JPH07206425A - Hexagonal platy zeolite particle material and its production - Google Patents

Abstract

PURPOSE:To efficiently produce a hexagonal platy zeolite particle material with high purity in a short time. CONSTITUTION:An alkali source, an alumina source and a silica source are prepd. as reactive starting materials so as to regulate the amt. of K2O to 7-12 pts.wt., the total amt. of Al2O3 and SiO2 to 5-15 pts.wt. and the molar ratio of SiO2:(Al2O3+SiO2) to 1:2 (expressed in terms of oxides) and the starting materials are mixed by stirring in an aq. soln. while causing gelling. The resulting suspension is heated to produce the objective novel hexagonal platy zeolite having a high aspect ratio of 10-30.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hexagonal plate-shaped zeolite particle material useful as a resin reinforcing agent and a method for producing the particle material with high purity and efficiency.

[0002]

2. Description of the Related Art Conventionally, natural zeolites made of crystalline aluminosilicates and synthetic zeolites obtained by, for example, hydrothermal crystallization have a multi-function such as an ion exchange function, an adsorption / molecular sieving function, and a catalytic function. Widely used as a raw material. For example, recently, synthetic zeolite has been used as a resin additive, for example, as an additive for improving the thermal stability of polyvinyl chloride resin and the anti-blocking property of polyolefin resin film, and has a new functionality. Has attracted attention as a material. However, when it is attempted to use the above natural and / or synthetic zeolite crystals as a reinforcing agent for plastics, for example, in the case of natural products, the quality such as purity is not uniform, and the synthetic zeolite particle material is Most of them have cubic or spherical particle morphology.
It was not satisfactory in terms of strength, purity or grain shape.

[0003]

DISCLOSURE OF THE INVENTION It is an object of the present invention to establish a hexagonal plate-like zeolite particle material having strength, purity or particle shape and the like, which can be used as a reinforcing agent for plastics and the like, and a novel production method thereof. And

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that the hexagonal plate-like zeolite particle substance of the present invention has an aspect ratio (ratio between projected area diameter and thickness). The present invention has been completed by finding that the above-mentioned problems can be solved by the method of 10) to 10). That is, according to the present invention, a starting material containing potassium hydroxide as an alkali source, an alumina source and a silica source is sufficiently agitated and mixed to cause uniform gelation, and then the obtained suspension is heated. It is a characteristic hexagonal plate-like zeolite particle material and a method for producing the same.

The hexagonal plate-like zeolite particle material of the present invention is
Composition formula K ₂ O: 20 to 30 parts by weight Al ₂ O _{3: 20~30} parts by weight SiO _2: molar ratio of Al ₂ O ₃ and SiO ₂ is 1: ₂ H ₂ O: expressed in 0 to 20 parts by weight It is a white hexagonal inorganic powder substance.

The hexagonal plate-shaped zeolite particle material of the present invention is
The composition in which the alkali source, the alumina source, and the silica source in the reaction starting materials are represented as oxides is K ₂ O: 7 to 12 parts by weight Al ₂ O ₃ + SiO ₂ : 5 to 15 parts by weight SiO ₂ : Al ₂ O ₃ The starting material having a molar ratio of SiO ₂ and SiO ₂ of 1: 2 is mixed in an aqueous solution with stirring while being gelled, and the resulting suspension is heated to produce a production method.

Examples of the alkali source of the present invention include potassium hydroxide, potassium carbonate, potassium hydrogen carbonate and the like. The above alkali sources can be used alone or in combination of two or more.

Any alumina source may be used as long as aluminum ions and aluminate ions can be obtained, and examples thereof include aluminum hydroxide and aluminum salts or aluminates with various inorganic acids, such as aluminum chloride and aluminum nitrate. Aluminum sulfate or the like can be used. These salts can be used alone or in combination.

Although various silicates can be used as the silica source, water glass and silica sol are preferred in the present invention.

When the starting material of the present invention is stirred and mixed while gelling, the temperature range of the reaction does not exceed 60 ° C., preferably room temperature to 40 ° C. The reaction time varies depending on the composition of the raw materials used and the like, but is usually 2 to 24 hours, preferably 6 to 12 hours.

The heating of the suspension in the next step can be carried out by putting the suspension obtained in the above reaction in a reaction vessel equipped with a reflux condenser and a stirrer. Heating the suspension is
Although it depends on the composition of the raw materials used, etc., usually 60 to
It is carried out in a suitable temperature range between 120 ° C., but especially 80-1
A temperature range of 10 ° C. is preferred. The time for heating the suspension varies depending on the reaction conditions such as temperature and volume, but is 6 to
It is 240 hours, preferably 24-72 hours.

The object of the present invention can be obtained by subjecting the above reaction product to filtration, washing with water and drying according to a conventional method. Washing with water at the time of separating the reaction product by filtration is carried out until the pH of the washing liquid becomes 10 or less.

The equilibrium water content of the solid substance obtained by filtration is
It is in the range of 10 to 20 parts by weight, but depending on the drying conditions,
It is possible to set the water content to 0 to 20 parts by weight, and the hexagonal plate-like shape is maintained even under these conditions. The drying temperature is
Although it depends on the water content of the dried product, it can be carried out in a temperature range of usually 50 to 200 ° C., preferably 60 to 120.
℃. The drying time depends on the drying temperature, etc.
Usually, it is 1 to 24 hours.

The physicochemical properties of the inorganic powder substance obtained by the production method of the present invention are determined according to a conventional method, for example, the chemical composition is determined by an atomic absorption method, and the water content is measured by an ignition loss. The ignition loss (igloss) was obtained by taking 1 g of the sample and measuring the weight loss when the sample reached a constant weight at 500 ° C. The powder X-ray diffraction spectrum was measured by powder X-ray diffraction (XR).
D; manufactured by Rigaku Denki Co., Ltd.).

Aspect ratio (ratio between projected area diameter and thickness)
Was determined by taking an electron microscope photograph with a scanning electron microscope and measuring the hexagonal plate-shaped particle image in the photograph using a scale.

The specific surface area is E. The density was measured by the T multipoint method, and the density was measured according to JIS K 6220.6.8.

Since the particulate material of the present invention has a unique shape of hexagonal plate-like crystals and a large aspect ratio of 10 to 30 as compared with the conventional zeolite particulate material, it is extremely advantageous when used as a reinforcing agent for plastics and the like. Is. Further, since the particulate matter can be produced with high purity and efficiency, it is industrially advantageous.

Further, the particulate matter of the present invention has the characteristic properties of conventionally known zeolites, namely, the ion exchange function, the adsorption / molecular sieving function and the catalytic function, so that petroleum refining, oxygen production, hydrogen For refining, drying process, radioactive waste treatment, detergent builder, soil modifier, feed additive, solar heat refrigeration system, etc., and improving the thermal stability of polyvinyl chloride resin as a resin additive, resistance of polyolefin resin film. It can also be used as a blocking property improver.

Further, cosmetic bases, abrasives, pharmaceuticals, agricultural chemicals,
It is extremely useful because it can be used as a carrier for supporting a fragrance, a fragrance or the like, or as a carrier for various chromatographies. The invention is explained in more detail in the following examples.

[0020]

【Example】

Example 1 Potassium hydroxide (KOH: 95%) in 240 ml of distilled water
Dissolve 48.84 g and add aluminum hydroxide (Al
₂ O ₃ : 65%) (18.83 g) is added to make a suspension. With further stirring, colloidal silica (SiO ₂ : 20%,
Catalyst Kasei Kogyo Co., Ltd .: trade name Cataloid) 72.13 g
Is gradually added dropwise. The resulting suspension at 30 ° C. for 6 hours,
After thorough stirring, a uniform suspension was obtained. When the composition of the mixture at the start of this reaction was expressed as an oxide, K ₂ O was 10.28 parts by weight, Al ₂ O _{3 was} 3.22 parts by weight, and SiO ₂ was 3.80 parts by weight. Then, this suspension was transferred to a reaction vessel equipped with a reflux condenser and a stirrer, and heated at 100 ° C. for 24 hours to be crystallized.

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 yield at this time was 99% or more, and the alumina source and silica source as starting materials could all be recovered as products.
The results of instrumental analysis of the inorganic powder substance obtained by the above synthesis method are shown in Table 1 below.

The result of the powder X-ray diffraction spectrum of the inorganic powder substance was as shown in FIG. From the pattern of this powder X-ray diffraction spectrum, it was confirmed that the above product was a high-purity K-type zeolite. Moreover, it was possible to confirm that the above-mentioned inorganic powder substance was a hexagonal plate-like substance by an electron micrograph (magnification: 10000 times).

Example 2 The same suspension as that used in Example 1 was transferred to a reaction vessel equipped with a reflux condenser and a stirrer, and heated at 80 ° C. for 72 hours to be crystallized. Then, a post-treatment was carried out in the same manner as in Example 1 to obtain a white inorganic powder substance. From the pattern of the powder X-ray diffraction spectrum, it was confirmed that the inorganic powder substance was high-purity K-type zeolite, and it was confirmed from the electron micrograph that it was a hexagonal plate crystal.

Example 3 According to the production method described in Example 1, the composition of the starting materials was as follows: K ₂ O = 12.0 parts by weight, Al ₂ O ₃ = 6.05 parts by weight,
A reaction was performed in the same manner as in Example 1 except that the amount of SiO ₂ was changed to 7.15 parts by weight to obtain a white inorganic powder substance. From the pattern of the powder X-ray diffraction spectrum, it was confirmed that the inorganic powder substance was high-purity K-type zeolite, and it was confirmed from the electron micrograph that it was a hexagonal plate crystal.

[0025]

[Table 1]

[0026]

According to the present invention, a novel hexagonal plate-like zeolite particle material and a specific hexagonal plate-like crystal having a large aspect ratio of 10 to 30 as compared with the conventional zeolite particle material and the particle material thereof are provided. It has been possible to provide a manufacturing method that can be manufactured efficiently and with good purity in a short time. Since the particulate material of the present invention has the above-mentioned excellent properties, it is extremely advantageous when used as a reinforcing agent for plastics and the like.

[Brief description of drawings]

FIG. 1 is a powder X-ray diffraction spectrum of a hexagonal plate K-type zeolite particle material obtained in Example 1 of the present invention.

Claims (4)

[Claims] 1. A composition in which an alkali source, an alumina source, and a silica source in a reaction starting material are expressed as oxides K ₂ O: 7 to 12 parts by weight Al ₂ O ₃ + SiO ₂ : 5 to 15 parts by weight SiO ₂ : Al ₂ O ₃ and SiO ₂ molar ratio is 1: 2 Hexagonal plate-like zeolite particles characterized in that the starting material is stirred and mixed in an aqueous solution while being gelled, and the resulting suspension is heated The method of manufacturing a substance. 2. The method for producing a hexagonal plate-like zeolite particle material according to claim 1, wherein the heating temperature is in the range of 60 to 120 ° C. 3. A composition formula K ₂ O: 20 to 30 parts by weight Al ₂ O ₃ : 20 to 30 parts by weight SiO ₂ : Al ₂ O ₃ and SiO _{2 have} a molar ratio of 1: 2 H ₂ O: 0 to 20. Hexagonal tabular zeolite particle material expressed in parts by weight. 4. The hexagonal plate-like zeolite particle material according to claim 3, wherein the aspect ratio is in the range of 10 to 30.