90 degrees. At this time, the sheet that does not crack is evaluated as ◯ (good), the sheet that cracks is evaluated as Δ (difficult), and the sheet that cracks is evaluated as × (defective).

[Specific tensile elongation]
A 15 mm × 100 mm test piece cut out from the adsorption sheet sample is dried at 120 ° C. for 1 hour, and the weight thereof is measured. Then, the dried sample is allowed to stand at 22 ° C. in a 40% RH atmosphere for 1 hour, and the maximum point elongation [%] is measured with a tensile / compression tester (TENSILON RTG-1310, manufactured by A & D Co., Ltd.). The distance between the chucks is 50 mm, and the tensile speed is 15 mm / min. From the obtained data, the specific tensile elongation is calculated by the following formula (ii).
Specific tensile elongation [% · m / g] = maximum point elongation [%] / sample width [m] / adsorption sheet basis weight [g / m ² ] ... (ii)

[Pore retention rate]
Approximately 100 mg of an adsorption sheet sample is collected, vacuum dried at 120 ° C. for 12 hours, and then weighed. Using an automatic specific surface area measuring device (Gemini 2375, manufactured by Micromeritix), the amount of nitrogen gas adsorbed at the boiling point (-195.8 ° C) of liquid nitrogen was adjusted to a relative pressure of 0.02 to 0.95. Measure 40 points while gradually increasing the temperature in the range to create an adsorption isotherm of the sample. Using the analysis software (GEMINI-PCW version 1.01) attached to the automatic specific surface area measuring device, set the surface area analysis range to 0.01 to 0.15 under BET conditions, and set the BET specific surface area [m ² / g]. Ask for. Then, the porosity is calculated by the following formula (iii) based on the BET specific surface area [m ^{2 / g] of the porous metal complex.}
Porosity [%] = {BET specific surface area of adsorption sheet [m ² / g] x 100 / (porosity of porous metal complex in adsorption sheet)} / (BET specific surface area of porous metal complex sample [m] ² / g]) × 100 ... (iii)
The higher the porosity, the higher the adsorption performance, indicating that the pores of the porous metal complex are not filled with a binder or the like (the pores are not closed).

[Sheet performance (water vapor adsorption amount)]
Approximately 100 mg of the porous metal complex (before treatment with water or organic solvent) is collected, vacuum dried at 120 ° C. for 12 hours, and then weighed. Using a high-precision gas / vapor adsorption amount measuring device (BELSORP-max, manufactured by Nippon Bell Co., Ltd.), increase the adsorption amount of water vapor at 25 ° C in the range of 0.02 to 0.95 while gradually increasing 40. Measure points and create an adsorption isotherm. Then, the amount of water vapor adsorbed [ml] per 1 g of the porous metal complex at a relative pressure of 0.95 is determined. As an evaluation of the sheet performance, an amount of water vapor adsorption of 410 ml / g or more is evaluated as 〇 (good), a value larger than 400 ml / g and less than 410 ml / g is evaluated as Δ (possible), and 400 ml / g or less is evaluated as × (defective).

[Workability]
In the examples and comparative examples, as workability, it is observed whether the step shape can be maintained by itself after the step processing.
The adsorption sheet sample is made to have a width of 30 cm and a length of 30 cm, and is theoretically passed through a corrugated processing machine capable of producing a corrugated paper having a width of 30 cm and a length of 21.4 cm. Then, after the corrugated adsorption sheet was allowed to stand for 24 hours at 22 ° C. in a 40% RH atmosphere, the recovery rate of the length was less than 20% (good) and 20% to less than 50% (good). Yes), 50% to 100% is evaluated as x (defective).

[Dissolution temperature in water]
When the dissolution temperature in water was actually measured with respect to the organic binder used in Examples and Comparative Examples by the following measuring method, it was the same as the catalog value except for the organic binder of Example 8. The catalog value of the organic binder of Example 8 was <99 ° C, but the measured value was 95 ° C.
4 mL of pure water and 0.02 g of an organic binder were placed in a 6 ml glass bottle. The glass bottle was placed in a water bath heated at intervals of 50 ° C. to 5 ° C. for 10 minutes. The organic binder in the bottle was stirred with a spatula every 2 minutes. The temperature at which the binder began to melt and became translucent was visually measured.

<Example 1>
And _{Fe (NO 3) 3 · 9H} 2 O16.2g (40mmol) and trimesic acid 7.5 g (36 mmol) was dissolved in water 32 ml, was synthesized porous metal complex was heated for 15 hours at 95 ° C.. As a result of evaluating the physical properties of the obtained porous metal complex by nitrogen adsorption measurement and water vapor adsorption measurement, the BET specific surface area was 1575 m ² / g and the water adsorption rate was 53%.
Then, the synthesized porous metal complex was immersed in water for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. This porous metal complex sample is 80% by mass (excluding solvent molecules), aramid fiber is 8% by mass as non-fibrillated fiber, aramid fiber is 5% by mass as fibrillated fiber, and the dissolution temperature in water is 70 as an organic binder. Polyvinyl alcohol (PVA) fibers at ° C (catalog value) are mixed at a ratio of 7% by mass, and adsorbed using a wet paper machine (manufactured by Toyo Boseki Engineering Co., Ltd., the same applies hereinafter) at a mass of ^{100 g / m 2 basis weight.} A sheet was prepared. Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Example 2>
80% by mass (excluding solvent molecules) of the porous metal complex sample obtained in the same manner as in Example 1, 10% by mass of aramid fibers as unfibrillated fibers, and 3% by mass of aramid fibers as fibrillated fibers. As an organic binder, polyvinyl alcohol (PVA) fibers having a dissolution temperature of 70 ° C. (catalog value) in water are mixed at a ratio of 7% by mass, and an adsorption sheet is prepared using a wet paper machine at a mass of ^{100 g / m 2 basis weight.} Made. Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Example 3>
80% by mass (excluding solvent molecules) of the porous metal complex sample obtained in the same manner as in Example 1, 8% by mass of aramid fibers as unfibrillated fibers, and 7% by mass of aramid fibers as fibrillated fibers. As an organic binder, polyvinyl alcohol (PVA) fibers having a dissolution temperature of 70 ° C. (catalog value) in water are mixed at a ratio of 5% by mass, and an adsorption sheet is prepared using a wet paper machine at a mass of ^{100 g / m 2 basis weight.} Made. Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Example 4>
80% by mass (excluding solvent molecules) of the porous metal complex sample obtained in the same manner as in Example 1, 8% by mass of aramid fibers as unfibrillated fibers, 9% by mass of aramid fibers as fibrillated fibers, As an organic binder, polyvinyl alcohol (PVA) fibers having a dissolution temperature of 70 ° C. (catalog value) in water are mixed at a ratio of 3% by mass, and an adsorption sheet is prepared using a wet paper machine at a mass of ^{100 g / m 2 basis weight.} Made. Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Example 5>
75% by mass (excluding solvent molecules) of the porous metal complex sample obtained in the same manner as in Example 1, 10% by mass of aramid fiber as a non-fibrillated fiber, and 6.3% by mass of aramid fiber as a fibrillated fiber. %, Polyvinyl alcohol (PVA) fiber having a dissolution temperature in water of 70 ° C. (catalog value) as an organic binder is mixed at a ratio of 8.7% by mass, and a wet papermaking apparatus is used at a mass of ^{100 g / m 2 basis weight.} A suction sheet was prepared for use. Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Example 6>
70% by mass (excluding solvent molecules) of the porous metal complex sample obtained in the same manner as in Example 1, 12% by mass of aramid fiber as a non-fibrillated fiber, and 7.5% by mass of aramid fiber as a fibrillated fiber. %, Polyvinyl alcohol (PVA) fiber having a dissolution temperature in water of 70 ° C. (catalog value) as an organic binder is mixed at a ratio of 10.5% by mass, and a wet papermaking apparatus is used at a mass of ^{100 g / m 2 basis weight.} A suction sheet was prepared for use. Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Example 7>
65% by mass (excluding solvent molecules) of the porous metal complex sample obtained in the same manner as in Example 1, 14% by mass of aramid fiber as a non-fibrillated fiber, and 8.8% by mass of aramid fiber as a fibrillated fiber. %, Polyvinyl alcohol (PVA) fiber having a dissolution temperature in water of 70 ° C. (catalog value) as an organic binder is mixed at a ratio of 12.2% by mass, and a wet papermaking apparatus is used at a mass of ^{100 g / m 2 basis weight.} A suction sheet was prepared for use. Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Example 8>
65% by mass (excluding solvent molecules) of the porous metal complex sample obtained in the same manner as in Example 1, 14% by mass of aramid fiber as a non-fibrillated fiber, and 8.8% by mass of aramid fiber as a fibrillated fiber. %, Polyvinyl alcohol (PVA) fiber having a dissolution temperature in water <99 ° C. (catalog value indicating the case where it starts to dissolve before boiling of water) as an organic binder is mixed at a ratio of 12.2% by mass, and the basis weight is 100 g. A suction sheet was prepared using a wet paper making device with a mass of / m ^2. Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Example 9>
80% by mass (excluding solvent molecules) of the porous metal complex sample obtained in the same manner as in Example 1, 8% by mass of rayon fiber as a non-fibrillated fiber, 5% by mass of rayon fiber as a fibrillated fiber, As an organic binder, polyvinyl alcohol (PVA) fibers having a dissolution temperature of 70 ° C. (catalog value) in water are mixed at a ratio of 7% by mass, and an adsorption sheet is prepared using a wet papermaking device at a mass of ^{100 g / m 2 basis weight.} Made. Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Example 10>
80% by mass (excluding solvent molecules) of the porous metal complex sample obtained in the same manner as in Example 1, 8% by mass of PET fiber as a non-fibrillated fiber, 5% by mass of aramid fiber as a fibrillated fiber, As an organic binder, polyvinyl alcohol (PVA) fibers having a dissolution temperature of 70 ° C. (catalog value) in water are mixed at a ratio of 7% by mass, and an adsorption sheet is prepared using a wet paper machine at a mass of ^{100 g / m 2 basis weight.} Made. Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Example 11>
Basolite C300 (manufactured by BASF) was used as the porous metal complex. As a result of physical property evaluation by nitrogen adsorption measurement and water vapor adsorption measurement, the BET specific surface area was 1609 m ² / g and the water adsorption rate was 43%.
Then, the porous metal complex was immersed in N, N-dimethylformaldehyde for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. This porous metal complex sample is 80% by mass (excluding solvent molecules), aramid fiber is 8% by mass as non-fibrillated fiber, aramid fiber is 5% by mass as fibrillated fiber, and the dissolution temperature in water is 70 as an organic binder. Polyvinyl alcohol (PVA) fibers at ° C. (catalog value) were mixed at a ratio of 7% by mass to prepare an adsorption sheet using a wet paper machine at a mass of ^{100 g / m 2 basis weight.} Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Example 12>
3 ml (10 mmol) of tetraisopropyl orthotitate and 2.5 g (15 mmol) of terephthalic acid were dissolved in 45 ml of N, N-dimethylformaldehyde and 5 ml of methanol, and heated at 150 ° C. for 15 hours to synthesize a porous metal complex. As a result of evaluating the physical properties of the obtained porous metal complex by nitrogen adsorption measurement and water vapor adsorption measurement, the BET specific surface area was 1199 m ² / g and the water adsorption rate was 38%.
Then, the synthesized porous metal complex was immersed in N, N-dimethylformaldehyde for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. This porous metal complex sample is 80% by mass (excluding solvent molecules), aramid fiber is 8% by mass as non-fibrillated fiber, aramid fiber is 5% by mass as fibrillated fiber, and the dissolution temperature in water is 70 as an organic binder. Polyvinyl alcohol (PVA) fibers at ° C. (catalog value) were mixed at a ratio of 7% by mass to prepare an adsorption sheet using a wet paper machine at a mass of ^{100 g / m 2 basis weight.} Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Example 13>
5.3 g (22.7 mmol) of zirconium chloride and 3.78 g (22.8 mmol) of terephthalic acid were dissolved in 500 ml of N, N-dimethylformaldehyde and heated at 120 ° C. for 24 hours to synthesize a porous metal complex. As a result of evaluating the physical properties of the obtained porous metal complex by nitrogen adsorption measurement and water vapor adsorption measurement, the BET specific surface area was 1283 m ² / g and the water adsorption rate was 42%.
Then, the synthesized porous metal complex was immersed in water for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. This porous metal complex sample is 80% by mass (excluding solvent molecules), aramid fiber is 8% by mass as non-fibrillated fiber, aramid fiber is 5% by mass as fibrillated fiber, and the dissolution temperature in water is 70 as an organic binder. Polyvinyl alcohol (PVA) fibers at ° C. (catalog value) were mixed at a ratio of 7% by mass to prepare an adsorption sheet using a wet paper machine at a mass of ^{100 g / m 2 basis weight.} Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Example 14>
The porous metal complex sample obtained in the same manner as in Example 14 was 80% by mass (excluding solvent molecules), 9.2% by mass of aramid fiber as a non-fibrillated fiber, and aramid fiber as a fibrillated fiber. A wet paper making device in which polyvinyl alcohol (PVA) fibers having a dissolution temperature of 70 ° C. (catalog value) in water are mixed at a ratio of 5% by mass as an organic binder at a ratio of 8% by mass to a basis weight of 100 g / m ^2. A suction sheet was prepared using. Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Example 15>
ZrOCl ₂ · _{8H 2} O200g and (0.62 mol) of fumaric acid 72 g (0.62 mol) N, was dissolved in N- dimethylformamide 2L and 700mL formic acid, was synthesized porous metal complex was heated for 6 hours at 130 ° C. .. As a result of evaluating the physical properties of the obtained porous metal complex by nitrogen adsorption measurement and water vapor adsorption measurement, the BET specific surface area was 884 m ² / g and the water adsorption rate was 33%.
Then, the synthesized porous metal complex was immersed in water for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. This porous metal complex sample is 80% by mass (excluding solvent molecules), aramid fiber is 8% by mass as non-fibrillated fiber, aramid fiber is 5% by mass as fibrillated fiber, and the dissolution temperature in water is 70 as an organic binder. Polyvinyl alcohol (PVA) fibers at ° C. (catalog value) were mixed at a ratio of 7% by mass to prepare an adsorption sheet using a wet paper machine at a mass of ^{100 g / m 2 basis weight.} Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Example 16>
12.87 g (55.2 mmol) of zirconium chloride and 9.45 g (52.5 mmol) of 2-aminoterephthalic acid are dissolved in 600 mL of N, N-dimethylformaldehyde and heated at 120 ° C. for 24 hours to synthesize a porous metal complex. did. As a result of evaluating the physical properties of the obtained porous metal complex by nitrogen adsorption measurement and water vapor adsorption measurement, the BET specific surface area was 949 m ² / g and the water adsorption rate was 32%.
Then, the synthesized porous metal complex was immersed in water for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. This porous metal complex sample is 80% by mass (excluding solvent molecules), aramid fiber is 8% by mass as non-fibrillated fiber, aramid fiber is 5% by mass as fibrillated fiber, and the dissolution temperature in water is 70 as an organic binder. Polyvinyl alcohol (PVA) fibers at ° C. (catalog value) were mixed at a ratio of 7% by mass to prepare an adsorption sheet using a wet paper machine at a mass of ^{100 g / m 2 basis weight.} Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Example 17>
3.6 ml (12.3 mmol) of tetraisopropyl orthotitanium and 3.6 g (19.9 mmol) of 2-aminoterephthalic acid were dissolved in 48 ml of N, N-dimethylformamide and 12 ml of methanol, and heated at 150 ° C. for 18 hours. A porous metal complex was synthesized. As a result of evaluating the physical properties of the obtained porous metal complex by nitrogen adsorption measurement and water vapor adsorption measurement, the BET specific surface area was 1248 m ² / g and the water adsorption rate was 43%.
Then, the synthesized porous metal complex was immersed in water for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. This porous metal complex sample is 80% by mass (excluding solvent molecules), aramid fiber is 8% by mass as non-fibrillated fiber, aramid fiber is 5% by mass as fibrillated fiber, and the dissolution temperature in water is 70 as an organic binder. Polyvinyl alcohol (PVA) fibers at ° C. (catalog value) were mixed at a ratio of 7% by mass to prepare an adsorption sheet using a wet paper machine at a mass of ^{100 g / m 2 basis weight.} Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Comparative example 1>
15 g (40 mmol) of alumnium nitrate and 4.32 g (20 mmol) of 1,4-naphthalenedicarboxylic acid were dissolved in 400 ml of water and heated at 180 ° C. for 24 hours to synthesize a porous metal complex. As a result of evaluating the physical properties of the obtained porous metal complex by nitrogen adsorption measurement and water vapor adsorption measurement, the BET specific surface area was 639 m ² / g and the water adsorption rate was 17%.
Then, the synthesized porous metal complex was immersed in water for 24 hours and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. 80% by mass of this porous metal complex sample (excluding solvent molecules), 8% by mass of aramid fiber as fibrillated fiber, 5% by mass of aramid fiber as fibrillated fiber, and 70 ° C. in water as an organic binder. Polyvinyl alcohol (PVA) fibers (catalog value) were mixed at a ratio of 7% by mass, and an adsorption sheet was prepared using a wet paper machine at a mass ^{having a basis weight of 100 g / m 2.} Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Comparative example 2>
80% by mass (excluding solvent molecules) of the porous metal complex sample obtained in the same manner as in Example 1, 8% by mass of aramid fibers as unfibrillated fibers, and 5% by mass of aramid fibers as fibrillated fibers. As an organic binder, polyvinyl alcohol (PVA) fibers having a dissolution temperature in water of 60 ° C. (catalog value) are mixed at a ratio of 7% by mass, and an adsorption sheet is prepared using a wet paper machine at a mass of ^{100 g / m 2 basis weight.} Made. Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Comparative example 3>
65% by mass (excluding solvent molecules) of the porous metal complex sample obtained in the same manner as in Example 1, 14% by mass of aramid fiber as a non-fibrillated fiber, and 8.8% by mass of aramid fiber as a fibrillated fiber. %, As an organic binder, polyvinyl alcohol (PVA) fibers having a dissolution temperature in water of> 100 ° C. (catalog value indicating the case where the water does not dissolve after boiling) are mixed at a ratio of 12.2% by mass, and the basis weight is 100 g. A suction sheet was prepared using a wet paper making device with a mass of / m ^2. Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Comparative example 4>
80% by mass (excluding solvent molecules) of the porous metal complex sample obtained in the same manner as in Example 1, 13% by mass of aramid fiber as a fibrillated fiber, and polyvinyl alcohol having a dissolution temperature in water of 70 ° C. as an organic binder. The (PVA) fiber was mixed at a ratio of 7% by mass, and a suction sheet was prepared using a wet paper machine at a mass of ^{100 g / m 2 basis weight.} In this comparative example, non-fibrillated fibers were not used. The adsorption sheet prepared above was further desolvated for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Comparative example 5>
80% by mass (excluding solvent molecules) of the porous metal complex sample obtained in the same manner as in Example 1, 13% by mass of aramid fiber as a non-fibrillated fiber, and 70 ° C. in water as an organic binder (catalog value). ) Polyvinyl alcohol (PVA) fibers were mixed at a ratio of 7% by mass to prepare an adsorption sheet using a wet paper machine at a mass of ^{100 g / m 2 basis weight.} In this comparative example, fibrillated fibers were not used. The adsorption sheet prepared above was further desolvated for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

<Comparative Example 6>
A-type silica gel (manufactured by Toyota Kako Co., Ltd.) was used as an adsorbent. As a result of physical property evaluation by nitrogen adsorption measurement and water vapor adsorption measurement, the BET specific surface area was 820 m ² / g and the water adsorption rate was 25%.
Then, the adsorbent was immersed in water for 24 hours and then filtered to obtain an adsorbent sample in which solvent molecules were adsorbed in the pores. 80% by mass of this adsorbent sample (excluding solvent molecules), 8% by mass of aramid fiber as non-fibrillated fiber, 5% by mass of aramid fiber as fibrillated fiber, and 70 ° C. in water as an organic binder ( Polyvinyl alcohol (PVA) fibers of (catalog value) were mixed at a ratio of 7% by mass, and an adsorption sheet was prepared using a wet papermaking apparatus at a mass of ^{100 g / m 2 basis weight.} Further, the solvent was removed for 24 hours under vacuum conditions at 130 ° C. to obtain an adsorption sheet sample. The supported sample, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

Tables 1 to 5 show the measurement results of the adsorption sheet samples obtained in Examples 1 to 17 and Comparative Examples 1 to 6.

From Tables 1 to 5, the adsorption sheets of Examples 1 to 17 are excellent in the supportability of the porous metal complex, the flexibility and processability of the sheet, and have sufficient adsorption performance. Understand.

According to the adsorption sheet, adsorption element, and adsorption / desorption treatment device of the present invention, it becomes possible to efficiently separate, recover, or adsorb and remove water, organic solvent, and substances to be adsorbed such as malodorous components. Therefore, it can be expected to greatly contribute to the industrial world.

1: Adsorption sheet 2: Adsorption rotor, 3: Motor, 4: High humidity gas,
5: Gas after dehumidification, 6: Low humidity gas, 7: Gas after humidification, 8: Heat source, 9: Fan 10: Dehumidifying / humidifying area dividing member, 11: Desiccant air conditioning system

Claims (6)

1. A porous metal complex having a metal and an organic ligand and having a water adsorption rate of 30% by mass or more at 25 ° C. and a relative pressure of 0.5.
   An adsorption sheet containing non-fibrillated fibers and fibrillated fibers.
2. The adsorption sheet according to claim 1, wherein the adsorption sheet contains an organic binder having a dissolution temperature in water of 65 ° C. to 100 ° C.
3. The adsorption sheet according to claim 1 or 2, wherein the specific tensile elongation is 5% m / g or more.
4. The adsorption sheet according to any one of claims 1 to 3, wherein the porous metal complex is contained in an amount of 60 to 85% by mass.
5. A suction element comprising the suction sheet according to any one of claims 1 to 4.
6. The adsorption element according to claim 5 and
   An adsorption means for introducing a substance to be adsorbed into the adsorption element and adsorbing the substance,
   A suction / desorption processing apparatus comprising: a desorption means for desorbing a substance to be adsorbed by the adsorption element, and continuously adsorbing / desorbing the substance to be adsorbed.
   

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