JP5366277B2 - Adsorbent-containing molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adsorbent-containing molded body which contains zeolite of 95 wt.% or more so as to maintain its adsorptivity and is obtained by a production method for a molded body capable of molding a fine shape having high hardness without using a large-scale device. <P>SOLUTION: The adsorbent-containing molded body is obtained by a production method including: a process of mixing the zeolite powders and a cellulose-based binder of 15-30 pts.wt.based on 100 pts.wt. of the zeolite powder; a process of kneading the mixture in a clay form; a process of cutting the kneaded clay body; and a heat treatment process of a clay body comprising s drying step of vaporizing the moisture in the cut clay body and a step of eliminating the cellulose-based binder in the moisture-vaporized clay body by heating. The final product of the molded body has a zeolite content of 95 wt.% or more and hardness of 18.0 N or higher. <P>COPYRIGHT: (C)2013,JPO&amp;INPIT

Description

  The present invention relates to a method for producing an adsorbent-containing molded article and an adsorbent-containing molded article, and more particularly to a method for producing an adsorbent-containing molded article having a high zeolite content and an adsorbent-containing molded article obtained by the production method.

  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 size of the macropores in the zeolite is in 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.

  In order to produce a molded product that maintains the same adsorptive power as zeolite powder, the zeolite content needs to be 95% by weight or more. However, it is difficult to make the zeolite powder itself highly contained because it has no aggregation property. Moreover, although 90 wt% zeolite beads are manufactured (see, for example, Patent Document 1), the beads are only in the shape of beads because they are kneaded using a clay-based material as a binder and manufactured by a granulator. The bead shape was inferior in size accuracy from the fine shape incorporated in the electronic component.

  Further, in the cited document 2, a microporous body made of an inorganic material and an organic binder are mixed, heated and crystallized to be zeoliteized, and the organic binder is burned off to obtain a 100% zeolite molded body. However, since Cited Document 2 uses a large apparatus such as a 100-t universal testing machine to extrude a molded product to a high pressure, the use of such a large apparatus increases the cost and is incorporated into an electronic component. It is difficult to form a fine shape. In addition, when the inventors made a similar trial without using a large apparatus, the molded product had low hardness or could not be hardened into the molded product because it was not extruded at a high pressure.

  Therefore, there has been a demand for a production method that can produce a fine shape that can incorporate a molded article having a zeolite content of 95% by weight or more into an electronic component without using a large apparatus.

JP-A-1-171554 JP 2000-327327 A

  An object of the present invention is to provide a method for producing an adsorbent-containing molded article of a zeolite-rich molded article containing a high amount of zeolite at 95% by weight or more so that the adsorption power can be maintained, and an adsorbent obtained by the production method. It is to provide a containing molded body.

  Another object of the present invention is to provide a method for producing an adsorbent-containing molded body having high hardness and capable of molding a fine shape without using a large apparatus.

Mixing the zeolite powder and the cellulosic binder according to the present invention;
Adding water to the mixture and kneading into a clay;
Cutting the kneaded clay body;
A heat treatment step of the clay body comprising a drying step of volatilizing the moisture in the cut clay body and a step of eliminating the cellulosic binder in the clay body from which the moisture has been volatilized by heating;
A method for producing an adsorbent-containing molded article having
Cellulosic binder is 15-30 parts by weight with respect to 100 parts by weight of the zeolite powder,
The zeolite content of the final molded product is 95% by weight or more,
There is provided a method for producing an adsorbent-containing molded article characterized by the above.

  Moreover, according to this invention, the adsorbent containing molded object obtained by the manufacturing method of the said adsorbent containing molded object is provided.

  As described above, according to the present invention, a molded body containing a high amount of zeolite to 95% by weight or more without using a large apparatus has high hardness, and a method for producing an adsorbent-containing molded body capable of molding a fine shape and the method It has become possible to provide an adsorbent-containing molded article obtained by the production method.

  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.

It is a figure which shows the hardness of the adsorbent containing molded object in the range specified by this invention.

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

  The zeolite powder used in the present invention may be either a hydrophilic zeolite or a hydrophobic zeolite, a method of preparing by a dealumination treatment using a mineral acid or the like using a natural zeolite or a synthetic zeolite as a starting material, or a silica source, It can be obtained by a direct synthesis method in which an alumina source, an alkali source and an organic mineralizer are mixed and crystallized. 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, the pore inlet may be a zeolite having an oxygen 8, 10 or 12 membered ring. In the present invention, those that preferentially adsorb organic gas and odor components over moisture are preferred.

  In the present invention, it is preferable to use hydrophobic zeolite as the zeolite powder to be added. Usually, when hydrophilic zeolite widely used as zeolite is added, it may generate heat up to around 200 ° C immediately after the addition by adsorbing the water of the solvent. Is easy to use.

  The molded product obtained by the present invention needs to have a zeolite content of 95% by weight or more, preferably 100% by weight, in order to produce a molded product that maintains the same adsorption capacity as the zeolite powder. The zeolite content according to the present invention is high, that is, the binder is small or does not contain a binder, so that it is difficult to produce a molded product that retains hardness, and it is necessary to make it brittle when producing a fine shape.

  The amount of the organic binder is 15 to 30 parts by weight, preferably 15 to 25 parts by weight with respect to 100 parts by weight of the zeolite powder. When the amount is less than 15 parts by weight with respect to 100 parts by weight of the zeolite powder, the binding force is insufficient to harden the zeolite powder into a molded body, and thus molding cannot be performed. On the other hand, if it is added in an amount exceeding 30 parts by weight, the organic binder is burned off by sintering when the molded body is dried, so that there are many gaps in the molded product and the hardness is lowered.

  The molded product can contain clay mineral as an auxiliary agent, and the molded body added with zeolite powder + organic binder + clay mineral has only organic binder + the same amount of organic binder as clay mineral added. There is a tendency for the hardness to be higher than that of the molded body. In the case of the above composition, sufficient hardness is obtained when the content of the clay mineral that does not disappear even at a high temperature to be sintered is about 5 parts by weight with respect to 100 parts by weight of the zeolite.

  The clay mineral + organic binder is preferably 20 to 35 parts by weight, more preferably 20 to 25 parts by weight with respect to 100 parts by weight of the zeolite powder. If it is less than 20 parts by weight, it is difficult to harden the molded product. On the other hand, when it is added in excess of 35 parts by weight, the content of the organic binder is increased, and there are many gaps in the sintered product after sintering, resulting in a decrease in hardness.

  If the amount of water added to the zeolite powder is not 70 parts by weight or more with respect to 100 parts by weight of the zeolite powder, it is difficult to mix and knead the zeolite powder in a clay state, preferably 80 to 200 parts by weight. When using hydrophilic zeolite for the zeolite powder, it is necessary to add more than when using hydrophobic zeolite.

  As the organic binder, a cellulose type is preferable, and for example, methyl cellulose is used.

  Examples of clay minerals include sepiolite (sepiolite, etc.), kaolin (kaolinite, nacrite, dickite, halloysite, etc.), antigolite (antigolite, amesite, chronsteadite, etc.), and virophilite (bilophyllite). Phyllite, talc, etc.), mica type (illite, sea green stone, ceradonite, sericite, muscovite, etc.), smectite (montmorillonite (bentonide), beidellite, nontronite, saponite, hectorite, etc.), balm cue Light system (balm curite), chlorite system (chlorite).

Among these, sepiolite is preferable because of its adsorption capacity. Adsorption capacity of sepiolite is located a specific surface area of 230~320m ² / g, greater than the 139~169m ² / g of zeolite (natural). Sepiolite has better water absorption performance against water and moisture, and sepiolite tends to begin to desorb the absorbed water at a considerably high speed, while zeolite has a rather strong water retention capability and therefore has poor moisture release. In the application of the present invention, water retention tends to be more important for installation inside an electronic component.

  In the present invention, water is added after mixing the zeolite powder and the organic binder, and the mixture is kneaded into a clay, and the clay is further kneaded with a kneader such as a three-roller, and then the kneaded product is blended. Therefore, it trains for 8 to 24 hours in a refrigerator (0 to 5 ° C.). Next, the clay-like kneaded product is extruded to a desired thickness to obtain a sheet-like clay body. When the sheet-like clay body is cut or die-cut in this state, it is difficult to cut it into a fine shape by sticking to the blade, so it is preferable to perform pre-drying at 50 to 70 ° C. for 1 to 10 minutes in order to reduce the moisture content. . After preliminary drying, the clay body is cut or die-molded into a desired shape, and heat treatment is performed to eliminate the organic binder in the molded body. The heat treatment is performed in steps of primary drying and secondary drying. In primary drying, in order to volatilize the water | moisture content of a clay body mainly, 200 to 400 degreeC is preferable, More preferably, it is 250 to 350 degreeC. In secondary drying, the temperature is preferably 500 ° C. to 800 ° C., more preferably 500 ° C. to 700 ° C., in order to eliminate the organic binder. It should be noted that heating above 800 ° C. may change the pore structure of the zeolite and reduce the adsorption performance. The drying time is preferably 1 hour to 3 hours.

  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
Hydrophobic zeolite powder 100g
(Product name: HiSiV3000, manufactured by Union Showa)
Cellulose binder 25g
(Product name: Serander, main component methylcellulose, manufactured by Yuken Industry Co., Ltd.)
The above materials were mixed at room temperature (23 ° C.). Next, 100 g of pure water is added and kneaded. The clay-like material is kneaded with three rolls, and the kneaded product is cultivated in a refrigerator (3 ° C.) for 12 hours.

  The kneaded product of the clay body was extruded with an extruder to obtain a sheet-like clay body having a thickness of 2 mm. Then, it was pre-dried at 60 ° C. for 5 minutes. Thereafter, the clay body was cut into 5 mm × 5 mm in order from the end of the sheet-like clay body using a cutter composed of a single blade having a linear length of 100 mm.

  Next, the clay body was primary dried at 300 ° C. for 2 hours and secondary dried at 600 ° C. for 2 hours in an electric furnace to eliminate the cellulosic binder, whereby a molded body having a zeolite content of 100% by weight was obtained.

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

<Evaluation>
"Extrudability"
The moldability until the above material was extruded into a sheet with an extruder was observed.

"hardness"
A molded product obtained to 5 mm × 5 mm × 2 mm was measured from the top using a digital force gauge (trade name: FGC-50, manufactured by SHIMPO), and the value at the time of cracking was measured, and 5 points were measured. Average values are shown. In actual use, there was no problem if the molded product had a hardness of 10 N or more in handling when installed inside an electronic component.

(Examples 2 to 4)
In Example 1, except that the amount of the cellulose-based binder was changed as shown in Table 1, it was dried in the same manner to produce a molded body and evaluated. The results are shown in Table 1.

(Example 5)
Hydrophobic zeolite powder 100g
Sepiolite powder 5g
(Product name: PANGEL, GROPO TOLSA (Spain))
Cellulose binder 20g
A clay body was produced in the same manner as in Example 1 using the above materials. Then, it was made to dry like Example 1 and the molded object was produced, and evaluation was performed. The results are shown in Table 1.

(Examples 6 to 8)
In Example 5, except that the amount of the cellulose-based binder was changed as shown in Table 1, it was dried in the same manner to produce a molded body and evaluated. The results are shown in Table 1.

Example 9
Hydrophilic zeolite powder (3A) 100g
Sepiolite powder 3g
Cellulose binder 18g
A clay body was produced in the same manner as in Example 1 except that 150 g of pure water was used. Then, it was made to dry like Example 1 and the molded object was produced, and evaluation was performed. The results are shown in Table 1.

(Comparative Example 1)
Hydrophobic zeolite powder 100g
Cellulose binder 35g
A clay body was produced in the same manner as in Example 1 using the above materials. Then, it was made to dry like Example 1 and the molded object was produced, and evaluation was performed. The results are shown in Table 2.

(Comparative Examples 2-3)
In Comparative Example 1, except that the amount of the cellulose-based binder was changed as shown in Table 2, it was dried in the same manner to produce a molded product, and evaluation was performed. The results are shown in Table 2.

(Comparative Example 4)
Hydrophobic zeolite powder 100g
Sepiolite powder 5g
Cellulose binder 35g
A clay body was produced in the same manner as in Example 1 using the above materials. Then, it was made to dry like Example 1 and the molded object was produced, and evaluation was performed. The results are shown in Table 2.

(Comparative Examples 5-6)
In Comparative Example 4, except that the amount of the cellulose-based binder was changed as shown in Table 2, it was dried in the same manner to produce a molded body and evaluated. The results are shown in Table 2.

(Comparative Example 7)
Hydrophobic zeolite powder 100g
Sepiolite powder 5g
Cellulosic binder 10g
A clay body was produced in the same manner as in Example 1 using the above materials. Then, it was made to dry like Example 1 and the molded object was produced, and evaluation was performed. The results are shown in Table 2.

(Comparative Example 8)
Hydrophobic zeolite powder 100g
Sepiolite powder 5g
A clay body was produced in the same manner as in Example 1 using the above materials. Then, it was made to dry like Example 1 and the molded object was produced, and evaluation was performed. The results are shown in Table 2.

(Comparative Example 9)
Hydrophobic zeolite powder 100g
Sepiolite powder 40g
A clay body was produced in the same manner as in Example 1 using the above materials. Then, it was made to dry like Example 1 and the molded object was produced, and evaluation was performed. The results are shown in Table 2.

  Since Examples 1 to 9 were within the scope of the present invention, a molded product having high hardness was obtained. In Examples 5 to 8, when the amount of sepiolite was increased by reducing the amount of the cellulose binder, a molded article having improved hardness as compared with the cellulose binder alone was obtained. In Example 9, a hydrophilic zeolite was used as the zeolite powder, and a molded article having a high hardness was obtained as in the case of the hydrophobic zeolite. However, since heat is generated when water is added, the cooling time is added, so that productivity is improved. A slight decrease was observed.

  Since Comparative Examples 1-6 had too many organic binders, there were many gaps in the sintered compact and the hardness was low. Since Comparative Examples 4 to 6 contain sepiolite, the hardness is higher than Comparative Examples 1 to 3, but the hardness is insufficient for actual use. In Comparative Example 7, since the organic binder was small, it was impossible to harden the zeolite powder as a compact. Since Comparative Example 8 did not contain an organic binder, even if water was added, it did not change from the powdered form of Bosobosapasa and could not be hardened as a molded body. In Comparative Example 9, since the amount of the clay mineral sepiolite is large, the hardness is high, so it does not form a sheet, cracks and the like are inferior in moldability, and has a low zeolite content and a low adsorption capacity.

  In Examples 1 to 8 and Comparative Examples 1 to 7, a graph in which the hardness is on the vertical axis and the cellulose content is on the horizontal axis with respect to 100 parts by weight of zeolite is shown in FIG. As can be seen from FIG. 1, an adsorbent-containing molded body having a high hardness can be obtained within the scope of the present invention.

  According to the production method of the present invention, a compact containing 95% by weight or more of zeolite has a high hardness without using a large apparatus, can form a fine shape, and can be widely used in the adsorption field.

Claims (6)

Zeolite content to a sorbent-containing molded article of Der Ru 5 mm × 5 mm × 2 mm or more 95 wt%, the adsorbent-containing formed body, wherein the hardness is not less than 18.0N.   Furthermore, the adsorbent containing molded object of Claim 1 containing a clay mineral.   The adsorbent-containing molded article according to claim 2, wherein the clay mineral is sepiolite. Mixing the zeolite powder and the cellulosic binder;
Adding water to the mixture and kneading into a clay;
Cutting the kneaded clay body;
An adsorbent-containing molded body comprising: a drying step for volatilizing water in the cut clay body; and a heat treatment step for the clay body comprising a step of eliminating the cellulose-based binder in the clay body from which the water has been volatilized by heating. A manufacturing method comprising:
The cellulose binder is 15 to 30 parts by weight with respect to 100 parts by weight of the zeolite powder,
The adsorbent-containing molded article according to claim 1, obtained by a method for producing an adsorbent-containing molded article having a zeolite content of 95% by weight or more in the final molded article.   The adsorbent-containing molded article according to claim 4, wherein a clay mineral is further mixed in the step of mixing the zeolite powder and the cellulose-based binder.   The adsorbent-containing molded article according to claim 5, wherein the clay mineral is sepiolite.

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