JP2009000621A - Method of manufacturing adsorbent-containing molded body and adsorbent-containing molded body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an adsorbent-containing molded body which is a high zeolite-containing molded body containing zeolite in a high concentration of 70 wt.% or higher to keep adsorbing capacity. <P>SOLUTION: The method of manufacturing an adsorbent-containing molded body involves steps of producing a silane alkoxide hydrolyzable solution, forming swollen gel by adding a zeolite to the silane alkoxide hydrolyzable solution, curing the swollen gel body by putting the swollen gel in a mold, and forming a dry gel body by drying the swollen gel body. In the manufacturing method, the silane alkoxide hydrolyzable solution production step is carried out in the presence of an acid catalyst and the silane alkoxide hydrolyzable solution contains water and alcohol as a solvent and the ratio of the alcohol in the solvent is 10 wt.% or higher and the zeolite is either one or both of a zeolite showing acidity and a zeolite showing alkalinity and the zeolite content in the dry gel body is 70 to 98 wt.%. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a method for producing an adsorbent-containing molded article and an adsorbent-containing molded article, and more specifically, a method for producing an adsorbent-containing molded article containing a high concentration of zeolite formed by a sol-gel method using zeolite and the production method. Relates to an adsorbent-containing molded article obtained by the above.

  Conventionally, zeolite has been used to adsorb gas components containing moisture, but it tends to adsorb more moisture than gas components in a high humidity environment, but the zeolite macropore size has a specific range. To selectively separate gases, adsorb outgas generated inside electronic parts and electronic products, adsorb refrigerator refrigerants, remove moisture in organic solvents, power plants from the viewpoint of environmental protection in recent years It is widely used for the adsorption separation of carbon dioxide from combustion exhaust gas.

  Patent Document 1 discloses a method for producing an adsorbent composition in which a mixed solution of a metal alkoxide solution and a synthetic zeolite is hydrolyzed to disperse the synthetic zeolite in porous glass and then dried. However, the synthetic zeolite content is as low as 30% by weight or less.

  Patent Document 2 discloses an inorganic composite functional material obtained by firing an inorganic composite gel at 500 ° C. by a sol-gel method from a mixture containing an organometallic alkoxide solution and an inorganic powder. However, the synthetic zeolite content is as low as 15 wt%.

  Patent Document 3 discloses a porous zeolite body in which clay and zeolite as an inorganic binder are kneaded and dispersed by a physical force such as a ball mill and calcined at 250 ° C. or higher.

  In order to produce a compact with the adsorption power of the zeolite powder maintained, the zeolite powder content needs to be 70% by weight or more, and it is desirable to maintain the hardness. However, the zeolite powder is difficult because it does not collect. Moreover, although 90 wt% zeolite beads have been produced (see, for example, Patent Document 4), since the clay-based material is kneaded as a binder and produced by a granulator, it has only a bead shape.

  Therefore, there has been a demand for a production method that can produce a compact having a zeolite of 70 wt.

  In addition, zeolites are classified into hydrophilic zeolite and hydrophobic zeolite as characteristics with respect to water, and the present inventors have roughly classified the zeolite using a hydrolyzed liquid in Japanese Patent Application No. 2006-11084 regarding hydrophobic zeolite. To form an adsorbent molded body. However, when a molded product is produced by mixing hydrophilic zeolite with the hydrolyzed liquid, the hydrophilic zeolite adsorbs moisture in the hydrolyzed liquid, and heat generation is not possible. It has been a problem to reduce heat generation due to moisture adsorption of hydrophilic zeolite.

  Further, in the method of gelling zeolite by mixing hydrophobic zeolite into the hydrolyzed solution, there are materials that take time for gelation depending on the physical properties of hydrophobic zeolite, and a method of gelling more easily has been desired. .

As described above, it has been desired that an adsorbent-containing molded article can be easily produced by gelling zeolite without classifying the zeolite as hydrophilic zeolite or hydrophobic zeolite.
JP-A-5-293371 Japanese Patent Laid-Open No. 3-285843 JP-A-62-297211 JP-A-1-171554

  The object of the present invention is obtained by a method for producing an adsorbent-containing molded article comprising a zeolite-rich molded article containing zeolite in a high concentration of 70% by weight or more so that the adsorption power can be maintained, and the production method. It is another object to provide an adsorbent-containing molded article.

  Another object of the present invention is to provide a method for producing an adsorbent-containing molded article that generates little heat even if hydrophilic zeolite is used as the zeolite.

  Another object of the present invention is to provide a method for producing a molded article containing an adsorbent by easily gelling zeolite without classifying the zeolite as hydrophilic zeolite or hydrophobic zeolite.

Producing a silane alkoxide hydrolyzate according to the present invention;
Adding a zeolite to the silane alkoxide hydrolysis solution to form a wet gel;
Placing the wet gel in a mold and curing to a wet gel body;
Drying the wet gel body to form a dry gel body;
In the method for producing an adsorbent-containing molded article having
The production process of the silane alkoxide hydrolyzed solution is using an acid catalyst,
The silane alkoxide hydrolyzed solution contains water and alcohol as a solvent, and the proportion of alcohol in the solvent is 10% by weight or more,
The zeolite is one or both of an acidic zeolite and an alkaline zeolite,
The dry gel body has a zeolite content of 70 to 98% by weight,
There is provided a method for producing an adsorbent-containing molded article characterized by the above.

Producing a silane alkoxide hydrolyzate according to the present invention;
Adding a zeolite to the silane alkoxide hydrolysis solution to form a wet gel;
Placing the wet gel in a mold and curing to a wet gel body;
Drying the wet gel body to form a dry gel body;
In the method for producing an adsorbent-containing molded article having
The production process of the silane alkoxide hydrolyzed solution is using an alkali catalyst,
The silane alkoxide hydrolyzed solution contains water and alcohol as a solvent, the proportion of alcohol in the solvent is 50 wt% or more and 100 wt% or less, and the solid content concentration of the silane alkoxide hydrolyzed solution is 5 to 20%. And
The zeolite is one or both of an acidic zeolite and an alkaline zeolite,
The dry gel body has a zeolite content of 70 to 98% by weight,
There is provided a method for producing an adsorbent-containing molded article characterized by the above.

  In addition, according to the present invention, there is provided an adsorbent-containing molded article obtained by the method for producing an adsorbent-containing molded article.

  As described above, the present invention has established conditions for molding a wet gel containing a high concentration of zeolite that is easy to mold, so that a molded body with a high hardness and high zeolite content can be used as a kneader or granulator. It can be obtained without using it.

  In addition, since zeolite is used in the present invention, the obtained molded body can adsorb organic gas and odor other than moisture with high efficiency and can be applied to various uses.

  In addition, a molded product with a higher content than that using an organic resin as a binder is obtained in a state of maintaining hardness, and can be sintered and dried at a lower temperature than using a clay-based material, using a granulator, etc. Can be formed without.

  Hereinafter, embodiments of the present invention will be described in detail.

  In the present invention, a wet gel body is obtained by adding zeolite to the hydrolyzed solution by the sol-gel method. This is because silica cannot be added to silica gel (gelled silane alkoxide (TEOS)) at a high concentration, so it is necessary to add it in a sol state.

  In the past, the present inventors classified zeolites as hydrophilic zeolites or hydrophobic zeolites, and produced adsorbent shaped bodies using silane alkoxide hydrolysates. As a result of intensive studies by the present inventors, it has been found that when zeolite is mixed with water to form a slurry, the zeolite mixture exhibits acidity or alkalinity. Then, the silane alkoxide hydrolyzate before and after mixing the zeolite is acidic or alkaline, that is, by controlling the pH value, gelation after mixing the zeolite can be easily performed. As a method for controlling the pH value, there are a method using an acid catalyst or an alkali catalyst as a catalyst used in the silane alkoxide hydrolysis solution, a method of adding an aqueous solution when zeolite is mixed with the silane alkoxide hydrolysis solution, and the like.

  As the hydrolysis solution according to the present invention, a silane alkoxide hydrolysis solution (sol) containing an acid catalyst or an alkali catalyst in silane alkoxide (TEOS) can be used. In order to add zeolite to the silane alkoxide hydrolyzate at a higher content, it is preferable to use an acid catalyst. Addition of acid-labile zeolite to an acid-catalyzed silane alkoxide hydrolysis solution may affect the crystal structure of the zeolite. And can be difficult. The acid catalyst is preferably a strong acid hydrochloric acid, and a weak acid such as acetic acid may cause zeolite precipitation depending on the type of zeolite. Examples of the alkali catalyst include an aqueous ammonia solution.

The concentration of hydrochloric acid (HCl) used as an acid catalyst in the silane alkoxide hydrolyzed solution is preferably [HCl] / [TEOS] = 0.01 to 0.4 in terms of molar ratio. At a molar ratio of [HCl] / [TEOS] = 0.01, it is difficult to proceed with silane alkoxide hydrolysis and it takes time. When the molar ratio exceeds [HCl] / [TEOS] = 0.4, the acid concentration becomes high and handling becomes dangerous. In the silane alkoxide hydrolyzate, when the HCl concentration is increased, the time until gelation is extended. This is because, with an HCl catalyst, the silane alkoxide is hydrolyzed to become a SiO ₂ linear polymer having an OH group, so that a zeolite powder-containing wet gel can be prepared. As the HCl concentration increases, hydrolysis proceeds and the SiO ₂ linear molecules are entangled. Therefore, it is considered that the time until wet gelation becomes longer even if zeolite is added.

Conventionally, when an alkali catalyst is used as the catalyst for the silane alkoxide hydrolysis solution, the hydrolysis solution itself is more easily gelled than the acid catalyst, and it has been difficult to mix zeolite. Furthermore, even if the silane alkoxide is hydrolyzed while suppressing the gelation of the hydrolyzed solution, it becomes SiO ₂ spherical particles with few OH groups, so even if zeolite is mixed, it is difficult to form a wet gel. Therefore, the inventors of the present invention, as a method for suppressing gelation even when an alkali catalyst is used in the silane alkoxide hydrolysis liquid, increase the proportion of alcohol in the solvent of the hydrolysis liquid and solidify the SiO ₂ particles that form a gel. A method for reducing the partial concentration was found, and it was further found that wet gelation can be easily obtained by using the method for controlling the pH value in combination even when the silane alkoxide becomes SiO ₂ spherical particles.

  In the present invention, the content of alcohol and water used for the solvent of the silane alkoxide hydrolyzate, particularly the content of alcohol, is very important and affects the degree of gelation when the zeolite is mixed. It plays the role of suppressing heat generation due to moisture adsorption of the water-soluble zeolite.

  The content of the alcohol with respect to the solvent of the silane alkoxide hydrolyzed solution when using the acid catalyst is 10% by weight or more. Preferably it is 30 weight% or more, More preferably, it is 40 weight% or more. The upper limit is 100% by weight, and even if the total amount of alcohol is hydrolyzed by moisture in the air, it takes time, but it takes time, so the zeolite may precipitate depending on the production viewpoint and the type of zeolite to be mixed. % Or less is preferable. By setting the alcohol content of the solvent to 10% by weight or more, the water content of the silane alkoxide hydrolyzate is reduced to the minimum necessary, so that heat generation due to moisture adsorption can be suppressed even when hydrophilic zeolite is used. Become.

  As the solid content concentration of the silane alkoxide hydrolyzate when using an acid catalyst, if the solid content concentration is too high, it is solidified when the zeolite is added, so the solid content concentration is preferably 50% by mass or less, and the lower limit is the solvent content. If it is absent, it becomes difficult to mix the zeolite, so 15 to 35% by weight is more preferable.

The content of the alcohol with respect to the solvent of the silane alkoxide hydrolyzed solution when using the alkali catalyst is 50 to 100% by weight, and the solid content concentration of the silane alkoxide hydrolyzed solution at that time is essential to be 5 to 20% by weight. is there. Preferably, the alcohol content is 65 to 95% by weight and the solid content concentration is 8 to 15% by weight. By reducing the water content to 50% by weight or more of the alcohol content of the solvent and reducing the solid content concentration of the SiO ₂ particles that form the gel in the hydrolyzed solution to 5 to 20% by weight, the above-mentioned alkaline catalyst It became possible to suppress the gelation of the hydrolyzed liquid during use.

  The alcohol used in the silane alkoxide hydrolysis solution solvent preferably has 4 or less carbon atoms, and lower alcohols such as methanol and ethanol have a shorter time to gelation. This is probably because higher alcohols having 5 or more carbon atoms have a high molecular weight and thus impede wet gelation of zeolite and silane alkoxide hydrolyzate.

  The silane alkoxide hydrolyzate is preferably obtained by stirring at room temperature for 1 minute or more, and by continuing stirring for 5 hours or more, the hardness of the molded article increases.

  Further, the silane alkoxide hydrolyzed solution obtained by stirring is allowed to stand at room temperature for 1 hour or more and 1 month or less, whereby the hardness becomes higher.

  The zeolite used in the present invention may be either hydrophilic or hydrophobic, and may be acidic or alkaline. Zeolite is prepared by natural aluminum or synthetic zeolite as a starting material by dealumination using mineral acid, etc., or direct synthesis in which silica source, alumina source, alkali source and organic mineralizer are mixed and crystallized. Obtained by law. Zeolite is a porous granular material used to separate substances according to the difference in molecular size, and has a structure with uniform pores. Therefore, the type of molecules that can be adsorbed depends on the type of zeolite. When adsorbing a gas component such as an organic component, the pore inlet diameter of the zeolite may be larger than the molecular diameter to be adsorbed. Usually, it is sufficient if the pore inlet is a zeolite with 8, 10, 12-membered rings of oxygen. In the present invention, those that preferentially adsorb organic gas and odor components over moisture are preferred.

  When the wet gel body contains a large amount of solvent, the volume shrinkage tends to be large and brittle during primary drying, so the solid content concentration of the wet gel body is preferably 30% by weight or more, and particularly preferably 45% by weight to 80% by weight.

  The molded product obtained by the present invention needs to have a zeolite content of 70 to 98% by weight in order to produce a molded product while maintaining the adsorption power of the zeolite powder, and from the viewpoint of adsorptivity, it is 80 to 95. It is preferable that it is weight%. Since the zeolite content according to the present invention is high, that is, there are few binders, it is difficult to produce a molded product that retains hardness, and it is necessary to make it brittle when producing fine shapes.

  In the present invention, it is preferable to form a wet gel having a pH of 8 or higher by adding zeolite to the silane alkoxide hydrolysis solution. Wet gelation itself is carried out if the silane alkoxide hydrolyzate is weak acid or weak alkali or higher, but the zeolite reacts in a straight chain in the acidic region, and the zeolite in the alkaline region reacts in a branched chain. The shape becomes alkaline when it is alkaline. Since the wet gel is naturally muddy, the pH value is preferably pH 8 or higher indicating alkalinity. In addition, since it solidifies from the smooth shape in an acidic region, it is hard to shape | mold compared with the muddy-like wet gel in an alkaline region pH8 or more. When adding zeolite showing alkalinity, when the zeolite content is set to 70% by weight or more, the wet gelation easily proceeds because the pH naturally shows 8 or more. When adding zeolite showing acidity, the pH value is less than 8 when the zeolite content is 70% by weight or more, and most of it shows an acidic range. Therefore, when the zeolite is mixed with the silane alkoxide hydrolyzate, the aqueous solution is used. Using the addition method, an aqueous ammonia solution or an aqueous sodium hydroxide solution is added as an aqueous solution to the agitated wet gel, and the wet gelation easily proceeds by adjusting the pH value of the wet gel to 8 or more.

When the silane alkoxide hydrolyzate and zeolite are mixed, it begins to change to a wet gel, and the state of the zeolite-containing wet gel is as follows:
(1) State with fluidity (state in which shape cannot be maintained when flowed on a flat surface) ... Change rate over 95% and 100% or less (2) State with little or no fluidity (clay-like) ... Change rate 10% over 95% or less (3) State of no fluidity (agar-like) ... Deformation rate 0% over 10% or less It changes in order as time passes.

The deformation rate in the present invention is 23 ° C./55% RH environment,
(I) A wet gel body molded to a diameter of 15 mm and a thickness of 5 mm is placed on a horizontal surface.
(Ii) Apply a 20N load to the wet gel body with a 10 mm diameter cylinder (material: SUS304 stainless steel). (Iii) 3 seconds after releasing the load (After the release, other load must be applied) The shape of the gel is maintained) and the thickness of the wet gel body is measured to calculate the deformation rate. Deformation rate = (distance recessed by load (mm) / 5 mm) × 100%
Indicated by

In the present invention, as a method of forming a dry gel body from a wet gel,
(A) A method in which a wet gel is formed into a sheet, the wet gel in a sheet is cut and dried to form a dry gel body,
(B) A method in which wet gels are put into respective molds to form dry gel bodies one by one,
Etc.

(A) A method of forming a wet gel in the form of a sheet, cutting the sheet-like wet gel and drying it to form a dry gel body is a wet gel obtained by mixing a silane alkoxide hydrolyzate and zeolite. While it is, put it in a mold and leave it to harden until it becomes a wet gel body with little or no fluidity with a deformation rate of more than 0% and 95% or less, and then the wet gel body is preferably is pressurized with ^{100g / cm 2 ~20kg / cm 2} , more preferably ^{1kg / cm 2 ~10kg / cm 2} , to form into a sheet. By pressurizing within the above range, the molded body can be made to have higher hardness. Since the wet gel body is pressurized, the deformation rate is over 95%, and it is difficult to mold in the liquid state with fluidity, and those that have been dried and solidified with a deformation rate of 0% will crack when cut. There was a trend. The deformation rate can be made within the scope of the present invention by changing the standing time. The obtained sheet-like wet gel body is then cut into various shapes such as a coin shape, a square shape, and the like with a blade or the like according to the application and dried. When trying to cut after the drying method described later, it is difficult to obtain the desired shape because the dried gel body breaks into pieces, etc. May enter. By cutting the wet gel body such as a sheet in this way, a large amount of the wet gel body of the desired shape can be obtained in a short time and the productivity can be improved.

As a method for drying a zeolite-containing wet gel body according to the present invention, primary drying is performed to volatilize the moisture and solvent content of the gel body, and further secondary drying is performed to increase the hardness by crystallizing the zeolite. Is preferred. In the primary drying, water and alcohol are volatilized, so that it can be dried at room temperature (23 ° C. ± 2 ° C.) or more, particularly preferably 23 ° C. to 120 ° C., more preferably 23 ° C. to 60 ° C. . The drying time is preferably 2 minutes to 30 minutes. In secondary drying, the dried gel body has low hardness because SiO ₂ in the zeolite is not crystallized, so it is preferable to dry at 140 ° C. or higher, and since the present invention can be dried at a lower temperature than the conventional production method, the upper limit is set. Is 800 ° C. or lower, more preferably 200 ° C. to 350 ° C. The drying time is preferably 1 hour to 3 hours.

  (B) The method of forming wet gels in each mold and forming individual dry gels individually is to form cylindrical shapes and various shapes that are difficult to produce by the above-mentioned method of forming and cutting the sheets. Can do. In the liquid state where the state of the wet gel put into the mold has a fluidity of more than 95% change rate and less than 100%, the surface does not become flat due to the surface tension of the wet gel when put into the mold. If there is no leakage, the air inside the mold will not escape and the wet gel will not enter into the fine holes, etc., and it tends to be difficult to mold well. It cannot be put into a mold.

The wet gel molded as described above undergoes the primary drying step of either (a) or (b) below,
(A) Step of removing the mold from the mold after primary drying as it is after the mold is placed (b) Step of removing from the mold and performing the primary drying after the mold is placed, followed by secondary drying. These primary and secondary drying conditions are the same as the method of forming the sheet and drying it after cutting.

  (A) In the step of removing the mold from the mold after primary drying as it is, the solvent in the wet gel is volatilized by the primary drying, and the mold can be easily removed from the mold by volume shrinkage. In order to easily remove the mold by volume shrinkage in this way, it is preferable that the moisture content in the state where there is almost no or no fluidity of the wet gel is 30% by weight or more and 80% by weight or less. If the water content is less than 30% by weight, the volume shrinkage is small, and it tends to break in the step of removing from the mold, and if it exceeds 80% by weight, the volume shrinkage is large and cracks and brittleness are likely to occur. As the shape, a cylindrical shape or the like is preferable. When the volumetric shrinkage of the rectangular shape is large, cracks may enter inside, so that the shape is often die-cut by the step (b) below.

  (B) After the mold is placed, the step of removing from the mold and performing primary drying is performed after the mold is released, so that it is not necessary to worry about volume shrinkage due to volatilization of the solvent of the wet gel. However, if a precise punching tool is not used when removing from the mold, it may dry out in the middle of the die-cutting process, so it is suitable for forming a square shape that makes it easy to produce a precise punching tool. Yes.

  Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to these examples.

(Example 1-1) ... Die-cut molding (a)
Silane alkoxide (TEOS) 25g
Pure water 23.5g
37.6g of methanol
1g of 2N hydrochloric acid (pH3)
(Molar ratio [HCl] / [TEOS] = 0.177)
The above material is stirred at room temperature (23 ° C.) for 5 minutes to prepare a silane alkoxide hydrolyzed solution (solid content concentration 26.8% by weight). Then, it mixed with 46.16g of hydrophilic zeolite (13X) which shows alkalinity, and produced the zeolite containing wet gel body (solid content concentration 45 weight%, pH10).

  The zeolite-containing wet gel body having a deformation rate of 20% was placed in a cylindrical mold having a diameter of 3 mm and a height of 3 mm, and was primarily dried at 120 ° C. for 5 minutes to prepare a dry gel body. The deformation rate is a value obtained by measuring the deformation rate of a wet gel body prepared in the same manner as described above. Next, the dried gel body was secondarily dried at 300 ° C. for 2 hours in an electric furnace to obtain a molded body having a zeolite content of 80% by weight.

  The obtained zeolite compact was evaluated according to the following evaluation method. The results are shown in Table 1.

<Evaluation>
"hardness"
A cylindrical molded body having a diameter of 2 mm and a height of 3 mm was produced, and the hardness of the molded body was measured using a digital force gauge (FGC-50, manufactured by SHIMPO), and the peak value at the time of crushing and breaking was measured. The measured value is an average value of the number of measurements N = 7.

"adsorption"
In order to examine the adsorption characteristics of the gas component of the molded body, a cylindrical molded body having a diameter of 2 mm × height of 3 mm and a tablet containing triethylamine (active ingredient content: 10%) are put in a closed container and 25 ° C./50%. It was left for 240 hours in an RH environment. Thereafter, the presence or absence of adsorption of the triethylamine component was detected and evaluated using a GC-MS apparatus (Automass, manufactured by JEOL Ltd.). The results are shown in Table 1.

`` Height accuracy (standard deviation σ) ''
The height (thickness) of the molded body is measured with three microscopes, and the height difference (maximum value−minimum value) of one molded body is calculated. This measurement is performed on 20 molded bodies, and the standard deviation is calculated.

(Example 1-2) ... Die-cut molding (a)
Silane alkoxide (TEOS) 25g
50.0g of pure water
7.09g of methanol
2N hydrochloric acid (pH3) 0.5g
(Molar ratio [HCl] / [TEOS] = 0.008)
The above material is stirred at room temperature (23 ° C.) for 5 minutes to prepare a silane alkoxide hydrolyzed solution (solid content concentration 26.8% by weight). Then, it mixed with 46.16g of hydrophilic zeolite (3A) which shows acidity, and it was pH3 when pH value was measured. Thereafter, 10 g of a 10% aqueous ammonia solution was added with stirring to adjust the pH to 8 or more to prepare a zeolite-containing wet gel (solid content concentration 45% by weight, pH 12). Other than that was carried out similarly to Example 1-1, and obtained and evaluated the molded object with a zeolite content rate of 80 weight%. The results are shown in Table 1.

(Example 1-3) ... Die-cut molding (b)
In the same manner as in Example 1-1, a zeolite-containing wet gel (solid content concentration: 45% by weight) was prepared.

  Next, the zeolite-containing wet gel body having a deformation rate of 20% was placed in a 3 × 3 × 3 mm-high square mold, then removed from the mold and first dried at 120 ° C. for 5 minutes to produce a dried gel body The dried gel body was secondarily dried in an electric furnace at 300 ° C. for 2 hours to obtain a molded body having a zeolite content of 80% by weight and evaluated. The results are shown in Table 1.

(Example 1-4) ... Die-cut molding (a)
Except having used the hydrophobic zeolite which shows alkalinity (brand name: HiSiV3000, Union Showa Co., Ltd.), the molded object with a zeolite content rate of 80 weight% was obtained and evaluated like Example 1-1. The results are shown in Table 1.

(Example 1-5) Die-cut molding (a)
Except for using an acidic hydrophobic zeolite (trade name: HiSiV1000, manufactured by Union Showa), a molded article having a zeolite content of 80% by weight was obtained and evaluated in the same manner as in Example 1-2. The results are shown in Table 1.

(Example 1-6) Die-cut molding (b)
A zeolite-containing wet gel (solid content concentration: 45% by weight) was prepared in the same manner as in Example 1-4.

  The zeolite-containing wet gel body having a deformation rate of 40% was placed in a 3 × 3 × 3 mm-high square mold, then removed from the mold and primary dried at 120 ° C. for 5 minutes to prepare a dry gel body. Next, the dried gel body was subjected to secondary drying in an electric furnace at 300 ° C. for 2 hours to obtain a molded body having a zeolite content of 80% by weight and evaluated. The results are shown in Table 1.

(Example 1-7) Cut molding Silane alkoxide (TEOS) 25 g
6.0g of pure water
Methanol 54.5g
1g of 2N hydrochloric acid (pH3)
The above material is stirred at room temperature (23 ° C.) for 5 minutes to prepare a silane alkoxide hydrolyzed solution (solid content concentration 26.8% by weight). Then, it was mixed with 46.16 g of hydrophilic zeolite (13X) showing alkalinity, placed in a petri dish with a diameter of 12 cm on a table kept horizontal, and allowed to stand for 3 minutes in an environment of 23 ° C./55% RH. A clay-like zeolite-containing wet gel body (solid content concentration: 45% by weight, pH: 10, deformation rate: 20%) was prepared. In addition, a deformation rate is the value which measured the deformation rate of the wet gel body for a measurement produced similarly.

The clay-like wet gel body was pressurized at 1 kg / cm ² to obtain a sheet-like wet gel body having a thickness of 3 mm. The obtained zeolite-containing wet gel body was cut into 3 × 3 × 3 mm with a cutter and then primary dried at 100 ° C. for 5 minutes to prepare a dry gel body. Next, the dried gel body was subjected to secondary drying in an electric furnace at 300 ° C. for 2 hours to obtain a molded body having a zeolite content of 80% by weight and evaluated. The results are shown in Table 1.

(Example 1-8) Cut molding Silane alkoxide (TEOS) 25 g
Pure water 23.5g
37.6g of methanol
2N hydrochloric acid (pH3) 0.5g
The above material is stirred at room temperature (23 ° C.) for 5 minutes to prepare a silane alkoxide hydrolyzed solution (solid content concentration 26.8% by weight). Thereafter, 23 g of hydrophilic zeolite (13X) showing alkalinity and 23 g of hydrophobic zeolite (HiSiV3000) showing alkalinity were mixed and placed in a petri dish with a diameter of 12 cm on a table kept horizontally, in an environment of 23 ° C./55% RH. The mixture was allowed to stand for 3 minutes to prepare a clay-like zeolite-containing wet gel body (solid content concentration 45% by weight, pH 10, deformation rate 20%) having no fluidity. Other than that was carried out similarly to Example 1-7, and obtained and evaluated the molded object of the zeolite content rate of 80 weight% whose ratio of hydrophilic zeolite (13X): hydrophobic zeolite (HiSiV3000) was 1: 1. The results are shown in Table 1.

(Example 1-9)
A silane alkoxide hydrolyzed solution was prepared in the same manner as in Example 1-8. Then, it was mixed with 46.16 g of hydrophilic zeolite (3A) showing acidity, placed in a petri dish with a diameter of 12 cm on a table kept horizontal, and allowed to stand for 5 minutes in an environment of 23 ° C./55% RH. A 3 mm sheet-like non-fluid agar-containing zeolite-containing wet gel (solid content concentration 45 wt%, pH 3, deformation rate 10%) was prepared.

  Otherwise, a molded product having a zeolite content of 80% by weight was obtained and evaluated in the same manner as in Example 1-8. The results are shown in Table 1.

(Example 2-1)
Silane alkoxide (TEOS) 25g
10g of pure water
40g of methanol
10% ammonia (pH 12) 1g
The above material is stirred at room temperature (23 ° C.) for 1 minute to produce a silane alkoxide hydrolyzed solution (solid content concentration 15.2% by weight). After that, it was mixed with 46.16 g of hydrophobic zeolite (HiSiV3000) showing alkalinity, placed in a petri dish with a diameter of 12 cm on a table kept horizontal, and allowed to stand in an environment of 23 ° C./55% RH for 3 minutes to be fluid A clay-like zeolite-containing wet gel body (solid content concentration 47% by weight, pH 12, deformation rate 20%) was prepared. In addition, a deformation rate is the value which measured the deformation rate of the wet gel body for a measurement produced similarly.

The clay-like wet gel body was pressurized at 1 kg / cm ² to obtain a sheet-like wet gel body having a thickness of 3 mm. The obtained zeolite-containing wet gel body was cut into 3 × 3 × 3 mm with a cutter and then primary dried at 100 ° C. for 5 minutes to prepare a dry gel body. Next, the dried gel body was secondarily dried at 300 ° C. for 2 hours in an electric furnace to obtain a molded body having a zeolite content of 80% by weight. Evaluation was performed in the same manner as in Example 1-1. The results are shown in Table 2.

(Example 2-2)
A molded body having a zeolite content of 80% by weight was obtained and evaluated in the same manner as in Example 2-1, except that the blend of pure water and methanol was changed to 22.5 g of pure water and 27.5 g of methanol. The results are shown in Table 2.

(Example 2-3)
A molded body having a zeolite content of 80% by weight was obtained and evaluated in the same manner as in Example 2-1, except that pure water and methanol were changed to 2.5 g of pure water and 47.5 g of methanol. The results are shown in Table 2.

(Example 2-4)
A molded product having a zeolite content of 80% by weight was obtained and evaluated in the same manner as in Example 2-1, except that pure water and methanol were mixed in pure water 27 g and methanol 111 g. The results are shown in Table 2.

(Example 2-5)
A silane alkoxide hydrolyzed solution was prepared in the same manner as in Example 2-1. Then, it was mixed with 46.16 g of hydrophilic zeolite (3A) showing acidity, placed in a petri dish with a diameter of 12 cm on a table kept horizontal, and allowed to stand for 5 minutes in an environment of 23 ° C./55% RH. A 3 mm sheet-like non-fluid agar-containing zeolite-containing wet gel (solid content concentration 47% by weight, pH 3, deformation rate 10%) was prepared.

  Otherwise, a molded product having a zeolite content of 80% by weight was obtained and evaluated in the same manner as in Example 2-1. The results are shown in Table 2.

(Comparative Example 2-1)
Silane alkoxide (TEOS) 25g
40g of pure water
Methanol 10g
10% ammonia (pH 12) 1g
The above material was stirred at room temperature (23 ° C.) to prepare a silane alkoxide hydrolyzed solution (solid content concentration: 15% by weight). However, the hydrolyzed solution gelled, and zeolite could not be mixed.

(Comparative Example 2-2)
Silane alkoxide (TEOS) 25g
10g of pure water
Methanol 20g
10% ammonia (pH 12) 1g
The above material was stirred at room temperature (23 ° C.) to prepare a silane alkoxide hydrolyzed solution (solid content concentration: 21% by weight). However, the hydrolyzed solution gelled and zeolite could not be mixed.

  According to the production method of the present invention, the shape containing the adsorbent-containing molding with high productivity can be produced with high accuracy and can be widely used in the adsorption field.

Claims (11)

Producing a silane alkoxide hydrolyzed solution;
Adding a zeolite to the silane alkoxide hydrolysis solution to form a wet gel;
Placing the wet gel in a mold and curing to a wet gel body;
Drying the wet gel body to form a dry gel body;
In the method for producing an adsorbent-containing molded article having
The production process of the silane alkoxide hydrolyzed solution is using an acid catalyst,
The silane alkoxide hydrolyzed solution contains water and alcohol as a solvent, and the proportion of alcohol in the solvent is 10% by weight or more,
The zeolite is one or both of an acidic zeolite and an alkaline zeolite,
The dry gel body has a zeolite content of 70 to 98% by weight,
A method for producing an adsorbent-containing molded article characterized by the above. Producing a silane alkoxide hydrolyzed solution;
Adding a zeolite to the silane alkoxide hydrolysis solution to form a wet gel;
Placing the wet gel in a mold and curing to a wet gel body;
Drying the wet gel body to form a dry gel body;
In the method for producing an adsorbent-containing molded article having
The production process of the silane alkoxide hydrolyzed solution is using an alkali catalyst,
The silane alkoxide hydrolyzed solution contains water and alcohol as a solvent, the proportion of alcohol in the solvent is 50 wt% or more and 100 wt% or less, and the solid content concentration of the silane alkoxide hydrolyzed solution is 5 to 20%. And
The zeolite is one or both of an acidic zeolite and an alkaline zeolite,
The dry gel body has a zeolite content of 70 to 98% by weight,
A method for producing an adsorbent-containing molded article characterized by the above.   The method for producing an adsorbent-containing shaped body according to claim 1 or 2, wherein the dry gel body has a zeolite content of 80 to 95 wt%.   The adsorbent-containing molded article according to any one of claims 1 to 3, wherein the step of forming the wet gel further includes a step of increasing the pH value to 8 or more when the pH value of the wet gel after addition of zeolite is less than 8. Manufacturing method.   The method for producing an adsorbent-containing molded article according to claim 4, wherein the step of increasing the pH value of the wet gel after the addition of oleite to 8 or more is a step of adjusting the pH value while stirring the wet gel. The step of curing the wet gel body is a step of curing the deformation rate of the wet gel body to more than 0% and 95% or less,
Pressurizing the wet gel body having a deformation rate of more than 0% and not more than 95% at 100 g / cm ^{2 to 20} kg / cm ² ;
The method for producing an adsorbent-containing molded body according to any one of claims 1 to 5, further comprising a step of cutting the pressurized wet gel body.   The method for producing an adsorbent-containing molded article according to any one of claims 1 to 6, wherein the drying temperature in the step of forming the dried gel body is primary drying at 23C to 120C.   The method for producing an adsorbent-containing shaped body according to claim 1, further comprising a step of secondary drying the dried gel body at 140 ° C. or higher.   The method for producing an adsorbent-containing molded article according to claim 8, wherein the secondary drying is performed at 200 to 350 ° C.   The method for producing an adsorbent-containing molded article according to any one of claims 1 to 9, wherein the solid content concentration of the wet gel is 30% by mass or more.   An adsorbent-containing molded article obtained by the method for producing an adsorbent-containing molded article according to any one of claims 1 to 10.