JP5439621B1 - Method for producing zeolite structure - Google Patents

Abstract

A zeolite structure that is easy to handle as an adsorbent and the like is provided.
A method for producing a zeolite structure according to the present invention includes a first step of pulverizing a first raw material made of inorganic glass with a dry ball mill to obtain a first powder, and a second step made of countless fine bamboo fibers. A second step of obtaining a raw material; a third step of mixing the first powder and the second raw material in a basic aqueous solution to obtain a first reaction solution; and depressurizing the first reaction solution; A fourth step of obtaining and a fifth step of hydrothermally treating the second reaction liquid to obtain a zeolite structure.
[Selection] Figure 1

Description

The present invention relates to the production how Ze zeolite structure.

  Patent Document 1 discloses a method for producing zeolite. This manufacturing method includes a first step of pulverizing alkali-free glass collected from a liquid crystal panel that is no longer needed to obtain a powder, a second step of bringing a powder into contact with a basic aqueous solution to obtain a hydrogel, And a third step of obtaining a zeolite by heat treatment.

  According to this production method, zeolite can be produced from waste glass, and inexpensive zeolite can be obtained. The zeolite thus obtained is a gas adsorbent, a gas separating agent, a deodorizing agent, a drying agent, a dehydrating agent, a dehumidifying agent, an ion exchange agent, a water drainage treatment agent, a filtering agent, a water quality improving agent, a soil improving agent, and an exhaust gas treating agent. It can be used for catalysts, fillers, additives, culture agents and the like.

JP 2012-116743 A

  However, existing zeolites are easily crushed from the secondary agglomerated state and are difficult to handle. For example, since existing zeolite is used for various applications, even if it is attempted to separate only the zeolite after mixing with foreign substances, the separation is extremely difficult.

  This invention is made | formed in view of the said conventional situation, Comprising: It is set as the problem which should be solved to provide the zeolite structure which is easy to handle as adsorption agent etc.

The method for producing a zeolite structure of the present invention includes a first step of pulverizing a first raw material made of inorganic glass by a dry ball mill to obtain a first powder,
A second step of obtaining a second raw material consisting of countless fine porous organic fibers;
A third step of mixing the first powder and the second raw material in a basic aqueous solution to obtain a first reaction liquid;
A fourth step of depressurizing the first reaction liquid to obtain a second reaction liquid;
And a fifth step of hydrotreating the second reaction solution to obtain a zeolite structure (claim 1).

Moreover, the zeolite structure of the invention features that it has a myriad of fine porous organic fibers, and a zeolite held in each pore of each said porous organic fibers.

  The zeolite structure of the present invention can be manufactured by the manufacturing method of the present invention. According to the inventors' confirmation, the zeolite structure thus obtained has a structure in which an infinite number of zeolites are held in pores of an infinite number of fine porous organic fibers.

  This zeolite structure prevents the organic matter from damaging the action effect of each zeolite because each porous organic fiber existing around each zeolite is entangled with organic matter such as cellulose in various applications. Also exhibits excellent effects.

  In addition, even if this zeolite structure is mixed with foreign substances in various applications, it is fibrous with countless fine porous organic fibers, so it can be separated from foreign substances relatively easily by a sieve or the like. is there.

  Therefore, according to the production method of the present invention, a zeolite structure that is easy to handle as an adsorbent or the like can be produced. Moreover, the zeolite structure of the present invention is easy to handle as an adsorbent or the like.

  According to the test results of the inventors, the first step is preferably pulverized by a dry ball mill in the first step. By pulverizing with a dry ball mill, the first powder exhibits high activity because individual particles have internal distortion. Further, according to the test results of the inventors, it is preferable that 90% by mass or more of the first powder has a particle size of 500 μm or less. By pulverizing to this extent, each particle has a large surface area and exhibits high activity.

  As the porous organic fiber, it is possible to employ artificial porous fibers such as expanded polystyrene as well as vegetable porous fibers such as bamboo fibers and palm fibers. In particular, the porous organic fiber is preferably bamboo fiber (claim 2). This is because the inventors have confirmed that the zeolite structure of the present invention can be produced using bamboo fibers as porous organic fibers. Moreover, since bamboo fiber is porous, it can adsorb | suck many adsorbates. Moreover, the effect of deodorizing etc. is anticipated with porous bamboo fiber. As the bamboo of the bamboo fiber, it is possible to adopt 孟 宗 bamboo, Japanese bamboo, bamboo bamboo and the like.

  The inorganic glass is preferably a waste glass material. In this case, the manufacturing cost of the zeolite structure can be reduced. Use of waste glass is also desirable from the viewpoint of recycling. As the waste glass, it is possible to employ a liquid crystal panel that is no longer necessary.

  The inorganic glass may be pearlite (claim 4). Perlite is a foam obtained by heat-treating pearlite. Its chemical composition is mainly composed of silicic acid and alumina, and its crystal structure is amorphous. For this reason, perlite can be handled as inorganic glass in the present invention. In addition, pearlite is excellent in chemical resistance, and is marketed as a heat insulating material and a water retaining material by controlling the foam structure.

  According to the method for producing a zeolite structure of the present invention, it is possible to provide a zeolite structure that is easy to handle as an adsorbent or the like. Moreover, the zeolite structure of the present invention is easy to handle as an adsorbent or the like.

It is process drawing which shows the manufacturing method of the zeolite structure of Example 1,2. It is a 500 times as many SEM photograph of the bamboo fiber used with the manufacturing method of Example 1,2. 4 is a 500-times SEM photograph of the zeolite structure of Test Product 1 according to Example 1. FIG. 4 is a SEM photograph of 10000 times the zeolite structure of Test Product 1 according to Example 1. 4 is a 500-times SEM photograph of the zeolite structure of Test Sample 2 according to Example 1. FIG. 4 is a SEM photograph of 10000 times the zeolite structure of Test Product 2 according to Example 1. 5 is a 500-times SEM photograph of the zeolite structure of Test Sample 3 according to Example 1. 4 is a SEM photograph of the zeolitic structure of Test Product 3 at a magnification of 10,000 according to Example 1. It is a graph which shows the pore size distribution of the zeolite structure of a comparative product and test products 1-3. 4 is a 100 times SEM photograph of heat-insulating pearlite used in the production method of Example 2. FIG. 4 is a 100 times SEM photograph of pearlite, which is a fine stone used in the production method of Example 2. 6 is a 200-times SEM photograph of a zeolite structure according to Example 2. 4 is a 1000-times SEM photograph of a zeolite structure according to Example 2. 4 is a SEM photograph of the zeolite structure at a magnification of 5000, according to Example 2.

  Embodiments 1 and 2 embodying the present invention will be described below with reference to the drawings.

Example 1
As shown in FIG. 1, in the first step S <b> 1, the waste glass material as the first raw material was pulverized using a dry ball mill. Specifically, 24-32 kg of waste glass was put into a dry ball mill, and pulverization was performed for 2 to 6 hours at a rotation speed ratio of 0.85 or 0.95 (N / Nc).

  In the dry ball mill used here, the inner wall of the pot is made of iron, the length of the pot is 725 mm, and the diameter of the pot is 725 mm. Each ball is made of steel and has a diameter of 10 mm, 15 mm or 30 mm. The filling rate of the balls with respect to the volume in the pot is 40 to 60%.

Waste glass is a panel glass for LCD (Liquid Crystal Display). The composition of the waste glass is 58.8% by mass of SiO ₂ , 17.1% by mass of Al ₂ O ₃ , 9.5% by mass of CaO, 0.3% by mass of Na ₂ O, and 14.3% for others. % By mass.

  According to the test results of the inventors, by pulverizing with a dry ball mill, the first powder exhibits high activity because individual particles are distorted inside. Table 1 shows the particle size of the first powder thus obtained.

  As shown in Table 1, 90% by mass or more of the obtained first powder has a particle size of 500 μm or less.

In the second step S2, countless fine bamboo fibers were obtained using a known technique. Here, “Takeho” manufactured by Nagasaki Kogyo Co., Ltd. was used as the bamboo fiber. A 500 times SEM photograph of this bamboo fiber is shown in FIG. The BET specific surface area of the bamboo fiber is 0.18946 m ² / g. In addition, for example, it is also possible to manufacture bamboo fiber by a manufacturing method disclosed in JP 2013-42753 A.

  In the third step S3 shown in FIG. 1, 14 ml of 1M aqueous sodium hydroxide solution, 0.91 g of the first powder, the second raw material, and 1.31 g of sodium aluminate are prepared, mixed, One reaction solution was obtained. The second raw material was 0 g, 0.3 g, 1 g, or 3 g. Here, sodium aluminate is an agent for replenishing aluminum and sodium necessary for producing zeolite from waste glass.

  In the fourth step S4, the first reaction solution was depressurized in order to make each pore in each fiber of the second raw material soaked with a basic aqueous solution and precipitate zeolite in each pore. In this way, the 2nd reaction liquid was obtained.

  In the fifth step, hydrothermal treatment was performed on the second reaction liquid at 95 ° C. for 12 hours. According to the tests by the inventors, when the hydrothermal treatment at a higher temperature and for a longer time is performed in the basic aqueous solution, the cellulose of the bamboo fiber is decomposed. After hydrothermal treatment, suction filtration and drying were performed to obtain a zeolite structure.

  The case where the second raw material was not added was used as a comparative product. Further, when 0.3 g of the second raw material is added, the zeolite structure of the test product 1 is added, when 1 g of the second raw material is added, the zeolite structure of the test product 2 and when 3 g of the second raw material is added, the test product 3 This zeolite structure was obtained.

A 500 times SEM photograph of the zeolite structure of Test Product 1 is shown in FIG. Moreover, the SEM photograph of 10,000 times of the zeolite structure of the test sample 1 is shown in FIG. The zeolite structure had a BET specific surface area of 3.2975 m ² / g.

A 500 times SEM photograph of the zeolite structure of Test Product 2 is shown in FIG. In addition, an SEM photograph of 10,000 times of the zeolite structure of Test Sample 2 is shown in FIG. The zeolite structure had a BET specific surface area of 2.0947 m ² / g.

A 500 times SEM photograph of the zeolite structure of Test Product 3 is shown in FIG. Moreover, the SEM photograph of 10,000 times of the zeolite structure of the test sample 3 is shown in FIG. The zeolite structure had a BET specific surface area of 2.4492 m ² / g.

  Moreover, the pore size distribution of the zeolite structures of the comparative product and the test products 1 to 3 is shown in FIG.

  As shown in FIGS. 3 to 8, it can be seen that the zeolite structure can be produced by the production method of Example 1. These zeolite structures have a structure in which an infinite number of A-type zeolites are held in pores of an infinite number of fine bamboo fibers. For this reason, these zeolite structures contain an abundance of extremely fine pores as shown in FIG.

  In various applications, these zeolite structures prevent each organic matter such as cellulose from interfering with the organic matter such as cellulose, and prevent the organic matter from damaging the action effect of each zeolite. Exhibits excellent effects.

  Moreover, even if these zeolite structures are mixed with foreign substances in various applications, they are fibrous with countless fine bamboo fibers, and therefore can be separated from foreign substances relatively easily by a sieve or the like. .

  Therefore, according to the manufacturing method of Example 1, a zeolite structure that is easy to handle as an adsorbent or the like can be manufactured. Moreover, the zeolite structure of Example 1 is easy to handle as an adsorbent or the like.

  Moreover, in the manufacturing method of Example 1, since the waste glass material is made into the 1st raw material, the manufacturing cost of a zeolite structure can be reduced.

(Example 2)
In the manufacturing method of Example 2, the first raw material is pearlite. The composition of perlite, SiO ₂ 75.0 wt%, Al ₂ O ₃ is 14.0 wt%, CaO 0.1 wt%, Na ₂ O is 3.5 wt%, K ₂ O 4.2 % By mass, 0.9% by mass of Fe ₂ O _{3 and} 2.3% by mass of others.

  A 100 times SEM photograph of the heat-insulating pearlite used in Example 2 is shown in FIG. In addition, the 100-times SEM photograph of the pearlite which is a fine stone is shown in FIG.

The conditions for the first step were as follows.
Pot inner wall: iron Ball: iron, diameter 15mm
Weight of first powder: 0.64kg
Total ball weight: 7.5kg
Pot rotation speed: 83rpm

  In the fifth step, hydrothermal treatment was performed on the second reaction solution at 150 ° C. for 84 hours. Other steps are the same as those in the first embodiment. In this way, a zeolite structure was obtained.

  A 200 times SEM photograph of the obtained zeolite structure is shown in FIG. 12, a 1000 times SEM photograph is shown in FIG. 13, and a 5000 times SEM photograph is shown in FIG.

  12-14, it turns out that a zeolite structure can be manufactured also by the manufacturing method of Example 2. FIG. These zeolite structures have a structure in which an infinite number of mordenite-type zeolite is held in each pore of an infinite number of fine bamboo fibers.

  Therefore, the manufacturing method of the second embodiment can achieve the same effects as those of the first embodiment. Further, the zeolite structure of Example 2 can achieve the same effects as those of Example 1. In particular, this zeolite structure is suitable for use as a material that adsorbs and separates radioactive cesium because the zeolite is a mordenite type.

  In the above, the present invention has been described with reference to the first and second embodiments. However, the present invention is not limited to the first and second embodiments, and can be appropriately modified and applied without departing from the spirit of the present invention. Needless to say.

  The present invention can be used for adsorbents and the like.

S1 ... 1st process S2 ... 2nd process S3 ... 3rd process S4 ... 4th process S5 ... 5th process

Claims (4)

A first step of pulverizing a first raw material made of inorganic glass with a dry ball mill to obtain a first powder;
A second step of obtaining a second raw material consisting of countless fine porous organic fibers;
A third step of mixing the first powder and the second raw material in a basic aqueous solution to obtain a first reaction liquid;
A fourth step of depressurizing the first reaction liquid to obtain a second reaction liquid;
And a fifth step of obtaining the zeolite structure by hydrothermally treating the second reaction liquid.   The method for producing a zeolite structure according to claim 1, wherein the porous organic fiber is bamboo fiber.   The method for producing a zeolite structure according to claim 1 or 2, wherein the inorganic glass is a waste glass material.   The method for producing a zeolite structure according to claim 1 or 2, wherein the inorganic glass is pearlite.

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