JPH05286710A - Novel spherical fine k-zeolite particles and their production - Google Patents

Abstract

PURPOSE:To easily produce spherical fine K-zeolite particles having narrow particle size distribution. CONSTITUTION:An aluminum salt is added to an aq. soln. of a potassium salt, colloidal silica is added to the resulting suspension and they are brought into a reaction. A suspension of a product obtd. by the reaction is aged at pH 14 and the solid matter is separated by filtration, washed and dried to produce spherical fine K-zeolite particles having narrow particle size distribution.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a new spherical K-type zeolite fine particle substance having a narrow particle size distribution and a novel method for producing the same.

[0002]

BACKGROUND ART As a conventional method for producing spherical zeolite particles, a method of spraying silica-alumina sol is known. This method is a method in which zeolite powder is pulverized into a fine powder, sprayed or granulated into a spherical shape by a rolling method, and then a spherical zeolite particle is obtained through a sieving step (JP-A-54-54). 62992).

However, the spherical zeolite particles obtained by the above method had a relatively large primary particle size and a wide particle size distribution. Therefore, for example, if the spherical particles are used as they are as an adsorbing filler, fine particles and coarse particles are unevenly distributed at the time of filling, and a uniform packed layer is not formed. In addition, when it is used as it is as a filler for cosmetics, there is a problem that voids are generated between particles and it lacks developability and it feels as graininess. Is required, which is not preferable as an industrial method for producing spherical zeolite particles.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a K-type zeolite fine particle substance having a spherical shape and a narrow particle size distribution range, and a simple production method thereof. More specifically, it is spherical and has a narrow particle size distribution range without controlling the particle shape and particle size distribution by a secondary method such as the conventional method.
An object of the present invention is to provide a type zeolite fine particle substance and a simple new production method thereof.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an aluminum salt is added to an aqueous solution of potassium salt, and colloidal silica is added to the obtained suspension to react. Let The suspension of the product obtained as a result of this reaction is then aged in the range of pH 14, the solid substance is filtered off, washed with water and dried to obtain a spherical inorganic powder substance, and It was found that they consist of K-type zeolite fine particles having a narrow particle size distribution range.
The present invention has been made based on such findings.

The novel K-type zeolite fine particle substance according to the present invention is a white spherical inorganic powder substance having the following composition. Al ₂ O _3: 15 to 30 _{wt%, SiO 2: Al 2 O} 3 molar ratio of SiO ₂ is 1: 1
5, K ₂ O: 10 to 30% by weight

The primary particle size of the K-type zeolite fine particle material of the present invention is 3.0 μm or less, and the 50% average particle size is 1
˜5 μm range, B.I. E. T. The specific surface area is 5 to ²⁰ m ² /
g, the refractive index is 1.48 to 1.53.

The method for producing the spherical K-type zeolite fine particle substance of the present invention having a narrow particle size distribution range will be described below.

In the K-type zeolite fine particle material of the present invention, first, an aluminum salt is added to an aqueous solution of potassium salt, and colloidal silica is added to the obtained suspension to react. The product suspension resulting from this reaction is then brought to pH 1
After aging in 4, the solid substance is filtered off, washed with water and dried. More specifically, for example, an aluminum salt is added to the above potassium salt aqueous solution, and colloidal silica (SiO ₂ : 20%) is added to the obtained suspension (pH at this time is 14) to cause a reaction. Then, the product suspension obtained as a result of this reaction (pH at this time is 14) is aged, and then the solid substance is filtered off, washed with water, and dried.

Examples of the potassium salt used in the present invention include potassium hydroxide, carbonate and bicarbonate, such as potassium hydroxide, potassium carbonate and potassium hydrogen carbonate, and especially potassium hydroxide. Is preferred.

The aluminum salt is an inorganic salt such as aluminum hydroxide, aluminum chloride, aluminum sulfate, aluminum nitrate or aluminum phosphate, and these salts may be used alone or in combination. The aluminum salt is dissolved or suspended in water, or is added as it is to the aqueous solution of the potassium salt with stirring.

Examples of colloidal silica include silicic acid and aqueous silica. The temperature when adding colloidal silica to the reaction system is not particularly limited, and is usually added dropwise to the reaction system at room temperature. When using amorphous solid silica,
It is suspended in advance in an aqueous solution of the above-mentioned potassium salt, or added as it is to the reaction system while stirring.

The concentration of colloidal silica is preferably such that the composition of silica represented by an oxide is in the range of 20 to 30%.

The aging temperature is from room temperature to 450 ° C, and preferably from 50 to 150 ° C. At this time, when the aging temperature is 100 ° C. or higher, it is carried out in a closed container. The aging time varies depending on the reaction conditions, but is 30 minutes to
It is 240 hours, preferably 2 to 24 hours.

The obtained reaction product is filtered, washed with water and dried according to a conventional method.

Washing with water is carried out until the pH of the washing liquid becomes 10 or less.

The drying temperature is between 50 and 200 ° C, preferably between 60 and 120 ° C. The drying time is
Although it varies depending on the drying temperature and the like, it is generally 1 to 24 hours.

The physicochemical properties of the inorganic powder substance obtained by the above-mentioned production method were determined by a conventional method. For example, the chemical composition is measured by an atomic absorption method, and the loss on ignition (Igloss) is measured when a constant weight is obtained at 500 ° C. for 1 g of the sample.
The line diffraction spectrum was measured using powder X-ray diffraction (XRD; manufactured by Rigaku Denki Co., Ltd.), and the average particle diameter was measured using Nikkiso Co., Ltd. Microtrack MK-II.

The primary particle diameter was determined by taking an electron micrograph with a scanning electron microscope and measuring the diameter of the spherical particle image in the photograph using a scale.

The specific surface area is E. T multipoint method, refractive index was measured by Appe refractometer, and bulk density was J
It was measured according to IS K 6220.6.8.

Since the spherical K-type zeolite fine particles obtained by the present invention have a refractive index of 1.48 to 1.53 and a small specific surface area, they can be used for various purposes. For example, it can be mixed with a thermoplastic resin such as polyethylene, polypropylene or vinyl chloride to be used for the purpose of imparting slip property or anti-blocking property to a resin molded product formed, for example, a biaxially stretched film.

Further, it can be used as a filler or a reinforcing agent for a thermosetting resin for molding or a coating for forming a coating, or as a ceramic base material, or as an internal filler for various papers or a coating filler for papers. ..

It is also useful as a carrier for carrying various cosmetic bases such as foundations, powders, creams, abrasives, toothpaste bases, pharmaceuticals, agricultural chemicals, fragrances, aromatics, etc. or various chromatography carriers. is there. The invention is explained in detail in the following examples.

[0024]

【Example】

(Example 1) 100 ml of distilled water was added with potassium hydroxide (KO
H: 95%) (159.3 g) is dissolved, and a solution in which 53.2 g of aluminum chloride is dissolved in 100 ml of distilled water is added to form a suspension. Colloidal silica (Si
O ₂ : 20%, 64.8 g of Catalyst Kasei Kogyo Co., Ltd., product name: Cataloid) is gradually added dropwise. Distilled water was added to the obtained suspension to make the total amount 400 ml, and the mixture was transferred to a 500 ml stainless steel container and stirred at 100 ° C for 18 hours. The chemical composition of the suspension obtained as a result of the above reaction is expressed by the molar ratio of oxides: H ₂ O / K ₂ O = 10, SiO ₂
/ Al ₂ O ₃ = 2.0, K ₂ O / Al ₂ O ₃ = 12.5
Met. After completion of the reaction, the reaction solution is cooled and the solid substance obtained by filtration is washed until the pH of the washing solution becomes 10.
Then, it was dried at 60 ° C. for 24 hours to obtain a white inorganic powder substance.

The results of the composition analysis of the inorganic powder substance obtained by the above production method are shown in Table 1 below.

Further, it can be confirmed from the pattern of the powder X-ray diffraction spectrum of the inorganic powder substance that the product is a high-purity K-type zeolite. The result of the powder X-ray diffraction spectrum was as shown in FIG.

The result of the particle size distribution measurement is that the 50% average particle size is 1.26 μm and the 90% particle size is 1.93 μm, and the inorganic powder substance is fine and very narrow. It shows that it has a particle size distribution range. The result is as shown in FIG.

Further, it was possible to confirm from the electron micrograph (magnification: 10,000 times) that the above-mentioned inorganic powder substance was spherical fine particles. The result is as shown in FIG.

(Example 2) By the same method as in Example 1, the molar ratio of the oxide composition in the suspension was H ₂ O / K ₂ O.
= 7.5, SiO ₂ / Al ₂ O ₃ = 2.0, K ₂ O / S
A suspension of i0 ₂ = 6.25 was prepared. After completion of the reaction, the reaction solution was cooled and then post-treated in the same manner as in Example 1. The results of composition analysis of the obtained inorganic powder substance are as shown in Table 1 below.

[0030]

[Table 1]

[0031]

Industrial Applicability According to the present invention, it is possible to provide a K-type zeolite fine particle substance having a spherical shape and a narrow particle size distribution range, and a novel and simple production method thereof. That is, the novel method for producing the substance does not require operations such as making spherical K-shaped zeolite fine particles having a narrow particle size distribution uniform in particle shape and particle size distribution by a secondary method like the conventional method. It is industrially extremely advantageous in that it can be produced by a simple method.

[Brief description of drawings]

FIG. 1 is a powder X-ray diffraction spectrum of K-type zeolite fine particles.

FIG. 2 shows a particle size distribution of K-type zeolite fine particles.

FIG. 3 shows an electron micrograph (magnification: 10,000 times) of K-type zeolite fine particles. The length of the white line in this figure is 1 μm.

Claims (6)

[Claims] 1. An aluminum salt is added to an aqueous solution of potassium salt, and colloidal silica is added to the obtained suspension to react. Next, a K-type zeolite fine particle substance obtained by aging the suspension of the product obtained as a result of this reaction at pH 14 and then filtering off the solid substance, washing with water and drying. 2. The K-type zeolite fine particle material according to claim 1, wherein the potassium salt is potassium hydroxide. 3. An aluminum salt is added to an aqueous solution of potassium salt, and colloidal silica is added to the obtained suspension to react. Next, a method for producing a K-type zeolite fine particle material obtained by aging the suspension of the product obtained as a result of this reaction at pH 14 and then filtering off the solid material, washing with water and drying. 4. The method for producing a K-type zeolite fine particle substance according to claim 3, wherein the potassium salt is potassium hydroxide. 5. The K-type zeolite fine particle material according to claim 1, wherein the aging temperature is in the range of room temperature to 450 ° C. 6. The method for producing a K-type zeolite fine particle material according to claim 3, wherein the aging temperature is in the range of room temperature to 450 ° C.