CN115087499A - Adsorption sheet, adsorption element, and adsorption treatment device using same - Google Patents
Adsorption sheet, adsorption element, and adsorption treatment device using same Download PDFInfo
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- CN115087499A CN115087499A CN202180011264.5A CN202180011264A CN115087499A CN 115087499 A CN115087499 A CN 115087499A CN 202180011264 A CN202180011264 A CN 202180011264A CN 115087499 A CN115087499 A CN 115087499A
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Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0407—Constructional details of adsorbing systems
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/261—Drying gases or vapours by adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/28—Selection of materials for use as drying agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- External Artificial Organs (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The adsorption sheet of the present invention contains a porous metal complex, non-fibrillated fibers and fibrillated fibers, wherein the porous metal complex has a metal and an organic ligand, and has a moisture adsorption rate of 30 mass% or more at 25 ℃ and a relative pressure of 0.5. This makes it possible to provide a porous metal complex which is excellent in the supporting property and the flexibility and workability of the sheet and can exhibit sufficient adsorption performance.
Description
Technical Field
The present invention relates to an adsorption sheet and an adsorption element for efficiently separating, recovering, or adsorbing and removing substances to be adsorbed, such as moisture, organic solvents, and malodorous components, and an adsorption treatment apparatus using the same.
Background
Porous materials such as activated carbon, silica gel, zeolite, and the like are used for various purposes such as deodorization, air and water purification, and separation and refinement of gas, and are indispensable materials for modern life. In recent years, a porous material, which is a novel porous material called a porous metal complex (MOF) or a Porous Coordination Polymer (PCP), has been discovered, in which metal ions capable of taking various coordination forms are combined with a cross-linking ligand having 2 or more teeth and self-assembled. These porous metal complexes have attracted attention because they have characteristics that are not possessed by conventional porous materials such as activated carbon, silica gel, and zeolite, i.e., characteristics such as a high specific surface area, a sharp pore distribution, and a high degree of structural design.
As such a porous metal complex, for example, patent document 1 discloses that a specific dicarboxylic acid metal complex is suitable as a gas storage material, particularly, a gas storage material containing methane as a main component. Patent document 2 discloses a porous metal complex synthesized from copper ions and trimesic acid, and discloses an adsorbent as an example of its use. Further, patent document 3 discloses that a porous metal complex obtained from metallic chromium or a chromium salt and trimesic acid is excellent particularly as a water vapor adsorbing material.
Such a porous metal complex may be hidden as an adsorbent for various gases. When used as an adsorbent, it is preferable to form a porous metal complex present as a powder into an adsorption element suitable for use so as to be able to contact with the operating fluid with less pressure loss.
Therefore, patent document 4 discloses, as a sheet containing a porous metal complex, a heat-resistant fiber, a clay mineral fiber having self-consolidation properties, and an absorbent sheet containing an organic binder.
Documents of the prior art
Patent document
[ patent document 1] Japanese patent laid-open publication No. 2001-348361 "
[ patent document 2] Japanese patent laid-open publication No. JP 2000-327628 "
[ patent document 3] Japanese patent laid-open publication No. 2007-51112 "
[ patent document 4] Japanese patent laid-open publication No. JP 2013-154301 "
Disclosure of Invention
Problems to be solved by the invention
However, the adsorption sheet disclosed in patent document 4 requires clay mineral fibers, and accordingly, the content ratio of the heat-resistant fibers is reduced, so that the sheet itself has no elasticity, and there is a problem that, for example, when the sheet is used as a filter, there is no paragraph.
Accordingly, it is an object of the present invention to provide an adsorption sheet and an adsorption element having excellent supporting properties of a porous metal complex, excellent flexibility and processability of a sheet, and sufficient adsorption performance, and an adsorption/desorption treatment apparatus using the same.
Means for solving the problems
The present inventors have intensively studied to solve the above problems, and finally completed the present invention. That is, the present invention is configured as follows.
[1] An absorbent sheet comprising a porous metal complex, non-fibrillated fibers and fibrillated fibers, wherein the porous metal complex comprises a metal and an organic ligand, and has a moisture absorption rate of 30 mass% or more at 25 ℃ and a relative pressure of 0.5.
[2] The absorbent sheet of the above item 1, which comprises an organic binder having a dissolution temperature in water of 65 to 100 ℃.
[3] The absorbent sheet according to 1 or 2, wherein the relative tensile elongation is 5% · m/g or more.
[4] The adsorption sheet according to any one of the above 1 to 3, characterized by containing 60 to 85 mass% of the porous metal complex.
[5] An adsorption element comprising the adsorption sheet described in any one of 1 to 4 above.
[6] An adsorption/desorption processing apparatus comprising the adsorption element of the above 5, an adsorption device for introducing a substance to be adsorbed into the adsorption element and adsorbing the substance, and a desorption device for desorbing the substance to be adsorbed by the adsorption element, wherein adsorption/desorption of the substance to be adsorbed is continuously performed.
Effects of the invention
With the above configuration, an absorbent sheet or the like having excellent supporting properties of the porous metal complex, and excellent flexibility and processability of the sheet and having sufficient absorption properties can be provided.
Drawings
Fig. 1 is a view showing an example of processing the absorbent sheet of the present invention into a wavy segment sheet.
Fig. 2 is a diagram showing an example of the adsorption element of the present invention.
Fig. 3 is a diagram showing an example of the adsorption and desorption processing apparatus according to the present invention.
Description of symbols 1: adsorption sheet, 2: adsorption rotor, 3: motor, 4: high-humidity gas, 5: dehumidified gas, 6: low-humidity gas, 7: humidified gas, 8: heat source, 9: the fan 10: dehumidification/humidification area switching means, 11: dehumidification air conditioning system
Detailed Description
The present invention will be described in detail below.
The adsorption sheet of the present invention contains a porous metal complex, non-fibrillated fibers and fibrillated fibers, wherein the porous metal complex has a metal and an organic ligand, and has a moisture adsorption rate of 30 mass% or more at 25 ℃ and a relative pressure of 0.5.
Here, the pressure at which the progress of adsorption is observed in a stopped state (the number of adsorbed molecules is equal to the number of desorbed molecules) under a constant pressure is referred to as an adsorption equilibrium pressure, and the relative pressure is a ratio of the adsorption equilibrium pressure to the saturated vapor pressure.
The adsorption sheet of the present invention contains a porous metal complex, and therefore can achieve high adsorption performance. Further, the porous metal complex is characterized in that the moisture adsorption rate at 25 ℃ and a relative pressure of 0.5 is 30 mass% or more, so that the sheet itself can hold a large amount of moisture, and high flexibility can be obtained at the time of sheet processing. Further, since flexibility can be sufficiently exhibited by the porous metal complex, an organic binder used in the past for imparting flexibility can be reduced, and as a result, the proportion of adsorption (pore blocking) of the side chain or the like of the organic binder in the pores of the adsorbent can be reduced, and further sufficient adsorption performance can be obtained. If the moisture adsorption rate is less than 30 mass%, the flexibility is poor.
Further, the absorbent sheet of the present invention contains both non-fibrillated fibers as well as fibrillated fibers. By containing the non-fibrillated fiber, for example, the segment shape can be maintained by itself even when the segment processing is performed, and the processability is excellent. In addition, by containing the fibrillated fibers, it is possible to effectively hold the porous metal complex particles, and not only it is excellent in the supporting property, but also it is possible to reduce the organic binder used in the past for imparting the supporting property. As a result, clogging of the pores can be reduced, and sufficient adsorption performance can be further obtained.
Further, the adsorption sheet of the present invention may contain an organic binder having a high melting point and a dissolution temperature in water of 65 to 100 ℃. By using the high-melting-point organic binder with the dissolving temperature of 65-100 ℃ in water, the pore blockage can be further reduced, and excellent adsorption performance can be obtained. When the water dissolution temperature is less than 65 ℃, the adsorption performance is insufficient due to pore clogging, and the adhesion is insufficient at a high temperature of more than 100 ℃ and the load bearing property is poor.
The porous metal complex according to the present invention is a porous material composed of a compound having a metal ion and an organic ligand. The form of the porous metal complex that can be used is not particularly limited, and a powder or a granule can be used. The porous metal complex having an average particle diameter of 0.1 to 200 μm is preferable, 1 to 100 μm is more preferable, and 1 to 80 μm is most preferable. If the average particle diameter is less than 0.1 μm, the yield in the formation of the adsorbent sheet may be reduced. If the average particle diameter is larger than 200 μm, it may be difficult to sufficiently support the porous metal complex on the adsorption sheet, and the porous metal complex may be more likely to fall off. The average particle diameter can be measured, for example, using a scanning electron microscope.
The BET specific surface area of the porous metal complex measured by 77K nitrogen adsorption method is not particularly limited, and is preferably 500m 2 More than g. If the BET specific surface area is less than 500m 2 In the case of the specific ratio,/g, it may be difficult to obtain sufficient adsorption performance. BET specific surface area is more preferably 1000m 2 More than g. The upper limit of the BET specific surface area is not particularly limited, and is preferably 6000m 2 The ratio of the carbon atoms to the carbon atoms is less than g. When the amount is larger than this range, the porous metal complex is difficult to produce. The BET specific surface area can be measured, for example, by the method described in the examples of the subsequent stage.
The metal ion constituting the porous metal complex is not particularly limited, and examples thereof include typical metal elements such as aluminum ion, and transition metal elements such as titanium ion, zirconium ion, iron ion, and copper ion. On the other hand, examples of the compound having a ligand include fumaric acid, 2-aminoterephthalic acid, 1, 4-naphthalenedicarboxylic acid, terephthalic acid, and trimesic acid. Specific examples of the porous metal complex include a porous metal complex composed of aluminum ions and terephthalic acid (BASF, Basolite a100), 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, a porous metal complex composed of zirconium ions and fumaric acid, a porous metal complex composed of zirconium ions and 2-aminoterephthalic acid, and a porous metal complex composed of titanium ions and 2-aminoterephthalic acid. These porous metal complexes have various BET specific surface areas depending on the synthesis method and purity even if they are the same, but in order to impart flexibility to the adsorption sheet, the water adsorption rate at 25 ℃ and a relative pressure of 0.5 is preferably 30% by mass or more, more preferably 35% by mass or more, and still more preferably 40% by mass or more. If the content is less than 30% by mass, the content of the organic binder needs to be increased in order to provide the absorbent sheet with sufficient flexibility. When the content of the organic binder is large, the proportion of the side chain or the like of the organic binder adsorbed in the pores of the adsorbent is large, and as a result, sufficient adsorption performance cannot be exhibited.
The content of the porous metal complex in the absorbent sheet of the present invention is preferably 60 to 85 mass%, more preferably 65 to 80 mass%. When the content is less than 60% by mass, it may be difficult to obtain sufficient adsorption performance. On the other hand, if the content is more than 85 mass%, it is difficult to sufficiently support the porous metal complex on the adsorption sheet, and the amount of the exfoliated product increases. In addition, sheet strength may also be significantly reduced.
The fiber diameter of the non-fibrillated fiber is preferably 5 μm or more, and more preferably 5 to 30 μm. The fiber length is preferably 1mm to 10mm, more preferably 2mm to 8 mm. When the fiber diameter of the coarse fibers is less than 5 μm and the fiber length is less than 1mm, the strength of the sheet is lowered, and it is difficult to maintain the segment shape by itself after segment processing, and it is difficult to process the sheet into an adsorbent element such as a honeycomb shape during post processing. If the fiber diameter of the non-fibrillated fiber is larger than 30 μm and the fiber length is larger than 10mm, the fiber does not have flexibility and is difficult to process. Further, fibers having different fiber diameters may be mixed.
The 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, nylon fibers, and the like; semi-synthetic fibers such as acetate fibers and triacetate fibers; rayon fibers; regenerated fibers such as copper ammonia fibers; plant fibers such as cotton, hemp, and fibers containing wood as a main component. 1 or 2 or more of these may be used.
The fibrillated fiber may be, for example, pulp, in addition to the fibrillated fiber of the above fiber. 1 or 2 or more of these may be used. The method of fibrillation is not particularly limited, and a general beating method can be employed. As a typical example, a method of fibrillating using a beater (beater) or a beater (beating aerator) such as a refiner may be mentioned. The fibrillated fiber is preferably 50ml or more and less than 800ml when measured in Canadian Standard Freeness (CSF) according to JIS P8121-2.
In the absorbent sheet of the present invention, the total content of the non-fibrillated fibers and the fibrillated fibers is preferably 5 to 25 mass%, more preferably 10 to 25 mass%. When the content is less than 5 mass%, it is difficult to sufficiently support the porous metal complex on the adsorption sheet, the amount of exfoliation increases, and the strength of the sheet may be significantly reduced. On the other hand, when the content is more than 25% by mass, it may be difficult to obtain sufficient adsorption performance.
The adsorption sheet in the invention contains an organic adhesive. Because the flexibility and strength of the absorbent sheet are improved. The organic binder is not particularly limited as long as it can bind the porous metal complex and the fibers. For example, polyvinyl alcohol polymers, polyacrylonitrile polymers, polyethylene polymers, polyester polymers, polyphenylene ether polymers, and the like can be used. In view of handling properties, polyvinyl alcohol polymers are preferred. The form of the organic binder is not particularly limited, and a fibrous material is preferably used because the adsorption sheet can be easily produced. The content of the organic binder in the absorbent sheet is preferably 3 to 15% by mass, and more preferably 4 to 12% by mass. When the amount is less than 3% by mass, the supporting property of the porous metal complex and the flexibility of the sheet are insufficient, and when the amount is more than 15% by mass, the porous metal complex is covered with the organic binder, and thus it tends to be difficult to obtain sufficient adsorption performance.
The water-soluble temperature of the organic binder is preferably 65 to 100 ℃ and more preferably 70 to 100 ℃. When the dissolution temperature in water is less than 65 ℃, the proportion of the binder side chain incorporated into the pores of the porous metal complex increases, and as a result, the adsorption performance may become insufficient. Further, the adhesive bond is insufficient at a high temperature of more than 100 ℃, and the load-bearing property is poor.
The water-soluble temperature of the organic binder can be measured by a conventional method. For example, the following methods are used: 100ml of pure water was put into a beaker and stirred, and heated with an oil bath until the water temperature became 50 ℃, 0.5g of an organic binder was added thereto, the water temperature was raised at a temperature rise rate of 2 ℃/min, and the temperature at which the binder started to dissolve until it became translucent was visually measured.
The absorbent sheet of the present invention exhibits a supporting property by fibrillated fibers and exhibits flexibility by a high moisture adsorption rate of a porous metal complex even when the content of an organic binder is small. As a result, sufficient adsorption performance can be exhibited by a small amount of the organic binder and the high adsorption performance of the porous metal complex itself.
The absorbent sheet of the present invention preferably has a relative tensile elongation of 5% m/g or more as an index of flexibility. When the ratio is less than 5% m/g, the flexibility of the sheet is poor, and cracks are generated during the honeycomb processing (block processing).
The adsorption sheet of the present invention may contain 1 or 2 or more kinds of porous metal complexes, and may further contain a porous material other than the porous metal complexes. The porous material contained in the adsorption sheet of the present invention is not particularly limited, and examples thereof include organic polymer porous materials such as activated carbon, zeolite, silica gel, activated alumina, aluminum phosphate, silicoaluminophosphate, and a styrene-divinylbenzene copolymer. Preferably, activated carbon, zeolite, silica gel, activated alumina, which are available at low cost, are used.
The thickness of the absorbent sheet of the present invention is preferably 0.1mm to 0.9mm, more preferably 0.1mm to 0.7 mm. When the thickness is less than 0.1mm, the sheet strength is significantly reduced, and therefore, it may be difficult to process the sheet into an adsorbent member such as a honeycomb structure in the post-processing. When the thickness is more than 0.9mm, the pressure loss of the suction element tends to be high when the suction sheet is processed into a honeycomb shape or the like.
The gram weight of the absorbent sheet of the present invention is preferably 25g/m 2 ～200g/m 2 . More preferably 40g/m 2 ～150g/m 2 . If the gram weight is less than 25g/m 2 The thickness of the sheet becomes thin, and the strength of the sheet may be significantly reduced, and it may become difficult to process the sheet into an adsorbent member such as a honeycomb in a post-process. In addition, if the gram weight is more than 200g/m 2 The thickness of the sheet becomes too large, and the pressure loss of the suction element during processing of a honeycomb or the like may become high.
The method for producing the absorbent sheet of the present invention is not particularly limited, and conventionally known processing methods can be used. Preferably, the method includes a wet sheet forming method in which the porous metal complex, the fibers, and the organic binder are dispersed in water, an organic solvent, or a mixture thereof, and the resulting dispersion is formed, dehydrated, and dried.
Here, the porous metal complex is preferably supplied to the sheet forming step by mixing the materials constituting the sheet in a state where the solvent molecules are contained in the pores thereof. When the porous metal complex does not have solvent molecules in the pores, there is a risk that the organic binder constituting the adsorption sheet is adsorbed in the pores. In this case, even if the sheet is formed into a sheet and subjected to a desolvation treatment described later, it is difficult to remove the organic binder trapped in the pores of the porous metal complex, and as a result, the adsorption performance of the adsorption sheet is deteriorated. That is, in the present invention, the pores of the porous metal complex are made to adsorb solvent molecules, whereby the organic binder or the like in the sheet forming step can be prevented from being adsorbed to the pores, and after the sheet forming step, the solvent molecules are removed from the pores by the desolvation treatment described later, whereby the adsorption performance of the adsorption sheet can be secured. In general, in the step of synthesizing the porous metal complex, solvent molecules are adsorbed in pores of the porous metal complex, but when the porous metal complex does not have solvent molecules in the pores or the amount of solvent molecules adsorbed is insufficient, the organic solvent can be adsorbed in the pores by the method described in the example described later. Here, the solvent molecules refer to water and general organic solvent molecules.
In the production of the adsorbent sheet of the present invention, after the sheet-forming step, a solvent removal treatment step of removing the solvent contained in the adsorbent sheet is performed. As described above, the porous metal complex is preferably formed into a sheet in a state where the solvent molecules are contained in the pores thereof, and in this case, it is difficult to obtain sufficient adsorption performance due to the solvent molecules in the pores of the porous metal complex. Therefore, in order to exhibit the adsorption performance, the sheet formation step is followed by a solvent removal treatment. The timing of the solvent removal treatment is not particularly limited as long as it is after the sheeting step.
The conditions for the solvent removal treatment are not particularly limited, and the temperature is preferably 50 to 300 ℃. If the temperature is less than 50 ℃, 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 is higher than 300 ℃, the pore structure of the porous metal complex may be destroyed, and in this case, it is difficult to obtain sufficient adsorption performance. More preferably from 80 ℃ to 200 ℃. Further, the solvent removal treatment can be carried out under reduced pressure to remove the solvent more efficiently. In this case, the pressure is not particularly limited, and may be appropriately adjusted according to the physical properties and the amount to be mixed of the porous metal complex, and is preferably 10, for example 3 Pa～10 -5 Pa, more preferably 10 -1 Pa～10 -5 Pa. The solvent removal treatment time is also not particularly limited, and is, for example, preferably 1 hour to 100 hours, more preferably 3 hours to 48 hours, and still more preferably 3 hours to 24 hours. Furthermore, the most preferred conditions for the desolvation treatment are: under the vacuum condition, the temperature is 80-200 ℃ and the time is 3-24 hours.
The absorbent sheet of the present invention may be used in a flat plate form, or may be used by being formed into a desired shape by being appropriately subjected to a corrugation process, a honeycomb process, a corrugation process, or the like. Fig. 1 shows an example of processing the absorbent sheet 1 into a wavy segment sheet as an absorbent sheet of the present invention. In particular, the folding process, the honeycomb process, and the corrugation process require a step of bending the sheet during the processing, and in this case, the porous metal complex sufficiently adsorbs moisture and then the sheet is processed to exhibit flexibility. The method for adsorbing moisture to the porous metal complex is not particularly limited, but a method of processing a room after humidification or while blowing steam is preferably used for convenience.
The suction element of the present invention is characterized by comprising the suction 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 used as long as it is appropriately selected according to the use and purpose. The shape of the suction sheet provided in the suction element of the present invention is not particularly limited, and for example, a suction sheet processed into a flat plate shape, a corrugated shape, a honeycomb shape, or the like can be used. For example, when the adsorption sheet processed into a corrugated shape is used as a direct-current adsorption element, and when the adsorption sheet processed into a honeycomb shape is used as a parallel-current adsorption element, the contact area with the gas to be treated can be increased to improve the removal efficiency of the adsorption object substance and the low pressure loss of the adsorption element. The parallel flow type adsorption element is superior to the orthogonal flow type adsorption element in preventing clogging due to mist and dust, reducing pressure loss, and reducing weight, and therefore the adsorption sheet provided in the adsorption element is preferably honeycomb-shaped.
Fig. 2 shows a suction rotor 2 in which a suction sheet of the present invention is wound in a rotor shape as an example of a suction element of the present invention. The adsorption rotor 2 has an adsorption sheet in a honeycomb shape.
The adsorption sheet of the present invention and the adsorption element having the adsorption sheet can be widely used for the purpose of reducing malodorous components in houses, vehicles, wall paper, furniture, interior materials, resin molded bodies, electric devices, and the like, for the purpose of separating and recovering organic solvents in air discharged from factories and the like, and for the purpose of humidity control and dehumidification.
In addition, an adsorption/desorption processing apparatus including the adsorption element of the present invention, an adsorption device for introducing and adsorbing an adsorption target substance into the adsorption element, and a desorption device for desorbing the adsorption target substance adsorbed by the adsorption element is also included in the scope of the present invention. The adsorption apparatus may be a pipe or the like for introducing air or gas containing an offensive odor substance such as an organic solvent and an adsorption target substance such as moisture. As a method for desorbing the substance to be adsorbed, there are a heating method, a method of reducing the system pressure, and the like, and as a desorption device, a pipe for introducing a heated gas, a heater, a pressure reducer, and the like can be considered. For desorption efficiency and economy, a device for introducing heated air is preferred.
Fig. 3 shows a dehumidifying air-conditioning system 11 as an example of the adsorption/desorption processing apparatus of the present invention. The dehumidification air-conditioning system 11 includes an adsorption rotor 2, a motor 3, a heat source 8 such as a heater, a fan 9, and a dehumidification/humidification area switching member 10. In the dehumidification air-conditioning system 11, when the high-humidity gas 4 containing moisture as the substance to be adsorbed is introduced, the moisture is adsorbed to the adsorption rotor 2 and is discharged as the dehumidified gas 5. When the low-humidity gas 6 heated by the heat source 8 is introduced, the moisture adsorbed by the adsorption rotor 2 is desorbed and discharged as humidified gas 7. The adsorption and desorption treatment device is suitable for dehumidification air-conditioning systems for factories and household dehumidification air-conditioning systems.
[ examples ] A method for producing a compound
The present invention will be described in more detail with reference to examples. The following examples are not intended to limit the nature of the present invention, and any design changes made in accordance with the spirit described above and below are included in the technical scope of the present invention.
First, the measurement method and evaluation method of the characteristic values obtained in examples and comparative examples are as follows.
[ Water adsorption Rate ]
About 100mg of the porous metal complex (before the treatment with water or an organic solvent) was taken out, and dried under vacuum at 120 ℃ for 12 hours, and then weighed. Using a high-precision gas/vapor adsorption amount measuring apparatus (BELSORP-max, manufactured by Bel, Japan) to measure 25The adsorption amount of water vapor at 0 ℃ to 0.95 ℃ is measured at 40 points while gradually increasing the relative pressure, and an adsorption isotherm is prepared. In this case, the target relative pressure is set to 0.001, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and the adsorption amount increase/decrease allowable capacity is set to 30cm at a relative pressure of 0 to 0.3 2 A relative pressure of 0.3 to 0.5 is set to 50cm 2 (g) the relative pressure is set to 30cm at 0.5-0 2 And/g, preparing an adsorption isotherm. Then, the amount of water adsorbed per 1g of the porous metal complex [ g ] was adjusted to a relative pressure of 0.5]The water adsorption rate [% was calculated by the following formula (i)]。
Moisture adsorption rate [% ] is moisture adsorption amount per 1g of adsorbent [ g ] × 100 … (i)
[ BET specific surface area ]
About 100mg of the porous metal complex (before the treatment with water or an organic solvent) was taken out, and dried under vacuum at 120 ℃ for 12 hours, and then weighed. An adsorption isotherm was prepared by measuring 40 points while gradually increasing the amount of nitrogen adsorbed at the boiling point (-195.8 ℃) of liquid nitrogen below a relative pressure of 0.02 to 0.95 using an automatic specific surface area measuring apparatus (Gemini 2375, manufactured by Micromeritics). The BET specific surface area [ m ] was determined by setting the surface area analysis range to 0.01 to 0.15 under the BET condition using analysis software (GEMINI-PCW version1.01) attached to an automatic specific surface area measuring apparatus 2 /g]。
[ Supported Property ]
A10 cm × 10cm test piece cut out from the adsorption piece sample was vertically fixed on a bench at a10 cm × 10cm flat portion, where a sphere (raw material: aluminum) having a diameter of 2.4cm and a mass of 20g was vertically impacted 10 times against the 10cm × 10cm flat portion of the test piece. The spheres rolled at a speed of 10 cm/s. As a result, the amount of the exfoliated porous metal complex was good when it was less than 0.1mg, poor when it was more than 10mg, and Δ when it was 0.1mg to 10 mg.
[ flexibility ]
In the examples and comparative examples, it was observed whether or not cracks were generated when the absorbent sheet was subjected to honeycomb processing (segment processing).
A test piece of 10cm × 10cm cut out from the sample of the adsorption piece was dried at 120 ℃ for 1 hour, and then allowed to stand at 22 ℃ for 1 hour in an atmosphere of 40% RH. The two ends of the test piece thus conditioned were held and bent by 90 degrees. In this case, the sheets were evaluated as good (good) if no cracking occurred, as difficult (difficult) if cracking occurred, and as poor (bad) if cracking occurred.
[ relative tensile elongation ]
A test piece of 15 mm. times.100 mm cut out from the sample of the adsorption piece was dried at 120 ℃ for 1 hour, and the weight thereof was measured. Then, the dried sample was allowed to stand at 22 ℃ under 40% RH for 1 hour, and the elongation at the maximum point [% ] was measured by a tensile/compression tester (TENSILON RTG-1310, manufactured by A & D). Further, the distance between the clamps was set to 50mm, and the drawing speed was set to 15 mm/min. From the obtained data, the relative tensile elongation was calculated by the following formula (ii).
Relative tensile elongation [%. m/g]Percent maximum point elongation [% ]]Width of sample [ m ]]Gram weight of adsorption sheet [ g/m ] 2 ]…(ii)
[ pore maintenance Rate ]
About 100mg of the adsorption sheet sample was taken, and weighed after vacuum drying at 120 ℃ for 12 hours. The adsorption isotherm of the sample was prepared by measuring 40 points while gradually increasing the adsorption amount of nitrogen gas at the boiling point (-195.8 ℃) of liquid nitrogen below a relative pressure of 0.02 to 0.95 using an automatic specific surface area measuring apparatus (Gemini 2375, manufactured by Micromeritics). The BET specific surface area [ m ] was determined by setting the surface area analysis range to 0.01 to 0.15 under the BET condition using analysis software (GEMINI-PCW version1.01) attached to an automatic specific surface area measuring apparatus 2 /g]. Then, based on the BET specific surface area [ m ] of the porous metal complex 2 /g]The pore maintenance ratio was calculated by the following formula (iii).
Pore maintenance [% ]][ BET specific surface area of adsorption sheet [ m ] 2 /g]X 100/(porous metal complex content in adsorption sheet) }/(BET specific surface area [ m ] of porous metal complex sample 2 /g])×100…(iii)
The higher the pore retention rate, the more the pores of the porous metal complex are not filled with a binder or the like (the pores are not blocked), and the higher the adsorption performance.
[ sheet Properties (Water vapor adsorption amount) ]
About 100mg of the porous metal complex (before the treatment with water or an organic solvent) was taken out, and dried in vacuum at 120 ℃ for 12 hours, and then weighed. An adsorption isotherm was prepared by measuring 40 points while gradually increasing the amount of water vapor adsorbed at 25 ℃ within a range of relative pressure of 0.02 to 0.95 using a high-precision gas/vapor adsorption amount measuring apparatus (BELSORP-max, manufactured by Bel, Japan). Then, the amount [ ml ] of water vapor adsorbed per 1g of the porous metal complex under a relative pressure of 0.95 was determined. As the evaluation of sheet properties, the amount of water vapor adsorbed was evaluated as "good" when the amount was 410ml/g or more, as "acceptable" when the amount was more than 400ml/g and less than 410ml/g, and as "bad" when the amount was 400ml/g or less.
[ processability ]
In the examples and comparative examples, it was observed whether the segment shape was self-maintained after the segment processing.
The absorbent sheet sample was prepared to have a width of 30cm x a length of 30cm and passed through a corrugating machine which theoretically could prepare corrugated paper having a width of 30cm x a length of 21.4 cm. Then, the suction sheet after the corrugation was left to stand in an atmosphere of 22 ℃ and 40% RH for 24 hours, and then evaluated as good (good) with a length recovery ratio of less than 20%, fair (acceptable) with a length recovery ratio of 20% to less than 50%, and x (poor) with a length recovery ratio of 50% to 100%.
[ temperature of dissolution in Water ]
The organic binders used in the examples and comparative examples were measured for their dissolution temperature in water by the following measurement method, and were the same as the index values except for the organic binder of example 8. The organic binder of example 8 has a catalogue value of <99 ℃ and an observed value of 95 ℃.
4mL of pure water and 0.02g of an organic binder were put in a 6mL glass bottle. The vial was placed in a water bath heated from 50 ℃ every 5 ℃ increment for 10 minutes. The organic adhesive in the jar was stirred with a spatula every 2 minutes. The temperature at which the binder started to dissolve until it was translucent was determined visually.
< example 1>
Mixing Fe (NO) 3 ) 3 ·9H 2 O16.2g (40mmol) and trimesic acid 7.5g (36mmol) was dissolved in 32ml of water, and heated at 95 ℃ for 15 hours to synthesize a porous metal complex. The physical properties of the obtained porous metal complex were evaluated by nitrogen adsorption measurement and water vapor adsorption measurement, and the BET specific surface area was 1575m 2 (ii)/g, moisture adsorption rate was 53%.
Then, the porous metal complex synthesized as described above was immersed in water for 24 hours, and then filtered to obtain a porous metal complex sample having solvent molecules adsorbed in pores. The porous metal complex sample was mixed at a ratio of 80 mass% (excluding solvent molecules), 8 mass% of aramid fiber as non-fibrillated fiber, 5 mass% of aramid fiber as fibrillated fiber, and 7 mass% of polyvinyl alcohol (PVA) fiber having a water-soluble dissolution temperature of 70 ℃ (catalog number) as organic binder, and the basis weight was 100g/m 2 The mass of (D) was measured by using a wet papermaking apparatus (manufactured by Toyo Boseki Co., Ltd., the same shall apply hereinafter) to prepare an adsorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< example 2>
The porous metal complex sample obtained in the same manner as in example 1 was mixed at a ratio of 80 mass% (excluding solvent molecules), 10 mass% of aramid fiber as non-fibrillated fiber, 3 mass% of aramid fiber as fibrillated fiber, and 7 mass% of polyvinyl alcohol (PVA) fiber having a water-soluble dissolution temperature of 70 ℃ (catalog number) as an organic binder, and the grammage was 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< example 3>
Aramid fibers as non-fibrillated fibers with 80 mass% of porous metal complex sample (except solvent molecules) obtained in the same manner as in example 18% by mass of fiber, 7% by mass of aramid fiber as fibrillated fiber, and 5% by mass of polyvinyl alcohol (PVA) fiber having a water-soluble temperature of 70 ℃ (index value) as an organic binder were mixed in such a ratio that the grammage became 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< example 4>
The porous metal complex sample obtained in the same manner as in example 1 was mixed in a ratio of 80 mass% (excluding solvent molecules), 8 mass% of aramid fiber as non-fibrillated fiber, 9 mass% of aramid fiber as fibrillated fiber, and 3 mass% of polyvinyl alcohol (PVA) fiber having a water-soluble dissolution temperature of 70 ℃ (catalog number) as an organic binder, and the grammage was 100g/m 2 The mass of (2) was measured by a wet papermaking apparatus to prepare an absorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< example 5>
75 mass% of the porous metal complex sample obtained in the same manner as in example 1 (except for solvent molecules), 10 mass% of aramid fiber as non-fibrillated fiber, 6.3 mass% of aramid fiber as fibrillated fiber, and 8.7 mass% of polyvinyl alcohol (PVA) fiber having a water-soluble dissolution temperature of 70 ℃ (catalog number) as an organic binder were mixed in such a ratio that the grammage became 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< example 6>
Porous metal complex obtained in the same manner as in example 1Sample 70 mass% (excluding solvent molecules), aramid fiber 12 mass% as non-fibrillated fiber, aramid fiber 7.5 mass% as fibrillated fiber, and polyvinyl alcohol (PVA) fiber 10.5 mass% as organic binder having a water-soluble temperature of 70 ℃ (catalog value) were mixed in a ratio such that the grammage became 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< example 7>
The porous metal complex sample obtained in the same manner as in example 1 was mixed at a ratio of 65 mass% (excluding solvent molecules), 14 mass% of aramid fiber as non-fibrillated fiber, 8.8 mass% of aramid fiber as fibrillated fiber, and 12.2 mass% of polyvinyl alcohol (PVA) fiber having a water-soluble dissolution temperature of 70 ℃ (catalog number) as an organic binder, and the basis weight was 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< example 8>
A porous metal complex sample obtained in the same manner as in example 1 was mixed at a ratio of 65 mass% (excluding solvent molecules), 14 mass% of aramid fiber as non-fibrillated fiber, 8.8 mass% of aramid fiber as fibrillated fiber, and 12.2 mass% of polyvinyl alcohol (PVA) fiber having a water-soluble temperature of <99 ℃ (index value indicating that melting started just before water boiling) as an organic binder, and the mixture was weighed to 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< example 9>
The porous metal complex sample obtained in the same manner as in example 1 was mixed at a ratio of 80 mass% (excluding solvent molecules), 8 mass% of rayon fiber as non-fibrillated fiber, 5 mass% of rayon fiber as fibrillated fiber, and 7 mass% of polyvinyl alcohol (PVA) fiber having a water-soluble temperature of 70 ℃ (catalog number) as an organic binder, and the grammage was 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< example 10>
The porous metal complex sample obtained in the same manner as in example 1 was mixed at a ratio of 80 mass% (excluding solvent molecules), 8 mass% of PET fibers as non-fibrillated fibers, 5 mass% of aramid fibers as fibrillated fibers, and 7 mass% of polyvinyl alcohol (PVA) fibers having a water-soluble dissolution temperature of 70 ℃ (catalog number) as an organic binder, and the grammage was 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< example 11>
Basolite C300 (manufactured by BASF) was used as the porous metal complex. Physical properties were evaluated by nitrogen adsorption measurement and water vapor adsorption measurement, and the BET specific surface area was 1609m 2 (ii)/g, water adsorption rate 43%.
Then, the porous metal complex is immersed in N, N-dimethyl formaldehyde for 24 hours, and then filtered to obtain a porous metal complex sample having solvent molecules adsorbed in pores. The porous metal complex sample was 80 mass% (excluding solvent molecules), and the aramid fiber as an unfibrillated fiber was 8 mass% 5 mass% of an aramid fiber as a fibrillated fiber and 7 mass% of a polyvinyl alcohol (PVA) fiber having a water-soluble temperature of 70 ℃ (catalog value) as an organic binder were mixed in such a ratio that the grammage became 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< example 12>
3ml (10mmol) of tetraisopropyl titanate and 2.5g (15mmol) of terephthalic acid were dissolved in 45ml of N, N-dimethylformaldehyde and 5ml of methanol, and heated at 150 ℃ for 15 hours to synthesize a porous metal complex. The physical properties of the obtained porous metal complex were evaluated by nitrogen adsorption measurement and water vapor adsorption measurement, and the BET specific surface area was 1199m 2 (ii)/g, water adsorption rate was 38%.
Then, the porous metal complex synthesized as described above was immersed in N, N-dimethylformaldehyde for 24 hours, and then filtered to obtain a sample of the porous metal complex having solvent molecules adsorbed in the pores. The porous metal complex sample was mixed at a ratio of 80 mass% (excluding solvent molecules), 8 mass% of aramid fiber as non-fibrillated fiber, 5 mass% of aramid fiber as fibrillated fiber, and 7 mass% of polyvinyl alcohol (PVA) fiber having a water-soluble dissolution temperature of 70 ℃ (catalog number) as organic binder, and the basis weight was 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for its load carrying property, flexibility, pore retention rate, water vapor adsorbing property and processability.
< example 13>
Zirconium chloride (5.3 g, 22.7mmol) and terephthalic acid (3.78 g, 22.8mmol) were dissolved in N, N-dimethylformaldehyde (500 ml), and the resulting solution was heated at 120 ℃ for 24 hours to synthesize a porous metal complex. The obtained porous metal complex was measured by nitrogen adsorption and water evaporationPhysical properties were evaluated by gas adsorption measurement, and the BET specific surface area was 1283m 2 (ii)/g, the moisture adsorption rate was 42%.
Then, the porous metal complex synthesized as described above was immersed in water for 24 hours, and then filtered to obtain a porous metal complex sample having solvent molecules adsorbed in pores. The porous metal complex sample was mixed at a ratio of 80 mass% (excluding solvent molecules), 8 mass% of aramid fiber as non-fibrillated fiber, 5 mass% of aramid fiber as fibrillated fiber, and 7 mass% of polyvinyl alcohol (PVA) fiber having a water-soluble dissolution temperature of 70 ℃ (catalog number) as organic binder, and the basis weight was 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< example 14>
The porous metal complex sample obtained in the same manner as in example 14 was mixed at a ratio of 80 mass% (excluding solvent molecules), 9.2 mass% of aramid fiber as non-fibrillated fiber, 5.8 mass% of aramid fiber as fibrillated fiber, and 5 mass% of polyvinyl alcohol (PVA) fiber as an organic binder having a water-soluble temperature of 70 ℃ (catalog number) to give a grammage of 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< example 15>
ZrOCl 2 ·8H 2 200g (0.62mol) of O and 72g (0.62mol) of fumaric acid were dissolved in 2L of N, N-dimethylformaldehyde and 700mL of formic acid, and the mixture was heated at 130 ℃ for 6 hours to synthesize a porous metal complex. The physical properties of the obtained porous metal complex were evaluated by nitrogen adsorption measurement and water vapor adsorption measurement, and the BET specific surface area was 884m 2 (ii) water adsorption rate: 33%.
Then, the porous metal complex synthesized as described above was immersed in water for 24 hours, and then filtered to obtain a porous metal complex sample having solvent molecules adsorbed in pores. The porous metal complex sample was mixed at a ratio of 80 mass% (excluding solvent molecules), 8 mass% of aramid fiber as non-fibrillated fiber, 5 mass% of aramid fiber as fibrillated fiber, and 7 mass% of polyvinyl alcohol (PVA) fiber having a water-soluble dissolution temperature of 70 ℃ (catalog number) as organic binder, and the basis weight was 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< example 16>
A porous metal complex was synthesized by dissolving 12.87g (55.2mmol) of zirconium chloride and 9.45g (52.5mmol) of 2-aminoterephthalic acid in 600mL of N, N-dimethylformamide and heating the resulting solution at 120 ℃ for 24 hours. The physical properties of the obtained porous metal complex were evaluated by nitrogen adsorption measurement and water vapor adsorption measurement, and the BET specific surface area was 949m 2 (ii) a water adsorption rate of 32%.
Then, the porous metal complex synthesized as described above was immersed in water for 24 hours, and then filtered to obtain a porous metal complex sample having solvent molecules adsorbed in pores. The porous metal complex sample was mixed at a ratio of 80 mass% (excluding solvent molecules), 8 mass% of aramid fiber as non-fibrillated fiber, 5 mass% of aramid fiber as fibrillated fiber, and 7 mass% of polyvinyl alcohol (PVA) fiber having a water-soluble temperature of 70 ℃ (catalog value) as organic binder, and the basis weight was 100g/m 2 The mass of (2) was measured by a wet papermaking apparatus to prepare an absorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< example 17>
A porous metal complex was synthesized by dissolving 3.6ml (12.3mmol) of tetraisopropyl titanate and 3.6g (19.9mmol) of 2-aminoterephthalic acid in 48ml of N, N-dimethylformamide and 12ml of methanol, and heating the resulting solution at 150 ℃ for 18 hours. The physical properties of the obtained porous metal complex were evaluated by nitrogen adsorption measurement and water vapor adsorption measurement, and the BET specific surface area was 1248m 2 (ii)/g, water adsorption rate 43%.
Then, the porous metal complex synthesized as described above was immersed in water for 24 hours, and then filtered to obtain a porous metal complex sample having solvent molecules adsorbed in pores. The porous metal complex sample was mixed at a ratio of 80 mass% (excluding solvent molecules), 8 mass% of aramid fiber as non-fibrillated fiber, 5 mass% of aramid fiber as fibrillated fiber, and 7 mass% of polyvinyl alcohol (PVA) fiber having a water-soluble dissolution temperature of 70 ℃ (catalog number) as organic binder, and the basis weight was 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< comparative example 1>
15g (40mmol) of aluminum nitrate and 4.32g (20mmol) of 1, 4-naphthalenedicarboxylic acid were dissolved in 400ml of water, and the mixture was heated at 180 ℃ for 24 hours to synthesize a porous metal complex. The physical properties of the obtained porous metal complex were evaluated by nitrogen adsorption measurement and water vapor adsorption measurement, and the BET specific surface area was 639m 2 (ii)/g, moisture adsorption rate was 17%.
Then, the porous metal complex synthesized as described above was immersed in water for 24 hours, and then filtered to obtain a porous metal complex sample having solvent molecules adsorbed in pores. The porous metal complex sample was 80 mass% (excluding solvent molecules), 8 mass% of aramid fiber as fibrillated fiber, 5 mass% of aramid fiber as fibrillated fiber, and organicPolyvinyl alcohol (PVA) fibers having a water-soluble temperature of 70 ℃ C (catalog number) were mixed at a ratio of 7 mass% to give a grammage of 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< comparative example 2>
The porous metal complex sample obtained in the same manner as in example 1 was mixed at a ratio of 80 mass% (excluding solvent molecules), 8 mass% of aramid fiber as non-fibrillated fiber, 5 mass% of aramid fiber as fibrillated fiber, and 7 mass% of polyvinyl alcohol (PVA) fiber having a water dissolution temperature of 60 ℃ (catalog number) as an organic binder, and the grammage was 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< comparative example 3>
The porous metal complex sample obtained in the same manner as in example 1 was mixed at a ratio of 65 mass% (excluding solvent molecules), 14 mass% of aramid fiber as non-fibrillated fiber, 8.8 mass% of aramid fiber as fibrillated fiber, and 12.2 mass% of polyvinyl alcohol (PVA) fiber as an organic binder, the dissolution temperature of which in water was > 100 ℃ (index value indicating that the fiber did not dissolve after boiling of water), and the grammage was 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for its load carrying property, flexibility, pore retention rate, water vapor adsorbing property and processability.
< comparative example 4>
80 mass% of a porous metal complex sample obtained in the same manner as in example 1 (except that the solvent was used)Molecule), 13 mass% of aramid fiber as fibrillated fiber, and 7 mass% of polyvinyl alcohol (PVA) fiber as an organic binder having a water-soluble temperature of 70 ℃, and the mixture is mixed so that the basis weight is 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. In addition, in this comparative example, non-fibrillated fibers were not used. The adsorption sheet prepared above was further subjected to desolvation treatment at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< comparative example 5>
The porous metal complex sample obtained in the same manner as in example 1 was mixed in a ratio of 80 mass% (excluding solvent molecules), 13 mass% of aramid fiber as non-fibrillated fiber, and 7 mass% of polyvinyl alcohol (PVA) fiber having a water-soluble temperature of 70 ℃ (catalog number) as an organic binder, and the grammage was 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. In addition, in this comparative example, non-fibrillated fibers were not used. The adsorption sheet prepared above was further subjected to desolvation treatment at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
< comparative example 6>
As the adsorbent, A-shaped silica gel (rich manufactured by Takara chemical Co., Ltd.) was used. Physical properties were evaluated by nitrogen adsorption measurement and water vapor adsorption measurement, and the BET specific surface area was 820m 2 (ii)/g, moisture adsorption rate was 25%.
Then, the adsorbent was immersed in water for 24 hours, and then filtered to obtain an adsorbent sample having solvent molecules adsorbed in the pores. The adsorbent material sample was mixed at a ratio of 80 mass% (excluding solvent molecules), 8 mass% of aramid fiber as non-fibrillated fiber, 5 mass% of aramid fiber as fibrillated fiber, and 7 mass% of polyvinyl alcohol (PVA) fiber having a water-soluble temperature of 70 ℃ (catalog number) as organic binder, and the basis weight was 100g/m 2 The mass of (2) was measured by using a wet papermaking apparatus to prepare an adsorbent sheet. Further, desolvation treatment was performed at 130 ℃ for 24 hours under vacuum conditions to obtain an adsorption sheet sample. The obtained sample was measured for load-bearing property, flexibility, pore-holding ratio, water vapor adsorption performance, and processability.
The measurement results of the absorbent sheet samples obtained in examples 1 to 17 and comparative examples 1 to 6 are shown in tables 1 to 5.
As is apparent from tables 1 to 5, the adsorption sheets of examples 1 to 17 were excellent in the supporting property of the porous metal complex and the flexibility and processability of the sheet, and had sufficient adsorption performance.
[ industrial applicability ]
The adsorption sheet, the adsorption element, and the adsorption/desorption processing apparatus according to the present invention can efficiently separate, recover, and adsorb and remove substances to be adsorbed, such as moisture, organic solvents, and malodorous components. Therefore, it can be expected to make a large contribution to the industry.
Claims (6)
1. An absorbent sheet comprising a porous metal complex, non-fibrillated fibers and fibrillated fibers, wherein the porous metal complex comprises a metal and an organic ligand, and has a moisture absorption rate of 30 mass% or more at 25 ℃ and a relative pressure of 0.5.
2. The absorbent sheet according to claim 1, wherein the organic binder has a water-soluble temperature of 65 to 100 ℃.
3. The absorbent sheet according to claim 1 or 2, wherein the relative 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 mass%.
5. An adsorption element comprising the adsorption sheet according to any one of claims 1 to 4.
6. An adsorption/desorption processing apparatus comprising the adsorption element according to claim 5,
An adsorption device for introducing the substance to be adsorbed into the adsorption element and adsorbing the substance,
And a desorption device for desorbing the substance to be adsorbed by the adsorption element, wherein the substance to be adsorbed is continuously adsorbed and desorbed.
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| JP2002239329A (en) * | 2001-02-21 | 2002-08-27 | Daikin Ind Ltd | Adsorption element and manufacturing method therefor |
| CN101484636A (en) * | 2006-07-05 | 2009-07-15 | 三菱制纸株式会社 | Sheetlike products and works |
| JP2013154302A (en) * | 2012-01-30 | 2013-08-15 | Showa Denko Kk | Adsorption sheet |
| JP2013154301A (en) * | 2012-01-30 | 2013-08-15 | Toyobo Co Ltd | Adsorption sheet and adsorption element using the same |
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| JP3917324B2 (en) | 1999-05-19 | 2007-05-23 | 大陽日酸株式会社 | Porous complexes and adsorbents |
| JP4737845B2 (en) | 2000-04-04 | 2011-08-03 | 大阪瓦斯株式会社 | Novel three-dimensional organometallic complex and gas adsorbent |
| KR20070051112A (en) | 2005-11-14 | 2007-05-17 | 삼성전자주식회사 | Apparatus for aligning manipulator of ion implantation equipment |
| JP2011183326A (en) * | 2010-03-10 | 2011-09-22 | Mitsubishi Paper Mills Ltd | Sheet-like material for dehumidification |
| JP6188724B2 (en) * | 2012-12-26 | 2017-08-30 | 昭和電工株式会社 | Gas separation material and gas separation method using metal complex |
| JP2017088542A (en) * | 2015-11-10 | 2017-05-25 | 株式会社豊田中央研究所 | Metal organic structure, adsorbent using the same and manufacturing method therefor |
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| JP2002239329A (en) * | 2001-02-21 | 2002-08-27 | Daikin Ind Ltd | Adsorption element and manufacturing method therefor |
| CN101484636A (en) * | 2006-07-05 | 2009-07-15 | 三菱制纸株式会社 | Sheetlike products and works |
| JP2013154302A (en) * | 2012-01-30 | 2013-08-15 | Showa Denko Kk | Adsorption sheet |
| JP2013154301A (en) * | 2012-01-30 | 2013-08-15 | Toyobo Co Ltd | Adsorption sheet and adsorption element using the same |
| CN105163846A (en) * | 2013-07-26 | 2015-12-16 | 昭和电工株式会社 | Molded article for hydrocarbon adsorption |
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