WO2019235429A1 - Adsorbing sheet, adsorbing sheet production method, and adsorbing element - Google Patents

Abstract

This adsorbing sheet contains at least one or more adsorbing materials (Ax: x = 1, 2, 3···n). When Axa represents the tap density of the adsorbing material (Ax), Axb represents the spherical volume calculated from the mean particle size of an adsorbing material particle when the adsorbing material particle is assumed to be spherically shaped, and Axc represents the weight ratio (%) of the adsorbing material contained in the adsorbing sheet, this adsorbing sheet is such that the mean particle count Axd contained per 1 g of the adsorbing sheet is represented by Formula 1, the total mean particle count of the at least one adsorbing material (Ax) contained per 1 g of the adsorbing sheet is represented by Formula 2, and the specific tensile strength of the adsorbing sheet is 2N·m/g or greater. Formula 1: Axd = (1/Axa) × (1/Axb) × (Axc/100) (counts/g) ··· Formula 2

Description

Adsorption sheet, production method of adsorption sheet, and adsorption element

The present invention relates to an adsorbent sheet for adsorbing and removing an organic solvent contained in air using an adsorbent, and an adsorbent sheet manufacturing method.

The present invention relates to an adsorbing element used in an exhaust gas treatment apparatus for adsorbing and removing malodorous components such as organic solvents contained in the air.

Conventionally, as an adsorbing sheet, an adsorbing sheet formed by mixing and forming an organic binder such as PVA (polyvinyl alcohol) and organic fibers or inorganic fibers and an adsorbent is known (for example, Japanese Patent Laid-Open No. Hei 9 (1998)). No. 9-94422 (Patent Document 1)).

Conventionally, as an adsorbing element, an adsorbent sheet containing an adsorbent, organic fiber, organic binder, inorganic binder, etc., is formed into a honeycomb shape by using a honeycomb forming adhesive with a honeycomb forming machine. (For example, see JP-A-10-352 (Patent Document 2)).

JP-A-9-94422 Japanese Patent Laid-Open No. 10-352

This adsorbing sheet is described in Patent Document 1 when an adsorbent of zeolite is included. Organic fibers and inorganic fibers, which are skeleton materials, play a role in the flexibility and mechanical strength of the adsorption sheet. In order to exhibit high performance as an adsorption sheet, it is effective to improve the content ratio of the adsorbent. However, since the content ratio of organic fibers and inorganic fibers, which are skeleton materials, is decreased, there is a problem that the flexibility and strength of the adsorbing sheet are lowered as a result.

If the adsorption element contains zeolite as an adsorbent, it is described in Patent Document 2. Zeolite may be in the form of powder, particles, or pellets. Organic fiber, which is a skeleton material, plays a role in the flexibility and mechanical strength of the adsorption element. In order to demonstrate high performance as an adsorbing element, it is effective to improve the content ratio of the adsorbent, but on the contrary, the content ratio of organic fibers and inorganic fibers, which are skeleton materials, decreases. There existed a subject that a softness | flexibility and intensity | strength fell.

Adsorbents in adsorbent sheets and adsorbent elements have specific apparent densities (bulk density (loose bulk density) and tap density), including the chemical type of the adsorbent (activated carbon, zeolite species, silica gel, etc.) The shape (particle diameter, fiber diameter, etc.) as a bulk is closely related. Even if the adsorbent content in the adsorbing sheet is the same, there is a difference in the number of particles calculated from the apparent density and the particle size, and the number of particles is too large and the entanglement of the skeleton material is reduced. There was a problem that practical strength could not be obtained.

The present invention has been made in view of the above problems, and an object of the present invention is to provide an adsorption sheet having excellent mechanical strength and adsorption performance as an adsorption sheet and a method for producing the same.

The present invention has been made in view of the above problems, and an object of the present invention is to provide an adsorbing element having both sufficient flexibility and strength as an adsorbing element and a high adsorbent content ratio.

As a result of diligent research to solve the above problems, the present inventors have finally completed the present invention. That is, the present invention is as follows.

This adsorbing sheet is an adsorbing sheet containing at least one kind of adsorbent (Ax: x = 1, 2, 3... N), wherein the adsorbent (Ax) has a tap density of Axa and adsorbent particles. If the spherical volume calculated from the average particle diameter of the adsorbent particles is Axb and the weight ratio (%) of the adsorbent contained in the adsorbent sheet is Axc, the adsorbent sheet is included per 1 g of the adsorbent sheet. The average particle number Axd is represented by the following formula 1.

The total average particle number of at least one kind of adsorbent (Ax) contained per 1 g of the adsorbing sheet is represented by the following formula 2. The adsorbent sheet has a specific tensile strength of 2 N · m / g or more.

In another embodiment, a total ratio of at least one kind of the adsorbent (Ax) contained in the adsorbing sheet is 40% by weight or more of the adsorbing sheet.

In another embodiment, the adsorbent (Ax) has a tap density of 0.1 g / cm ³ or more.

In another embodiment, the adsorbent (Ax) is zeolite.

In this method for manufacturing an adsorbent sheet, an adsorbent sheet manufacturing method including at least one adsorbent (Ax: x = 1, 2, 3... N), wherein the tap density of the adsorbent (Ax) is set. Assuming that Axa is a spherical volume calculated from the average particle diameter of adsorbent particles when the adsorbent particles are spherical, Axb and the weight ratio (%) of the adsorbent contained in the adsorbent sheet is Axc, per 1 g of the adsorbent sheet The average particle number Axd contained in is represented by the following formula 1.

The total average particle number of at least one kind of adsorbent (Ax) contained per 1 g of the adsorbing sheet is represented by the following formula 2. The adsorbent sheet has a specific tensile strength of 2 N · m / g or more.

In another embodiment, in addition to the adsorbent (Ax), an organic fiber (B-1) having a melting point or a pyrolysis temperature of 300 ° C. or higher, and an organic component (B-2) having a pyrolysis temperature of less than 300 ° C. including.

In another embodiment, the organic fiber is at least one polymer selected from an aramid polymer, a benzimidazole polymer, a benzoxazole polymer, and a polyimide polymer.

In another embodiment, the organic component is at least one selected from polyvinyl alcohol polymers, polyacrylonitrile polymers, and polyvinylpyrrolidone polymers.

In this adsorbing element, a honeycomb using an adsorbing sheet (adsorbing element precursor) having a large number of air passages including at least one kind of adsorbent (Ax ,: x = 1, 2, 3... N). An adsorbing element having a slab structure, wherein the adsorbent (Ax) has a tap density of Axa, and when the adsorbent particles are assumed to be spherical, the spherical volume calculated from the average particle diameter of the adsorbent particles is Axb, and the adsorbent ( Assuming that the weight ratio (%) of Ax) contained in the adsorption sheet is Axc, the average number of particles Axd contained per 1 g of the adsorption sheet is expressed by the following formula 1.

The total average particle number of at least one kind of the adsorbent (Ax) contained per 1 g of the adsorbing sheet is represented by the following formula 5. The plane compression strength of the adsorption element is 3 kPa or more.

The adsorption element according to claim 9, wherein the adsorption sheet has fibers as a skeleton material.

In another embodiment, the suction sheet has a thickness of 0.16 mm to 0.25 mm.

In another form, the honeycomb structure has a cell count of 30 / cm ² to 70 / cm ² .

In another embodiment, the total ratio of at least one kind of the adsorbent (Ax) included in the adsorption element is 40% by weight or more of the adsorption element. The adsorbing element according to item.

In another embodiment, the adsorbent (Ax) has a tap density of 0.1 g / cm ³ or more.

In another embodiment, the adsorbent (Ax) is zeolite.

The adsorbing sheet and the manufacturing method thereof enable an adsorbing sheet having excellent mechanical strength and adsorbing performance as an adsorbing sheet and a manufacturing method thereof.

This adsorbing element makes it possible to provide an adsorbing element having both sufficient flexibility and strength as an adsorbing element and a high adsorbent content ratio.

It is a figure which shows the various characteristics of each Example of a suction sheet in Embodiment 1, and each comparative example. The relationship between the sheet | seat intensity | strength (N * m / g) after baking of each Example and each comparative example of the adsorption sheet in Embodiment 1, and the total number (piece / g) of the adsorbent particle | grains contained in an adsorption sheet is shown. FIG. FIG. 6 is a diagram showing a honeycomb shape that is the shape of the adsorption element in the second embodiment. 4 is a partial enlargement of an adsorbent that adopts a honeycomb-like shape that is the shape of the adsorbing element in the second embodiment. It is a figure which shows the various characteristics of each Example of each adsorption sheet in Embodiment 2, and each comparative example.

(Embodiment 1)
The suction sheet and the manufacturing method thereof according to Embodiment 1 based on the present invention will be described below with reference to the drawings. In the embodiments described below, when referring to the number, amount, and the like, the scope of the present invention is not necessarily limited to the number, amount, and the like unless otherwise specified. The same parts and corresponding parts are denoted by the same reference numerals, and redundant description may not be repeated. It is planned from the beginning to use the structures in the embodiments in appropriate combinations.

[Mixed paper making by wet manufacturing method (making paper with adsorbent added internally)]
When an adsorbent and a skeleton material such as organic fiber / inorganic fiber are mixed and made to obtain an adsorbent sheet, the adsorbent reduces the entanglement points between the skeleton materials. Therefore, from the viewpoint of the bulk density and particle size of the adsorbent, it is preferable that the specific volume representing the volume per unit weight is smaller because the occupied volume of the adsorbent becomes smaller and the entanglement points between the skeleton materials are difficult to reduce. Actually, it is synonymous with that an adsorbent having a large density which is the reciprocal of the specific volume is preferable.

The shape of the adsorbent includes powder, granule, fiber, etc. Considering the amount contained in the adsorbent sheet, not a single powder, a single particle, and a single fiber, but a large amount of powder, particles, and fibers. Generally, it is supported. Therefore, the packing density as an aggregate of powder, particles, and fibers includes loose bulk density and tap density (also called bulk density), but an adsorbent sheet filled with an adsorbent at a high content ratio is assumed. To achieve this, the tap density representing the densely packed state is particularly important.

When the mixed papermaking is wet papermaking, the adsorbent is preferably powdered or granular, particularly preferably powdery. The tap density of the powder is preferably 0.1 g / cm ³ to 2.0 g / cm ³ , more preferably 0.2 g / cm ³ to 1.0 g / cm ³ .

[Relationship with particle size]
The particle size of the adsorbent (Ax) can be evaluated by laser diffraction or the like, and the average particle size is preferably in the range of 0.001 μm to 30.0 μm, more preferably in the range of 0.01 μm to 20 μm. The particle size of the adsorbent is likely to depend on the type of adsorbent, and in particular, the crystal size of zeolite is likely to vary depending on the crystal species. Depending on the crystal type of the zeolite, there is a crystal size of 3 μm or less, in which case it is difficult to obtain a complete dispersion state, and in laser diffraction, a particle size larger than the actual particle size (secondary particle size) may be seen. is there. In that case, the average value of the crystal size, which is the minimum unit confirmed by image analysis such as SEM, is regarded as the average particle size.

The adsorbent in the embodiment is activated carbon or zeolite. Activated carbon and zeolite are excellent for adsorbing and desorbing low concentrations of organic compounds.

In the case of activated carbon, examples of the form include powder having an average particle diameter of 10 μm to 50 μm or fibers having an average fiber diameter of 10 μm to 30 μm. The raw material for the activated carbon is not particularly specified, but there are insulator pattern, coal, pitch, phenol resin, polyacrylonitrile, cellulose and the like.

The adsorbent in the embodiment is preferably zeolite. Zeolite has a high heat-resistant temperature and is less reactive with an organic solvent during adsorption than activated carbon, so it has excellent heat resistance and low risk of heat generation. Further, since zeolite has a sharper pore structure than activated carbon, it has excellent adsorption performance for organic solvents and the like. In the case of zeolite, the form is a powder having an average particle size of 1 μm to 20 μm. Some zeolites are naturally produced, but artificial synthetic zeolites are suitable. Specific examples include beta type, ZSM-5 type, ferrierite type, mordenite type, L type, Y type, and A type.

The adsorbent in the embodiment is more preferably high silica zeolite having a high silica / alumina ratio. This is because high silica zeolite is less susceptible to moisture and humidity in the gas to be treated when adsorbing an organic solvent or the like from the gas to be treated. The silica / alumina ratio is preferably 15 or more, and more preferably 50 or more.

The adsorption element in the embodiment includes at least one adsorbent. One or more of the various activated carbons and zeolites described above may be selected. When a plurality of adsorbents are selected, the ratio is not particularly limited. The adsorbent may be appropriately selected according to the processing conditions of the gas to be processed.

The tap density of the adsorbent (Ax) is [Axa], the spherical volume calculated from the average particle diameter when the adsorbent particles are assumed to be spherical is [Axb], and the weight ratio of the adsorbent contained in the adsorbent sheet is [Axc]. ], The average number of particles [Axd] contained per 1 g of the adsorbing sheet is expressed as [Equation 1] below.

As described above, when adsorbents and skeleton materials such as organic fibers and inorganic fibers are mixed and made to obtain adsorbent sheets, the adsorbents reduce the entanglement points between the skeleton materials, leading to a decrease in the strength of the adsorbent sheets. Cheap. Therefore, in order to obtain a practical strength, it is preferable to suppress the total number of particles to a certain amount or less, and the total average number of particles of at least one kind of adsorbent Ax contained per 1 g of the adsorption sheet is expressed by the following [Equation 2]. It is preferable that it is 8.0 * 10 < ¹² > or less.

[Organic fiber B-1]
The organic component (B) in the present embodiment is a component that supports the adsorbent (Ax) at the time of manufacturing the adsorbing sheet and acts as a carrier that is also supported after forming the adsorbing sheet, and is a pulp-like or short fiber having a fiber length of about 10 mm or less. Organic fibers, especially fibers having a melting point or a thermal decomposition temperature of 300 ° C. or more and excellent heat resistance. If the thermal decomposition temperature is less than 300 ° C., a significant decrease in strength is inevitable at high temperatures encountered during the adsorption / desorption operation. Specifically, it is a fiber made from aramid, meta-aramid, polybenzimidazole (PBI), polybenzoxazole (PBO), polyimide, polyamideimide, polyetherketone or the like.

[Organic binder B-2]
The organic component (B) preferably contains a substance having a thermal decomposition temperature of less than 300 ° C. in addition to the heat-resistant organic component (B-1). The low temperature decomposable organic component (B-2) has a function of a binder for supporting the adsorbent (Ax) on the adsorbing sheet at a high ratio during the production of the adsorbing sheet. Examples of the low temperature decomposable organic component include PVA (polyvinyl alcohol), starch, polyacrylonitrile and the like, and PVA is preferable.

If the adsorbent (Ax) is coated with the low temperature decomposable organic component (B-2) and the adsorption performance is extremely low, the low temperature decomposable organic component (B-2) is converted into a carbide by heat-treating the adsorbent sheet. Alternatively, it is possible to reduce the amount of the adsorbent (Ax) coating by dissociation and disappearance.

[Inorganic binder C]
In the present embodiment, an inorganic binder (C) may be added to fix and maintain the adsorbent (Ax) and the skeleton material at a high temperature of the adsorbent sheet. For example, it is soluble in water, the binder is uniformly dispersed in the sheet, and is cured by reaction, gelation, etc. during the heat treatment, and the adsorbent and the skeleton material are firmly fixed during the curing. The thermal decomposition temperature is 300 ° C or higher, reaction heat is generated by a highly reactive organic solvent, the catalytic property causing the ignition and combustion of the sheet is low, and the adsorption performance of the adsorbent (Ax) is lowered by the coating. It is preferable that it is a difficult thing. For example, phosphate binders such as sodium hexametaphosphate and silicate binders such as sodium silicate are preferred.

[Adsorbent Ax content]
The amount of adsorbent (Ax) contained in the heat-resistant adsorbent sheet of the present embodiment is preferably 40% by weight or more. Considering adsorption performance and productivity, and dropping of adsorbent, 50% by weight or more is preferable. If the content of the adsorbent (Ax) is less than 40%, sufficient adsorption performance cannot be obtained. There is no upper limit on the weight of the adsorbent (Ax), but 80% by weight is the limit to maintain sufficient sheet strength. If it exceeds 80% by weight, the flexibility of the adsorbing sheet is insufficient and it becomes difficult to process. The amount of the organic component (B) contained in the heat-resistant adsorbing sheet of the present embodiment is 5% to 60% by weight as the total amount of the organic component and its thermal oxide used at the time of manufacturing the adsorbing sheet.

If the content of the organic component (B) is less than 5%, the adsorbent carrying capacity is insufficient, and if it is 60% or more, the amount of adsorbent used must be reduced. When the inorganic binder component (C) is contained in the adsorption sheet of the present embodiment, the inorganic binder component (C) is preferably 5% by weight to 30% by weight. If it is less than 5% by weight, the fixing property between the adsorbent (Ax) and the skeleton material becomes poor, and if it exceeds 30%, the flexibility is insufficient, which is not preferable.

[Method of manufacturing suction sheet]
The adsorbing sheet of the present embodiment can be manufactured by a wet papermaking method using, for example, an adsorbing material (Ax), an organic component (B) and an inorganic binder (C), and if necessary, glass fiber and a polymer flocculant. it can.

[Concept of B-1 and B-2 in manufacturing method]
The organic component (B) used in the production method of the adsorbing sheet of the present embodiment is low temperature decomposable that thermally decomposes at 150 ° C. to 300 ° C. in addition to the heat-resistant organic fiber (B-1) such as aramid fiber. It is desirable to use an organic component (B-2). The low temperature decomposable organic component (B-2) serves as a binder for bonding the (Ax) component to the (B-1) component and the (B-1) components during wet papermaking.

The component (B-2) covers the adsorbent of the final adsorbing element (adsorbing element of the present embodiment) after forming a sheet-like material or honeycomb-like material. It is also possible to reduce the coating of the adsorbent of the final adsorbing element (adsorbing element of the present embodiment) by using (B-2) as a carbide or decomposing and disappearing.

When the heat treatment is performed on the sheet-like material and the honeycomb-like material, it is preferably performed in an air atmosphere using a heating oven or the like. The heat treatment temperature is equal to or lower than the melting point or decomposition temperature (T1 ° C.) of the heat-resistant organic component (B-1), preferably 5 ° C. to 20 ° C. (T 1-5 ° C. to T 1-20 ° C.), and the low temperature decomposition component (B-2). ) Decomposition temperature (T2 ° C.) or higher, preferably at a decomposition temperature of 100 ° C. to 200 ° C. or higher (T2 + 100 ° C. to T2 + 200 ° C.), and the treatment time is 1 minute to 60 minutes, preferably 1 minute to 30 minutes. . Usually, 350 ° C. to 450 ° C. and 1 minute to 10 minutes.

The specific tensile strength of the adsorption sheet is preferably 2 N / m · g or more. If the strength is less than 2 N / m · g, the adsorbing sheet is likely to break or crack, which is not practical.

The basis weight (g / m ² ) of the adsorption sheet is not particularly limited, but is preferably 10 g / m ² to 200 g / m ² . When it is less than 10 g / m ² , the mechanical strength of the sheet becomes weak and the mechanical strength of the honeycomb structure cannot be maintained. If it exceeds 200 g / m ² , the thickness of the sheet becomes too thick, so that the flexibility of the sheet is lost, and cracking of the sheet and dropping of the adsorbent are likely to occur.

(Example)
A method for measuring various characteristics of the adsorption sheet in the present embodiment is as follows. Various characteristics of each example and each comparative example are shown in FIG. 1 and FIG.

(1) Measuring method of adsorbent tap density About 40 g of adsorbent is put into a constant-weight container and vacuum dried at 180 ° C. for 15 hours or more. After allowing to cool in a desiccator for 20 minutes, the dry mass is measured to the order of 0.1 mg. Let the mass of this dry sample be S (g). Put all of this dry sample in a 200 mL graduated cylinder and tap the bottom of the graduated cylinder for 3 minutes (tap the bottom of the graduated cylinder). Read the volume (mL) after 3 minutes to the order of 1 mL. Assuming that the filling volume is A (mL), the tap density L (g / mL) is obtained by the following equation 3. Since 1 mL is 1 cm ³ , the unit of the tap density L is synonymous with g / mL and g / cm ³ .

(2) Method of measuring the average particle size of the adsorbent and calculating the sphere volume when the particles are assumed to be spherical When the adsorbent is confirmed by SEM image observation in advance, the crystal particle size is 3 μm or more. Calculates the average particle size of the adsorbent using the average particle size measurement method by SEM image analysis when the crystal particle size is smaller than 3 μm. To do.

<Measuring method of average particle diameter by laser diffraction / scattering particle size distribution analyzer>
LA-950V2 from Horiba, Ltd. is used as the measurement device, wet circulation type cell (flow cell) is used as the measurement cell, and sodium hexametaphosphate (0.1 mass% aqueous solution) is used as the dispersion medium. For setting the refractive index of an object, an aluminum silicate-water system (refractive index: 1.66-1.33) is used.

[Measurement procedure]
1. Inject a specified amount of dispersion medium into the measurement cell, perform initial adjustment of the optical system, and perform blank measurement.

2. After the blank measurement, the adsorbent is put into the cell so that the transmittance of the dispersion medium falls within the range of about 90% to 70%.

3. After applying ultrasonic waves (frequency 20 kHz) for about several seconds for defoaming, measurement is performed once.

4. After the measurement, ultrasonic waves are applied for a specified time (5 minutes) to disperse the sample, and then the measurement is performed again.

5. Analysis is performed from data obtained by applying ultrasonic waves for a specified time (5 minutes) and measuring again, and the median diameter (particle diameter at which the cumulative frequency is 50%) is defined as the average particle diameter.

<Measuring method of average particle diameter by SEM image analysis>
A Hitachi scanning electron microscope (SU1510) is used as the measuring device, and the acceleration voltage is 15.0 kV.

[Measurement procedure]
1. Put double-sided tape on the SEM observation stand, spread the adsorbent on the double-sided tape, and remove the excessive amount of adsorbent.

2. Platinum vapor deposition is performed on the SEM observation platform coated with the adsorbent.
3. 1. SEM image observation device Set the observation platform.

4). Take 3 pictures at 3000 times with the above acceleration voltage.
5. Print on A4 paper at the maximum size that fits all the photos taken at 3000x on the paper.

6. Draw two diagonal lines with a pencil on the printed photo, select 20 particles with a clear boundary on the diagonal line, and measure the two points of the minor axis and major axis with a ruler. The length of the SEM photograph scale (μm) is measured with a ruler, and the minor axis and major axis of the particle measured with the ruler are converted into μm.

7.6. The above operation is performed with three photographs taken at 3000 times, the short diameter and long diameter of a total of 60 particles are calculated, and the average value of all values is taken as the average particle diameter (μm) by SEM observation.

<Calculation method of sphere volume when particle is assumed to be spherical>
When the average particle diameter calculated by laser diffraction or SEM image analysis is R (μm), the spherical volume Q (cm ³ / piece) per particle when the particle is assumed to be spherical is obtained by the following equation 4.

(3) Method for measuring specific tensile strength Measured according to JIS-P-8113 “Paper and paperboard—Testing method for tensile properties”. The test width was 15 mm and the length was 50 mm.

The adsorbing sheet of the present invention will be described in detail based on the following examples and comparative examples.
<Example 1>
The adsorbent A1 has a tap density of 0.54 g / cm ³ , ZSM-5 (MFI) zeolite having an average particle diameter of 3.3 μm by laser diffraction is 37.5% by weight, and the adsorbent A2 has a tap density of 0.36 g / cm ³ . 37.5% by weight of cm ³ , Y-type (FAU) zeolite having an average particle size calculated from SEM image analysis of 1.2 μm, and pulp-like and short-fiber aramid fibers (heat-resistant organic component: B) as the heat-resistant organic component -1) and 17% by weight of PVA (low-temperature thermally decomposable organic component: B-2) as a thermally decomposable organic binder, and a weight of 100 g / m ² basis weight. A use sheet was made.

Next, this sheet-like material was impregnated with a 20% by weight aqueous solution of sodium hexametaphosphate as an inorganic binder, dried with air at 100 ° C., and fixed to a 5% by weight sodium hexametaphosphate sheet to obtain a precursor sheet. Thereafter, heat treatment was performed in a baking furnace at 400 ° C. for about 3 minutes to obtain an adsorption sheet.

<Example 2>
The adsorbent A1 has a tap density of 0.39 g / cm ³ , ZSM-5 (MFI) zeolite having an average particle diameter of 9.9 μm by laser analysis is 37.5% by weight, and the adsorbent A2 has a tap density of 0.34 g / cm ³ . 37.5% by weight of cm ³ , Y-type (FAU) zeolite having an average particle size of 0.7 μm calculated from SEM photographic analysis, and pulp-like and short-fiber aramid fibers (heat-resistant organic component: B) as the heat-resistant organic component -1) and 17% by weight of PVA (low-temperature thermally decomposable organic component: B-2) as a thermally decomposable organic binder, and a weight of 100 g / m ² basis weight. A use sheet was made.

Next, this sheet-like material was impregnated with a 20% by weight aqueous solution of sodium hexametaphosphate as an inorganic binder, dried with air at 100 ° C., and fixed to a 5% by weight sodium hexametaphosphate sheet to obtain a precursor sheet. Thereafter, heat treatment was performed in a baking furnace at 400 ° C. for about 3 minutes to obtain an adsorption sheet.

<Example 3>
The adsorbent A1 has a tap density of 0.58 g / cm ³ , 37.5% by weight of ZSM-5 (MFI) zeolite having an average particle size of 4.8 μm by laser analysis, and the adsorbent A2 has a tap density of 0.34 g / cm ³ . 37.5% by weight of cm ³ , Y-type (FAU) zeolite having an average particle size of 0.7 μm calculated from SEM photographic analysis, and pulp-like and short-fiber aramid fibers (heat-resistant organic component: B) as the heat-resistant organic component -1) and 17% by weight of PVA (low-temperature thermally decomposable organic component: B-2) as a thermally decomposable organic binder, and a weight of 100 g / m ² basis weight. A use sheet was made.

Next, this sheet-like material was impregnated with a 20% by weight aqueous solution of sodium hexametaphosphate as an inorganic binder, dried with air at 100 ° C., and fixed to a 5% by weight sodium hexametaphosphate sheet to obtain a precursor sheet. Thereafter, heat treatment was performed in a baking furnace at 400 ° C. for about 3 minutes to obtain an adsorption sheet.

<Example 4>
Adsorbent A1 has a tap density of 0.54 g / cm ³ , ZSM-5 (MFI) zeolite (MFI) having an average particle diameter of 3.2 μm by laser analysis is 60% by weight, and adsorbent A2 has a tap density of 0.36 g. 37.5% by weight of Y-type (FAU) zeolite having an average particle size calculated from SEM photographic analysis of 1.2 μm / cm ³ , and pulp-like and short fibrous aramid fibers (heat-resistant organic component: B-1) 17% by weight and PVA (low-temperature thermally decomposable organic component: B-2) 8% by weight as a thermally decomposable organic binder at a weight of 100 g / m ² basis weight. A sheet was created using.

Next, this sheet-like material was impregnated with a 20% by weight aqueous solution of sodium hexametaphosphate as an inorganic binder, dried with air at 100 ° C., and fixed to a 5% by weight sodium hexametaphosphate sheet to obtain a precursor sheet. Thereafter, heat treatment was performed in a baking furnace at 400 ° C. for about 3 minutes to obtain an adsorption sheet.

<Example 5>
The adsorbent A1 has a tap density of 0.39 g / cm ³ , ZSM-5 (MFI) zeolite having an average particle diameter of 9.9 μm by laser analysis of 75% by weight, and pulp and short fiber aramid fibers as heat-resistant organic components 17% by weight of (heat-resistant organic component: B-1) and 8% by weight of PVA (low-temperature thermally-decomposable organic component: B-2) as a thermally decomposable organic binder have a basis weight of 100 g / m ^2. Sheet material was prepared using a wet papermaking machine by weight.

Next, this sheet-like material was impregnated with a 20% by weight aqueous solution of sodium hexametaphosphate as an inorganic binder, dried with air at 100 ° C., and fixed to a 5% by weight sodium hexametaphosphate sheet to obtain a precursor sheet. Thereafter, heat treatment was performed in a baking furnace at 400 ° C. for about 3 minutes to obtain an adsorption sheet.

<Example 6>
As adsorbent A1, ZSM-5 (MFI) zeolite having a tap density of 0.58 g / cm ³ , an average particle diameter of 4.8 μm by laser analysis is 75% by weight, and pulp-like and short-fiber aramid fibers as heat-resistant organic components 17% by weight of (heat-resistant organic component: B-1), 8% by weight of PVA (low-temperature thermally decomposable organic component: B-2) as a thermally decomposable organic binder, and a basis weight of 100 g / m ² A sheet was prepared using a wet papermaking machine.

Next, this sheet-like material was impregnated with a 20% by weight aqueous solution of sodium hexametaphosphate as an inorganic binder, dried with air at 100 ° C., and fixed to a 5% by weight sodium hexametaphosphate sheet to obtain a precursor sheet. Thereafter, heat treatment was performed in a baking furnace at 400 ° C. for about 3 minutes to obtain an adsorption sheet.

<Example 7>
As adsorbent A1, ZSM-5 (MFI) zeolite having a tap density of 0.54 g / cm ³ , an average particle diameter of 3.2 μm by laser analysis is 75% by weight, and pulp and short fiber aramid fibers as heat-resistant organic components 17% by weight of (heat-resistant organic component: B-1) and 8% by weight of PVA (low-temperature thermally-decomposable organic component: B-2) as a thermally decomposable organic binder have a basis weight of 100 g / m ^2. Sheet material was prepared using a wet papermaking machine by weight.

Next, this sheet-like material was impregnated with a 20% by weight aqueous solution of sodium hexametaphosphate as an inorganic binder, dried with air at 100 ° C., and fixed to a 5% by weight sodium hexametaphosphate sheet to obtain a precursor sheet. Thereafter, heat treatment was performed in a baking furnace at 400 ° C. for about 3 minutes to obtain an adsorption sheet.

<Example 8>
Adsorbent A1 has a tap density of 0.59 g / cm ³ , an average particle size calculated from SEM image analysis of 0.8 μm beta type ( ^* BEA) zeolite, 75% by weight, and heat-resistant organic pulp and short fibers 17% by weight of aramid fiber (heat-resistant organic component: B-1) and 8% by weight of PVA (low-temperature thermally decomposable organic component: B-2) as a thermally decomposable organic binder, basis weight 100 g / m ^A sheet-like material was prepared using a wet papermaking machine with a weight of ² .

Next, this sheet-like material was impregnated with a 20% by weight aqueous solution of sodium hexametaphosphate as an inorganic binder, dried with air at 100 ° C., and fixed to a 5% by weight sodium hexametaphosphate sheet to obtain a precursor sheet. Thereafter, heat treatment was performed in a baking furnace at 400 ° C. for about 3 minutes to obtain an adsorption sheet.

<Comparative Example 1>
The adsorbent A1 has a tap density of 0.39 g / cm ³ , ZSM-5 (MFI) zeolite having an average particle diameter of 10.7 μm by laser analysis is 15% by weight, and the adsorbent A2 has a tap density of 0.34 g / cm 3. 60% by weight of Y-type (FAU) zeolite having an average particle size of 0.7 μm calculated from SEM image analysis, and 17 pulp-like and short fibrous aramid fibers (heat-resistant organic component: B-1) as heat-resistant organic components Using a wet papermaking machine with a weight of 8% by weight of PVA (low-temperature thermally decomposable organic component: B-2) as a thermally decomposable organic binder and a weight of 100 g / m ² , a sheet-like material is obtained. Created.

Next, this sheet-like material was impregnated with a 20% by weight aqueous solution of sodium hexametaphosphate as an inorganic binder, dried with air at 100 ° C., and fixed to a 5% by weight sodium hexametaphosphate sheet to obtain a precursor sheet. Thereafter, heat treatment was performed in a baking furnace at 400 ° C. for about 3 minutes to obtain an adsorption sheet.

<Comparative example 2>
Adsorbent A1 has a tap density of 0.54 g / cm ³ , ZSM-5 (MFI) zeolite having an average particle diameter of 3.2 μm by laser analysis is 15% by weight, and adsorbent A2 has a tap density of 0.36 g / cm ^3. 60% by weight of Y-type (FAU) zeolite with an average particle size calculated from SEM image analysis of 1.3 μm, and pulp-like and short-fiber aramid fibers (heat-resistant organic component: B-1) as the heat-resistant organic component 17% by weight, 8% by weight of PVA (low-temperature thermally decomposable organic component: B-2) as a thermally decomposable organic binder, and a weight of 100 g / m ² basis weight. Created.

Next, this sheet-like material was impregnated with a 20% by weight aqueous solution of sodium hexametaphosphate as an inorganic binder, dried with air at 100 ° C., and fixed to a 5% by weight sodium hexametaphosphate sheet to obtain a precursor sheet. Thereafter, heat treatment was performed in a baking furnace at 400 ° C. for about 3 minutes to obtain an adsorption sheet.

<Comparative Example 3>
The adsorbent A1 has a tap density of 0.34 g / cm ³ , an average particle diameter calculated from SEM image analysis of 0.7 μm, 75% by weight of Y-type (FAU) zeolite, and heat-resistant organic components such as pulp and short fibers 17% by weight of aramid fiber (heat-resistant organic component: B-1), 8% by weight of PVA (low-temperature thermally decomposable organic component: B-2) as a thermally decomposable organic binder, and a basis weight of 100 g / m ² A sheet-like material was prepared using a wet papermaking machine at a weight of

Next, this sheet-like material was impregnated with a 20% by weight aqueous solution of sodium hexametaphosphate as an inorganic binder, dried with air at 100 ° C., and fixed to a 5% by weight sodium hexametaphosphate sheet to obtain a precursor sheet. Thereafter, heat treatment was performed in a baking furnace at 400 ° C. for about 3 minutes to obtain an adsorption sheet.

The adsorbing sheet of the present embodiment is an adsorbing sheet manufactured by a wet papermaking method having at least one adsorbent, and the adsorbent is compatible with the strength of the adsorbing sheet and the high content weight ratio of the adsorbent. An organic component having a melting point or a thermal decomposition temperature of 300 ° C. or higher and an organic component having a thermal decomposition temperature of less than 300 ° C. are appropriately set based on the total number of particles contained in the sheet calculated from the bulk density and particle size of the adsorbent. And an inorganic binder as a skeleton material are excellent in flexibility and strength as an adsorbing sheet, and adsorbing performance is also excellent because the adsorbent content weight ratio is extremely high.

As shown in each of the above Examples and Comparative Examples, the strength of the adsorbing sheet is clearly different depending on the total number of adsorbent particles contained in the adsorbing sheet, and the total number of particles is 8.0 × 10 ¹² or less. Thus, an adsorbing element sheet having sufficient strength for practical use could be obtained.

(Embodiment 2)
The adsorption element according to Embodiment 2 based on the present invention will be described below with reference to the drawings. In the embodiments described below, when referring to the number, amount, and the like, the scope of the present invention is not necessarily limited to the number, amount, and the like unless otherwise specified. The same parts and corresponding parts are denoted by the same reference numerals, and redundant description may not be repeated. It is planned from the beginning to use the structures in the embodiments in appropriate combinations.

[Mixed paper making by wet manufacturing method (making paper with adsorbent added internally)]
When the adsorbent and the skeleton material such as organic fiber or inorganic fiber are mixed and made, and the adsorbent sheet is obtained by using a honeycomb molding machine with a honeycomb forming adhesive to obtain an adsorbing element formed into a honeycomb shape, the adsorbent is a skeleton. It reduces the tangling points between materials. Therefore, from the viewpoint of the bulk density and particle size of the adsorbent, it is preferable that the specific volume representing the volume per unit weight is smaller because the occupied volume of the adsorbent becomes smaller and the entanglement points between the skeleton materials are difficult to reduce.

Actually, it is synonymous with the fact that an adsorbent having a large density, which is the reciprocal of the specific volume, is preferable. Adsorbents can be in the form of powder, granule, fiber, etc. Considering the amount contained in the adsorbent element, a large amount of powder, particles and fibers are supported instead of one powder, one particle and one fiber. It is common to be done. Therefore, there are loose bulk density and tap density (also referred to as bulk density) as the packing density of powder, particles, and fiber aggregates. The tap density representing a more densely packed state is particularly important.

When the mixed papermaking is wet papermaking, the adsorbent is preferably powdered or granular, particularly preferably powdery. The tap density of the powder is preferably 0.1 g / cm ³ to 2.0 g / cm ³ , more preferably 0.2 to 1.0 g / cm ³ .

[Relationship with particle size]
The particle diameter of the adsorbent (Ax) can be evaluated by laser diffraction or the like, and the average particle diameter is preferably in the range of 0.001 μm to 30.0 μm, more preferably 0.01 μm to 20 μm. The particle size of the adsorbent may depend on the type of adsorbent. In particular, the crystal size of zeolite is likely to vary depending on the crystal species. Depending on the crystal type of the zeolite, there is a crystal size of 3 μm or less, in which case it is difficult to obtain a complete dispersion state, and in laser diffraction, a particle size larger than the actual particle size (secondary particle size) may be seen. is there. In that case, the average value of the crystal size, which is the smallest unit confirmed by image analysis such as SEM (Scanning Electron Microscope), is regarded as the average particle diameter.

The adsorbent in the embodiment is activated carbon or zeolite. Activated carbon and zeolite are excellent for adsorbing and desorbing low concentrations of organic compounds.

In the case of activated carbon, examples of the form include powder having an average particle diameter of 10 μm to 50 μm or fibers having an average fiber diameter of 10 μm to 30 μm. The raw material for the activated carbon is not particularly specified, but there are insulator pattern, coal, pitch, phenol resin, polyacrylonitrile, cellulose and the like.

The adsorbent in the embodiment is preferably zeolite. Zeolite has a high heat-resistant temperature and is less reactive with an organic solvent during adsorption than activated carbon, so it has excellent heat resistance and low risk of heat generation. Further, since zeolite has a sharper pore structure than activated carbon, it has excellent adsorption performance for organic solvents and the like. In the case of zeolite, the form is a powder having an average particle size of 1 μm to 20 μm. Some zeolites are naturally produced, but artificial synthetic zeolites are suitable. Specific examples include beta type, ZSM-5 type, ferrierite type, mordenite type, L type, Y type, and A type.

The adsorbent in the embodiment is more preferably high silica zeolite having a high silica / alumina ratio. This is because high silica zeolite is less susceptible to moisture and humidity in the gas to be treated when adsorbing an organic solvent or the like from the gas to be treated. The silica / alumina ratio is preferably 15 or more, and more preferably 50 or more.

The adsorption element in the embodiment includes at least one adsorbent. One or more of the various activated carbons and zeolites described above may be selected. When a plurality of adsorbents are selected, the ratio is not particularly limited. The adsorbent may be appropriately selected according to the processing conditions of the gas to be processed.

The tap density of the adsorbent (Ax) is [Axa], the spherical volume calculated from the average particle diameter when the adsorbent particles are assumed to be spherical is [Axb], and the weight ratio of the adsorbent contained in the adsorbent sheet is [Axc]. ], The average number of particles [Axd] contained per 1 g of the adsorbing element is expressed as [Equation 1] below.

As described above, when adsorbents and skeleton materials such as organic fibers and inorganic fibers are mixed and made to obtain adsorbent sheets, the adsorbents reduce the entanglement points between the skeleton materials, leading to a decrease in the strength of the adsorbent sheets. Cheap. Therefore, in order to obtain a practical strength, it is preferable to suppress the total number of particles to a certain amount or less, and the total average number of particles of at least one kind of adsorbent Ax contained per 1 g of the adsorption sheet is expressed by the following [Equation 2]. It is preferable that it is 8.0 * 10 < ¹² > or less.

[Organic fiber B-1]
The organic component (B) in the present embodiment is a component that supports the adsorbent (Ax) at the time of manufacturing the adsorbing sheet and acts as a carrier that is also supported after forming the adsorbing sheet, and is a pulp-like or short fiber having a fiber length of about 10 mm or less. Organic fibers, especially fibers having a melting point or a thermal decomposition temperature of 300 ° C. or more and excellent heat resistance. If the thermal decomposition temperature is less than 300 ° C., a significant decrease in strength is inevitable at high temperatures encountered during the adsorption / desorption operation. Specifically, it is a fiber made from aramid, meta-aramid, polybenzimidazole (PBI), polybenzoxazole (PBO), polyimide, polyamideimide, polyetherketone or the like.

[Organic binder B-2]
The organic component (B) preferably contains a substance having a thermal decomposition temperature of less than 300 ° C. in addition to the heat-resistant organic component (B-1). The low temperature decomposable organic component (B-2) has a function of a binder for supporting the adsorbent (Ax) on the adsorbing sheet at a high ratio during the production of the adsorbing sheet. Examples of the low temperature decomposable organic component include PVA (polyvinyl alcohol), starch, polyacrylonitrile and the like, and PVA is preferable.

If the adsorbent (Ax) is coated with the low temperature decomposable organic component (B-2) and the adsorption performance is extremely low, the low temperature decomposable organic component (B-2) is converted into a carbide by heat-treating the adsorbent sheet. Alternatively, it is possible to reduce the amount of the adsorbent (Ax) coating by dissociation and disappearance.

[Inorganic binder C]
In the present embodiment, the adsorbent (Ax) and the skeletal material are fixedly maintained at a high temperature in the adsorbent sheet, and the adsorbent sheet having a large number of air passages as shown in FIGS. An inorganic binder (C) may be applied to fix and maintain the flute portion 2a and the liner portion 2b that constitute the structure.

For example, it is soluble in water, the binder is uniformly dispersed in the sheet, and is cured by reaction, gelation, etc. during heat treatment, and the adsorbent and the skeleton material are firmly fixed during the curing. In addition, the thermal decomposition temperature is 300 ° C or higher, reaction heat is generated by a highly reactive organic solvent, the catalytic property causing the ignition and combustion of the sheet is low, and the adsorption performance of the adsorbent (Ax) is lowered by the coating. It is preferable that it is a thing which is hard to carry out. For example, phosphate binders such as sodium hexametaphosphate and silicate binders such as sodium silicate are preferred.

The inorganic binder (C-1) for fixing and maintaining the adsorbent (Ax) and the constituent fibers, and the inorganic binder (C-2) for fixing and maintaining the flute portion 2a and the liner portion 2b constituting the honeycomb are made of the same type of binder. There is no need to use it, and it is desirable to use a binder that is more suitable for productivity.

[Adsorbent Ax content]
The amount of adsorbent (Ax) contained in the adsorbing element of the present embodiment is preferably 40% by weight or more. Considering adsorption performance and productivity, and dropping of adsorbent, 50% by weight or more is preferable. If the content of the adsorbent (Ax) is less than 40%, sufficient adsorption performance cannot be obtained. The upper limit of the weight of the adsorbent is not limited, but 80% by weight or less is the limit for maintaining the shape of the adsorbing element. If it exceeds 80% by weight, the flexibility of the adsorbing sheet is insufficient and it becomes difficult to process. The amount of the organic component (B) contained in the adsorption element of the present embodiment is the combined amount of the organic component used in the production of the adsorption element precursor (precursor element) and the thermal oxide when heat treatment is performed. As 5 to 60% by weight.

If the content of the organic component (B) is less than 5%, the adsorbent carrying capacity is insufficient, and if it is 60% or more, the amount of adsorbent used must be reduced. The amount of the inorganic binder component (C) contained in the adsorption element of the present embodiment is 5% by weight to 30% by weight. If it is less than 5% by weight, the fixing property between the adsorbent (Ax) and the skeleton material becomes poor, and if it is 30% by weight or more, the flexibility is insufficient, which is not preferable.

[Honeycomb structure]
The structure of the adsorption element in the present embodiment is preferably a honeycomb structure from the viewpoint of mechanical strength and manufacturing cost, and the number of cells is preferably 30 cells / cm ² to 70 cells / cm ² . More preferably, the number of cells is 50 to 70 cells / cm ² . If the number of cells is less than 30 cells / cm ² , the adsorption performance decreases, and if it exceeds 70 cells / cm ² , it is necessary to reduce the thickness of the sheet constituting the partition walls of the honeycomb structure. The strength becomes weak and the sheet cannot be manufactured. The cell shape of the honeycomb structure is not particularly specified, but taking the cell shape shown in FIG. 1 as an example, the wave height is 1 mm to 3 mm and the wavelength is 2 mm to 4 mm. More preferably, the wave height is 1 mm to 1.6 mm and the wavelength is 2 mm to 2.6 mm. Here, the honeycomb-like structure represents a general three-dimensional structure composed of a plurality of small spaces (cell shapes) surrounded by side walls.

The partition wall thickness of the honeycomb structure constituting the adsorption element in the present embodiment is preferably 0.16 mm to 0.25 mm. When the thickness is less than 0.16 mm, it is necessary to make the thickness of the sheet constituting the partition thinner, but the mechanical strength of the sheet becomes weak and the sheet cannot be manufactured. When the thickness exceeds 0.25 mm, the partition wall becomes thick, and the aforementioned number of cells cannot be obtained.

The basis weight of the sheet constituting the adsorption element in the present embodiment is preferably 65 g / m ² to 90 g / m ² . When it is less than 65 g / m ² , the mechanical strength of the sheet becomes weak, and the mechanical strength of the honeycomb structure after the heat treatment cannot be maintained. When it exceeds 90 g / m ² , the partition wall becomes thick and the aforementioned number of cells cannot be obtained.

[Method of manufacturing adsorption element]
The adsorbing element in the present embodiment was formed into a honeycomb shape by using a honeycomb forming machine and a sheet-shaped material with an adsorbent (Ax), an organic component (B), and an inorganic binder (C) using a honeycomb forming machine. After preparing the honeycomb-like material (precursor element), the precursor element is heated to a temperature equal to or lower than the melting point or decomposition temperature of the heat-resistant organic component of the organic component (B), and at a temperature equal to or higher than the decomposition temperature of the low-temperature decomposable organic component. It can be produced by thermally oxidizing and decomposing low temperature decomposable organic components by heat treatment for min to 60 min, and most of them are carbides or decomposed and disappeared.

[Concept of B-1 and B-2 in manufacturing method]
The organic component (B) used in the production of the adsorbing element of the present embodiment is a low-temperature decomposable organic component that thermally decomposes at 150 ° C. to 300 ° C. in addition to the heat-resistant organic fiber (B-1) such as an aramid fiber. It is desirable to use (B-2). The low temperature decomposable organic component (B-2) serves as a binder for bonding the (Ax) component to the (B-1) component and the (B-1) components during wet papermaking. The component (B-2) covers the adsorbent of the final adsorbing element (adsorbing element of the present embodiment) after forming a sheet-like material or honeycomb-like material. It is also possible to reduce the coating of the adsorbent of the final adsorbing element (adsorbing element of the present embodiment) by using (B-2) as a carbide or by decomposing and disappearing.

When the heat treatment is performed on the sheet-like material and the honeycomb-like material, it is preferably performed in an air atmosphere using a heating oven or the like. The heat treatment temperature is lower than the melting point or decomposition temperature (T1 ° C.) of the heat-resistant organic component (B-1), preferably 5 ° C. to 20 ° C. lower (T 1-5 to T 1-20 ° C.), and the low temperature decomposition component (B-2) The decomposition time (T2 ° C.) or higher, preferably the decomposition temperature of 100 ° C. to 200 ° C. or higher (T2 + 100 to T2 + 200 ° C.), and the treatment time is 1 minute to 60 minutes, preferably 1 minute to 30 minutes. Usually, 350 to 450 ° C. for 1 to 10 minutes.

The planar compressive tensile strength of the adsorption element is preferably 3 kPa or more. If the strength is less than 3 kPa, the adsorbing element is apt to be crushed, and a large number of air passages are not crushed.

The basis weight (g / m ² ) of the adsorption sheet is not particularly limited, but is preferably 10 g / m ² to 200 g / m ² . If it is less than 10 g / m ² , the mechanical strength of the sheet becomes weak, and the mechanical strength of the honeycomb structure cannot be maintained. If it exceeds 200 g / m ² , the thickness of the sheet becomes too thick, so that the flexibility of the sheet is lost, and cracking of the sheet and dropping of the adsorbent are likely to occur.

(Example)
A method for measuring various characteristics of the adsorption sheet in the present embodiment is as follows. Various characteristics of each example and each comparative example are shown in FIG.

(1) Measuring method of adsorbent tap density About 40 g of adsorbent is put into a constant-weight container and vacuum dried at 180 ° C. for 15 hours or more. After allowing to cool in a desiccator for 20 minutes, the dry mass is measured to the order of 0.1 mg. Let the mass of this dry sample be S (g). Put all of this dry sample in a 200 mL graduated cylinder and tap the bottom of the graduated cylinder for 3 minutes (tap the bottom of the graduated cylinder). Read the volume (mL) after 3 minutes to the order of 1 mL. Assuming that the filling volume is A (mL), the tap density L (g / mL) is obtained by the following equation. Since 1 mL is 1 cm ³ , the unit of the tap density L is synonymous with g / mL and g / cm ³ .

(2) Method of measuring the average particle size of the adsorbent and calculating the sphere volume when the particles are assumed to be spherical When the adsorbent is confirmed by SEM image observation in advance, the crystal particle size is 3 μm or more. Calculates the average particle size of the adsorbent using the average particle size measurement method by SEM image analysis when the crystal particle size is smaller than 3 μm. To do.

<Measuring method of average particle diameter by laser diffraction / scattering particle size distribution analyzer>
LA-950V2 from Horiba, Ltd. is used as the measurement device, wet circulation type cell (flow cell) is used as the measurement cell, and sodium hexametaphosphate (0.1 mass% aqueous solution) is used as the dispersion medium. For setting the refractive index of an object, an aluminum silicate-water system (refractive index: 1.66-1.33) is used.

[Measurement procedure]
1. Inject a specified amount of dispersion medium into the measurement cell, perform initial adjustment of the optical system, and perform blank measurement.

2. After the blank measurement, the adsorbent is put into the cell so that the transmittance of the dispersion medium falls within the range of about 90% to 70%.

3. After applying ultrasonic waves (frequency 20 kHz) for about several seconds for defoaming, measurement is performed once.

4. After the measurement, ultrasonic waves are applied for a specified time (5 minutes) to disperse the sample, and then the measurement is performed again.

5. Analysis is performed from data obtained by applying ultrasonic waves for a specified time (5 minutes) and measuring again, and the median diameter (particle diameter at which the cumulative frequency is 50%) is defined as the average particle diameter.

<Measuring method of average particle diameter by SEM image analysis>
A Hitachi scanning electron microscope (SU1510) is used as the measuring device, and the acceleration voltage is 15.0 kV.

[Measurement procedure]
1. Put double-sided tape on the SEM observation stand, spread the adsorbent on the double-sided tape, and remove the excessive amount of adsorbent.

2. Platinum vapor deposition is performed on the SEM observation platform coated with the adsorbent.
3. 1. SEM image observation device Set the observation platform.

4). Take 3 pictures at 3000 times with the above acceleration voltage.
5. Print on A4 paper at the maximum size that fits all the photos taken at 3000x on the paper.

6. Draw two diagonal lines with a pencil on the printed photo, select 20 particles with a clear boundary on the diagonal line, and measure the two points of the minor axis and major axis with a ruler. The length of the SEM photograph scale (μm) is measured with a ruler, and the minor axis and major axis of the particle measured with the ruler are converted into μm.

7.6. The above operation is performed with three photographs taken at 3000 times, the short diameter and long diameter of a total of 60 particles are calculated, and the average value of all values is taken as the average particle diameter (μm) by SEM observation.

<Calculation method of sphere volume when particle is assumed to be spherical>
When the average particle diameter calculated by laser diffraction or SEM image analysis is R (μm), the spherical volume Q (cm ³ / piece) per particle when the particle is assumed to be spherical is obtained by the following equation 4.

(3) Method for measuring specific tensile strength Measured according to JIS-P-8113 “Paper and paperboard—Testing method for tensile properties”. The test width was 15 mm and the length was 50 mm.

(4) Measuring Method of Plane Compressive Strength Measured according to JIS-Z-0403-1 “Cardboard—Part 1: Plane Compressive Strength Test Method”. The test width was 30 mm and the length was 30 mm.

The adsorption element of the present invention will be described in detail based on the following examples and comparative examples.
<Example 11>
The adsorbent A1 has a tap density of 0.54 g / cm ³ , ZSM-5 (MFI) zeolite having an average particle diameter of 3.3 μm by laser diffraction is 37.5% by weight, and the adsorbent A2 has a tap density of 0.36 g / cm ³ . 37.5% by weight of cm ³ , Y-type (FAU) zeolite having an average particle size of 1.2 μm calculated from SEM image analysis, pulp-like and short-fiber aramid fibers (heat-resistant organic component: B-1) is 17% by weight, PVA (low-temperature thermally decomposable organic component: B-2) as a thermally decomposable organic binder is 8% by weight, and a wet paper machine with a basis weight of 75 g / m ^2. A use sheet was made.

Next, this sheet-like material was impregnated with a 7% by weight aqueous solution of sodium hexametaphosphate as an inorganic binder, dried with air at 100 ° C., and fixed to a 5% by weight sodium hexametaphosphate sheet to obtain a precursor sheet.

Next, this precursor sheet was formed into a honeycomb (adsorption element precursor) having 15 cells / cm ² using a polyvinyl acetate emulsion having a solid content of 50% as an adhesive for forming a honeycomb, using a honeycomb forming machine. The amount of the honeycomb forming adhesive used in this case is about 3% by weight based on the weight of the sheet after impregnation. Thereafter, the honeycomb-shaped material was heat-treated in air at 400 ° C. for about 3 minutes to obtain an adsorbing element.

<Example 12>
The adsorbent A1 has a tap density of 0.39 g / cm ³ , ZSM-5 (MFI) zeolite having an average particle diameter of 9.9 μm by laser analysis is 37.5% by weight, and the adsorbent A2 has a tap density of 0.34 g / cm ³ . cm ³ , 37.5% by weight of Y-type (FAU) zeolite having an average particle size of 0.7 μm calculated from SEM photographic analysis, pulp-like and short-fiber aramid fibers (heat-resistant organic component: B-1) is 17% by weight, PVA (low-temperature thermally decomposable organic component: B-2) as a thermally decomposable organic binder is 8% by weight, and a wet paper machine with a basis weight of 100 g / m ^2. A use sheet was made.

Next, this sheet-like material was impregnated with a 7% by weight aqueous solution of sodium hexametaphosphate as an inorganic binder, dried with air at 100 ° C., and fixed to a 5% by weight sodium hexametaphosphate sheet to obtain a precursor sheet.

Next, this precursor sheet was formed into a honeycomb honeycomb (adsorption element precursor) having a cell number of 15 / cm ² using a polyvinyl acetate emulsion having a solid content of 50% as an adhesive for forming the honeycomb using a honeycomb forming machine. did. The amount of the honeycomb forming adhesive used in this case is about 3% by weight based on the weight of the sheet after impregnation. Thereafter, the honeycomb-shaped material was heat-treated in air at 400 ° C. for about 3 minutes to obtain an adsorbing element.

<Example 13>
Adsorbent A1 has a tap density of 0.54 g / cm ³ , ZSM-5 (MFI) zeolite having an average particle diameter of 3.2 μm by laser analysis is 60% by weight, and adsorbent A2 has a tap density of 0.36 g / cm ^3. 37.5% by weight of Y-type (FAU) zeolite having an average particle diameter of 1.2 μm calculated from SEM photo analysis, pulp-like and short-fiber aramid fibers (heat-resistant organic component: B- 1) 17% by weight, PVA (low-temperature thermally decomposable organic component: B-2) as a thermally decomposable organic binder, 8% by weight, using a wet papermaking machine with a basis weight of 75 g / m ² A material was created.

Next, this sheet-like material was impregnated with a 7% by weight aqueous solution of sodium hexametaphosphate as an inorganic binder, dried with air at 100 ° C., and fixed to a 5% by weight sodium hexametaphosphate sheet to obtain a precursor sheet.

Next, this precursor sheet was formed into a honeycomb (adsorption element precursor) having 15 cells / cm ² using a polyvinyl acetate emulsion having a solid content of 50% as an adhesive for forming a honeycomb, using a honeycomb forming machine. The amount of the honeycomb forming adhesive used in this case is about 3% by weight based on the weight of the sheet after impregnation. Thereafter, the honeycomb-shaped material was heat-treated in air at 400 ° C. for about 3 minutes to obtain an adsorbing element.

<Example 14>
As adsorbent A1, ZSM-5 (MFI) zeolite having a tap density of 0.39 g / cm ³ , an average particle size of 9.9 μm by laser analysis is 75% by weight, pulp-like and short-fiber aramid as heat-resistant organic components Fiber (heat-resistant organic component: B-1) is 17% by weight, PVA (low-temperature thermally decomposable organic component: B-2) as a thermally decomposable organic binder is 8% by weight, and the basis weight is 75 g / m ^2. Sheet material was prepared using a wet papermaking machine by weight.

Next, this sheet-like material was impregnated with a 20% by weight aqueous solution of sodium hexametaphosphate as an inorganic binder, dried with air at 100 ° C., and fixed to a 5% by weight sodium hexametaphosphate sheet to obtain a precursor sheet.

Next, this precursor sheet was formed into a honeycomb (adsorption element precursor) having 15 cells / cm ² using a polyvinyl acetate emulsion having a solid content of 50% as an adhesive for forming a honeycomb, using a honeycomb forming machine. The amount of the honeycomb forming adhesive used in this case is about 3% by weight based on the weight of the sheet after impregnation.

<Comparative Example 11>
The adsorbent A1 has a tap density of 0.39 g / cm ³ , ZSM-5 (MFI) zeolite having an average particle diameter of 10.7 μm by laser analysis is 15% by weight, and the adsorbent A2 has a tap density of 0.34 g / cm ^3. In addition, a Y-type (FAU) zeolite having an average particle size of 0.7 μm calculated from SEM image analysis was used as a 60% by weight heat-resistant organic component, and pulp-like and short fibrous aramid fibers (heat-resistant organic component: B-1) were used. 17% by weight, 8% by weight of PVA (low-temperature thermally decomposable organic component: B-2) as a thermally decomposable organic binder, and a sheet-like material using a wet papermaking machine at a weight of 75 g / m ² basis weight. Created.

Next, this sheet-like material was impregnated with a 20% by weight aqueous solution of sodium hexametaphosphate as an inorganic binder, dried with air at 100 ° C., and fixed to a 5% by weight sodium hexametaphosphate sheet to obtain a precursor sheet.

Next, this precursor sheet was formed into a honeycomb (adsorption element precursor) having 15 cells / cm ² using a polyvinyl acetate emulsion having a solid content of 50% as an adhesive for forming a honeycomb, using a honeycomb forming machine. However, since the strength of the sheet was weak, cracks and breaks of the sheet were conspicuous at the time of honeycomb formation, and proper honeycomb formation could not be performed.

<Comparative Example 12>
Adsorbent A1 has a tap density of 0.54 g / cm ³ , ZSM-5 (MFI) zeolite having an average particle diameter of 3.2 μm by laser analysis is 15% by weight, and adsorbent A2 has a tap density of 0.36 g / cm ^3. 60% by weight of Y-type (FAU) zeolite having an average particle size calculated from SEM image analysis of 1.3 μm, pulp-like and short-fiber aramid fibers (heat-resistant organic component: B-1) as the heat-resistant organic component 17% by weight, 8% by weight of PVA (low-temperature thermally decomposable organic component: B-2) as a thermally decomposable organic binder, and a sheet-like material using a wet papermaking machine at a weight of 75 g / m ² It was created.

Next, this precursor sheet was formed into a honeycomb (adsorption element precursor) having 15 cells / cm ² using a polyvinyl acetate emulsion having a solid content of 50% as an adhesive for forming a honeycomb, using a honeycomb forming machine. However, since the strength of the sheet was weak, cracks and breaks of the sheet were conspicuous at the time of honeycomb formation, and proper honeycomb formation could not be performed.

<Comparative Example 13>
Adsorbent A1 has a tap density of 0.34 g / cm ³ , an average particle size calculated from SEM image analysis of 0.7 μm, 75% by weight of Y-type (FAU) zeolite, a pulp as a heat-resistant organic component, and short fibers 17% by weight of aramid fiber (heat-resistant organic component: B-1), 8% by weight of PVA (low-temperature thermally-decomposable organic component: B-2) as a thermally decomposable organic binder, and a basis weight of 75 g / m 2 A sheet-like material was prepared using a wet papermaking machine with a weight of

Next, this sheet-like material was impregnated with a 20% by weight aqueous solution of sodium hexametaphosphate as an inorganic binder, dried with air at 100 ° C., and fixed to a 5% by weight sodium hexametaphosphate sheet to obtain a precursor sheet. Thereafter, heat treatment was performed in a baking furnace at 400 ° C. for about 3 minutes to obtain an adsorption sheet.

Next, this precursor sheet was formed into a honeycomb (adsorption element precursor) having 15 cells / cm ² using a polyvinyl acetate emulsion having a solid content of 50% as an adhesive for forming a honeycomb, using a honeycomb forming machine. However, since the strength of the sheet was weak, cracks and breaks of the sheet were conspicuous at the time of honeycomb formation, and proper honeycomb formation could not be performed.

The adsorbing element of this embodiment has at least one kind of adsorbent, and the adsorbent is calculated from the bulk density and particle size of the adsorbent so that both the strength of the adsorbent and the high content weight ratio of the adsorbent are compatible. By appropriately setting the total number of particles contained in the adsorbing element, an organic component having a melting point or a thermal decomposition temperature of 300 ° C. or higher, an organic component having a thermal decomposition temperature of less than 300 ° C., and an inorganic binder as a skeleton material The adsorbing element is excellent in flexibility and strength, and the adsorbent content weight ratio is extremely high, and the adsorbing performance is excellent.

As described above, the strength of the adsorbing element is clearly different depending on the total number of adsorbent particles contained in the adsorbing element, and by making the total number of particles not more than 8.0 × 10 ¹² , sufficient strength for practical use can be obtained. An adsorbing element with a large area was obtained.

The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

2a Flute section, 2b liner section.

Claims (15)

1. An adsorbent sheet containing at least one adsorbent (Ax: x = 1, 2, 3... N),
   The tap density of the adsorbent (Ax) is Axa,
   When the adsorbent particles are assumed to be spherical, the spherical volume calculated from the average particle diameter of the adsorbent particles is Axb,
   When the weight ratio (%) of the adsorbent contained in the adsorbent sheet is Axc,
   The average number of particles Axd contained per 1 g of the adsorption sheet is represented by the following formula 1.
   

   

   The total average particle number of at least one kind of the adsorbent (Ax) contained per 1 g of the adsorbing sheet is represented by the following formula 2.
   

   

   An adsorptive sheet having a specific tensile strength of 2 N · m / g or more.
2. The adsorbent sheet according to claim 1, wherein a total ratio of at least one kind of adsorbent (Ax) contained in the adsorbent sheet is 40% by weight or more of the adsorbent sheet.
3. The adsorption sheet according to claim 1 or 2 whose tap density of said adsorption material (Ax) is 0.1 g / cm ³ or more.
4. The adsorbent sheet according to any one of claims 1 to 3, wherein the adsorbent (Ax) is zeolite.
5. A method for producing an adsorbent sheet containing at least one adsorbent (Ax: x = 1, 2, 3... N),
   The tap density of the adsorbent (Ax) is Axa,
   When the adsorbent particles are assumed to be spherical, the spherical volume calculated from the average particle diameter of the adsorbent particles is Axb,
   When the weight ratio (%) of the adsorbent contained in the adsorbent sheet is Axc,
   The average number of particles Axd contained per 1 g of the adsorption sheet is represented by the following formula 1.
   

   

   The total average particle number of at least one kind of the adsorbent (Ax) contained per 1 g of the adsorbing sheet is represented by the following formula 2.
   

   

   The manufacturing method of an adsorption sheet whose specific tensile strength of the said adsorption sheet is 2 N * m / g or more.
6. 6. In addition to the adsorbent (Ax), the organic fiber (B-1) having a melting point or a thermal decomposition temperature of 300 ° C. or higher and an organic component (B-2) having a thermal decomposition temperature of less than 300 ° C. are included. The manufacturing method of the adsorption sheet of description.
7. The method for producing an adsorption sheet according to claim 6, wherein the organic fiber is at least one polymer selected from an aramid polymer, a benzimidazole polymer, a benzoxazole polymer, and a polyimide polymer.
8. The method for producing an adsorption sheet according to claim 6 or 7, wherein the organic component is at least one selected from a polyvinyl alcohol polymer, a polyacrylonitrile polymer, and a polyvinylpyrrolidone polymer.
9. An adsorbing element having a honeycomb-like structure using an adsorbing sheet (adsorbing element precursor) having at least one kind of adsorbent (Ax ,: x = 1, 2, 3... N) and having a large number of air passages. There,
   The tap density of the adsorbent (Ax) is Axa,
   When the adsorbent particles are assumed to be spherical, the spherical volume calculated from the average particle diameter of the adsorbent particles is Axb,
   When the weight ratio (%) of the adsorbent (Ax) contained in the adsorbent sheet is Axc,
   The average number of particles Axd contained per 1 g of the adsorption sheet is represented by the following formula 1.
   

   

   The total average particle number of at least one kind of the adsorbent (Ax) contained per 1 g of the adsorbing sheet is represented by the following formula 5.
   

   

   An adsorption element having a plane compressive strength of 3 kPa or more.
10. The adsorption element according to claim 9, wherein the adsorption sheet has fibers as a skeleton material.
11. The adsorption element according to claim 9 or 10, wherein the adsorption sheet has a thickness of 0.16 to 0.25 mm.
12. The adsorption element according to any one of claims 9 to 11, wherein the honeycomb structure has a cell number of 30 / cm ² to 70 / cm ² .
13. The adsorption element according to any one of claims 9 to 12, wherein a total ratio of at least one kind of the adsorbent (Ax) included in the adsorption element is 40% by weight or more of the adsorption element. .
14. The adsorption element according to any one of claims 9 to 13, wherein a tap density of the adsorbent (Ax) is 0.1 g / cm ³ or more.
15. The adsorption element according to any one of claims 9 to 14, wherein the adsorbent (Ax) is zeolite.

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