JP3077740U - Granular zeolite-based soil conditioner starting from waste containing a silicic acid component and / or an aluminum component - Google Patents

Abstract

(57) [Problem] To provide a granular soil conditioner using waste containing a silicic acid component and / or an aluminum component. SOLUTION: A waste product containing a silicic acid component and / or an aluminum component is used as a starting material, and a reaction product obtained by mixing with an aqueous alkali solution and performing hydrothermal synthesis at a predetermined silane ratio is subjected to cation substitution. What was kneaded with a molding material and water, molded into granules with a granulator and heated and dried, or
A reaction product obtained by mixing a reaction product obtained by mixing a waste product containing a silicic acid component and / or an aluminum component with an aqueous alkali solution and performing hydrothermal synthesis at a predetermined silane ratio, and a molding material The mixture obtained by kneading the mixture with water and a shirasu balloon and water is formed into granules by a granulator and dried by heating.

Description

[Detailed description of the invention]

[0001]

[Technical field to which the invention belongs]

 The present invention relates to a reaction product obtained by mixing a waste containing a silicic acid component and / or an aluminum component with an aqueous alkali solution and subjecting the reaction product obtained by hydrothermal synthesis to a predetermined silane ratio to cation substitution. The present invention relates to a granular zeolite-based soil improver obtained by kneading a molding material and water or a mixture of the reaction product, the molding material, a shirasu balloon, and water into a predetermined granule by a granulator, and drying by heating. .

[0002]

[Prior art]

 BACKGROUND ART Conventionally, waste containing a silicate component and / or an aluminum component has been reprocessed and used as a raw material, or mixed with cement or the like for use. In recent years, it has been known that cation exchangeable substances are synthesized from the above wastes and used as soil improvement materials. Examples of soil improvement materials include bentonite, natural zeolite, and organic compost. Etc. are used.

[0003]

[Problems to be solved by the invention]

 However, conventional soil conditioners have a low ability to retain cations, so the cations necessary for plant growth are washed away by infiltration water such as rainwater, so that fertilizer retention is low and acidification of the soil is difficult. However, there were problems such as the weak effect of suppressing water, the inability to improve water permeability, and the high price.

[0004]

[Means for Solving the Problems]

 In view of the above-mentioned conventional problems, the present invention is obtained by mixing a waste containing a silicate component and / or an aluminum component with an aqueous alkali solution and performing hydrothermal synthesis at a predetermined sulphone ratio. A cation-exchanged reaction product, a molding material and water are kneaded, formed into predetermined granules by a granulator, and then heated and dried, or a zeolite-based soil conditioner, or a silicate component and / or an aluminum component. Is mixed with an aqueous alkali solution, and the reaction product obtained by performing hydrothermal synthesis at a predetermined silane ratio, the cation-substituted product, a molding material, a shirasu balloon, and water are kneaded. Another object of the present invention is to provide a zeolite-based soil conditioner which has been formed into predetermined granules by a granulator and then dried by heating. When granulation is performed using the above-mentioned shirasu balloon, the granular material can have a porous structure. Further, by making the particle size of a spherical particle having a diameter of 2.3 to 10 mm, it can be used as a substitute for sand, pebbles and the like.

[0005]

[Embodiment of the invention]

 Hereinafter, embodiments of the present invention will be described.

The zeolite-based soil conditioner described in the present invention is obtained by mixing a waste containing a silicate component and / or an aluminum component as a starting material, mixing with an aqueous alkali solution, and performing hydrothermal synthesis at a predetermined silicate ratio. The reaction product obtained by cation substitution of the obtained reaction product, a molding material and water are kneaded, formed into granules by a granulator, and then heat-dried or discarded containing a silicate component and / or an aluminum component. Cation-substituted reaction product obtained by mixing the product with the aqueous alkali solution and performing hydrothermal synthesis at a predetermined slag ratio, and kneading the molding material, shirasu balloon and water Is formed into granules by a granulator and then dried by heating.

The waste containing a silicate component and / or an aluminum component refers to industrial waste such as alkaline waste liquid or waste glass mainly containing a silicate component, and industrial waste mainly containing an aluminum component. Industrial waste and natural waste that mainly contain a silicate component and an aluminum component. Industrial waste that mainly contains a silicate component includes rice, wheat, and other grasses. Examples include rice husks, plants and diatomaceous earth.

[0008] The above grasses are a family of monocotyledonous plants, and are all herbs except bamboo. Grains such as rice, wheat, corn, millet, leeks, oats, etc. all belong to this family and are important agricultural groups. It is widely distributed as weeds, such as Japanese pampas grass and Japanese cypress, and there are more than 10,000 species of 600 genera. An amorphous silica is contained in a seed shell or a plant body of a solanaceous plant, and the content ratio is particularly large in a seed shell. The amorphous silica has a high reaction activity and can elute the silicate component into the alkaline aqueous solution by mixing with a strong alkaline aqueous solution and heating.

[0009] The diatomaceous earth is a diatom remains, most of which are unicellular algae, that is, siliceous sediments made of diatom shells, and usually contains clay, volcanic ash, organic matter, and the like. Wherein the essence is hydrous amorphous silicon dioxide. Diatomaceous earth is widely used for adsorbents, filtration aids, heat insulators, cold insulators, fillers, abrasives, etc.In some applications, diatomaceous earth is crushed to make it suitable for the intended use. Purification is common.

The cullet of the waste glass mentioned above refers to a cullet of silicate glass, and cullets such as silicate glass, soda-lime glass, potassium lime glass, lead glass, barium glass, and borosilicate glass are exemplified. be able to.

[0011] The industrial waste mainly containing the aluminum component refers to an alkaline waste liquid of aluminum waste, aluminum dross, and the like. The above-mentioned alkaline waste liquid refers to a solution obtained by dissolving aluminum scraps discharged in an aluminum product manufacturing process in an alkaline solution, an alkaline washing waste solution of an aluminum mold, or a solution obtained by dissolving aluminum sludge during alumite production in an alkaline aqueous solution. Waste water generated when washing the formwork for manufacturing aluminum products such as aluminum sashes, bearings, valves, precision tools, valves, wires and plates, etc., and alkali sludge from aluminum sludge during the production of alumite. Can be exemplified. In addition, the aluminum dross is one in which aluminum oxide generated in the aluminum dissolving step is entangled with metallic aluminum to form dross and covers the surface of the molten aluminum.

[0012] The waste containing the silicic acid component and the aluminum component refers to natural waste and industrial waste containing both of the above components. It refers to volcanic eruption products, volcanic glass, etc., and industrial waste refers to incinerated ash, sludge, etc. Examples of incinerated ash include fly ash, clinker ash, etc., coal ash, and foundry sand. And incinerated ash of combustible waste such as municipal waste and sludge, and incinerated ash of solidified fuel.

The above-mentioned aqueous alkali solution is a hydroxide of an alkali metal which is soluble in water, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, lithium hydroxide and the like. It is preferable to use an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide. It is possible to carry out the reaction at an alkali concentration of 0.5 to 4.5 N during the reaction. In order to improve efficiency and avoid dissolution of the reaction product, it is preferable to carry out the reaction at an alkali concentration of 2 to 4N. Further, the heating temperature at the time of performing the hydrothermal treatment in the pressure-resistant reaction vessel is preferably higher than 60 ° C, particularly preferably 120 to 230 ° C. The heat treatment can use saturated steam, infrared radiation, microwave heating, and induction heating, and these heat treatments can be combined. On the other hand, if ultrasonic oscillation is added to the reaction vessel during the hydrothermal treatment, the reaction proceeds rapidly, and the ultrasonic frequency at this time is preferably 18 to 500 kHz.

[0014] The sulphide ratio is represented by (a ratio of silicon to aluminum converted to a molecular ratio of SiO ₂ and Al ₂ O ₃ ) × 1.7, and the composition of the zeolite which is the reaction product to be produced is It determines the type of thing. That is, the ash ratio of the volcanic eruption products is about 3-4, and the artificial zeolite obtained by performing the heat treatment with alkali using only the eruptive material is a mixture of philipsite and mordenite. The pore size is 0.4-0.5 nm for philipsite and 0.6-0.7 nm for mordenite, and the cation exchange capacity is approximately 380 cmol (+) kg ^{-1 for} philipsite and approximately mornite for mordenite. It is 300 cmol (+) kg ^-1 and has a deodorizing effect.

The artificial zeolite obtained by performing a heat treatment with alkali using only incinerated ash as a raw material is hydroxysodalite, which has a small pore size and a cation exchange capacity of 480 cmol (+) kg ^{−. It} is as large as ¹ , but has no deodorizing effect. The addition of glass or diatomaceous earth to volcanic fall products or incineration ash increases the diatom ratio, but adding aluminum dross to the fall volcanic products or incineration ash lowers the diatom ratio. For example, by adding 20% by weight or more of glass or diatomaceous earth to the solid content of incinerated ash, the diatom ratio becomes 2 or more, and the proportion of philipsite in the obtained artificial zeolite increases. .

Further, when waste glass or diatomaceous earth is added in an amount of 40 to 50% by weight based on the solid content of the incineration ash, and the silicate ratio is set to 2.5 or more, almost all of the artificial zeolite becomes a Philippine site. Furthermore, when the amount of glass or diatomaceous earth is increased to 60% by weight or more to increase the diatom ratio to 4 or more, the proportion of faujasite in the artificial zeolite increases. On the other hand, the addition of aluminum dross to the incinerated ash lowers the sulphate ratio and increases the production of hydroxysodalite in the artificial zeolite obtained by heat treatment with alkali.

The above-mentioned cation substitution is the substitution of a zeolite composition, which is a reaction product, with a cation. As the cation, NH ₄ ⁺ , K ⁺ , and Ca required for plant growth are used. Each cation such as ²⁺ and Mg ²⁺ can be exemplified. Further, the method of replacing the zeolite composition, which is the reaction product, with a cation is carried out by immersing the zeolite composition in an aqueous solution containing each of the cations and shaking the zeolites in a conventional manner. Done.

Further, the above zeolite composition has a cation exchange capacity of about 300 to 400 cmol (+) kg ⁻¹ and has a large ability to retain cations. When the material is used as a soil conditioner, the aggregate structure of the soil can be formed, so that the water permeability is good, the air permeability becomes active, and the renewal of the soil gas component becomes easy. In addition, it is possible to prevent cations in the soil from flowing out due to infiltration water such as rainwater, and to improve fertilizer holding. Furthermore, the above-mentioned polyvalent cation-substituted zeolite compositions such as Ca ²⁺ and Mg ²⁺ have excellent adsorption capacity, and can cause crop growth impairment and disease development due to accumulation of salts in soil due to excessive fertilization. It has an effect of adsorbing ions and suppressing the above-mentioned obstacles.

The above-mentioned molding material serves as a base when the cation-substituted zeolite composition is mixed and molded, and examples thereof include Portland cement, bentonite, and methylcellulose. Although not adopted in the embodiment of the present invention, a thermoplastic resin such as polyethylene can be used as a molding material.

The above-mentioned shirasu balloon is a balloon-like hollow body obtained by firing and foaming glassy volcaniclastic material (shirasu) widely distributed in southern Kyushu, Tohoku and Hokkaido at around 1000 ° C. Most of the gas generated during foaming is water.

The above-mentioned granular material refers to spherical particles formed in a range of 2.3 to 10.0 mm in diameter, and the cation-substituted zeolite composition, the forming agent and water are mixed in a weight ratio of 4%. : 3: 3, or a cation-substituted zeolite composition, a molding agent, a shirasu balloon and water are mixed at a weight ratio of 4: 2: 1: 3, and the mixture is kneaded and then mixed with a granulator. It was molded and dried by heating at 90 to 140 ° C. Further, when granulation is carried out by mixing a shirasu balloon, the molding material is hardened while the water contained in the shirasu balloon evaporates during heating and drying, so that a porous granular material is obtained. The particle size can be adjusted according to the purpose of use, but in the present invention, the above particle size range is adopted in order to enable the soil conditioner to be used as sand and pebbles. In addition, the soil conditioner of the present invention includes a granular form having no voids because it does not contain shirasu balloons, and a granular form having voids because it contains shirasu balloons.

Hereinafter, embodiments of the present invention will be described with reference to FIGS. 1 and 2. FIG. 1 shows that the cation-substituted zeolite composition of the present invention, a molding agent and water are kneaded at a weight ratio of 4: 3: 3, molded by a granulator, and dried by heating at about 120 ° C. FIG. 2 is an explanatory view showing the shape of a granular soil conditioner, and FIG. 2 shows a mixture of a cation-substituted zeolite composition, a forming agent, a shirasu balloon and water at a mixing ratio (weight ratio) of 4: 2: 1: 3. FIG. 3 is an explanatory diagram showing the shape of a granular soil conditioner obtained by kneading the mixture, forming the mixture with a granulator, and heating and drying at about 120 ° C.

The particle size of the soil conditioner can be adjusted according to the purpose of use. However, in the present invention, the soil conditioner has a diameter of 2.3 in order to have a use as sand or pebbles. It is formed into spherical particles in the range of up to 10.0 mm. The mixing ratio is not limited, and can be changed depending on the type of the molding material, the target particle size, and the like.

In FIG. 1, 1 represents a granular soil conditioner. The granular soil conditioner 1 is a spherical particle formed in a range of 2.3 to 10.0 mm in diameter, and is usually made of Portland cement as a base material 2 and a cation-substituted zeolite is provided inside and outside the base material 2. Composition 3 is present in a dispersed state.

When the cation-substituted zeolite composition 3 present on the surface of the base material 2 is mixed with the soil, the cation-substituted zeolite composition 3 is ion-exchanged with cations in the soil, thereby being useful for the work that has been substituted. Slow release of various cations results in soil with good fertility. In addition, when salt accumulation occurs due to excessive fertilization, excess ions can be adsorbed to suppress an increase in salt concentration in the soil.

In FIG. 2, reference numeral 4 denotes a granular soil conditioner produced by mixing a shirasu balloon. The granular soil conditioner 4 is also a spherical particle having a diameter of 2.3 to 10.0 mm similarly to the above-mentioned granular soil conditioner 1, and is usually made of Portland cement as a base material 5. The ion-substituted zeolite composition 6 and the shirasu balloon 7 having voids are present in a dispersed state. The soil conditioner having pores shown in FIG. 2 has the same effect as the soil conditioner shown in FIG. 1, but the specific surface area is increased due to the presence of the pores in the base material 5 and the soil conditioner is not included in the soil. When mixed, the frequency of contact between the cation-substituted zeolite composition 6 contained in the base material 5 and the cations present in the soil increases, and the cation-substituted zeolite composition 6 becomes more positive than the soil conditioner shown in FIG. The sustained release of ions is facilitated, and the salt cations accumulated due to excessive fertilization can be further adsorbed. In addition, the pores are effective for improving the colonization of microorganisms that improve the condition of the soil.

Next, an embodiment of the present invention will be described, but the present invention is not limited to this embodiment.

【Example】

(Example 1) 20 g and 4N of fly ash having a non-crystalline aluminum silicate content of 95% and a silicate ratio of about 2.5 (obtained from Matsuura Power Station Co., Ltd., Fly Ash Association) After 200 ml of an aqueous sodium hydroxide solution was placed in the pressure-resistant reaction vessel and the lid was closed, the mixture was heated until the internal temperature reached 120 ° C. while oscillating 25 kHz ultrasonic waves at 600 W. After maintaining this state for 3 hours, the steam was evacuated and returned to atmospheric pressure, and the internal reaction product was taken out. The structure was confirmed by X-ray diffraction without washing the reaction product with water. As a result, it was confirmed that a zeolite composition mainly composed of philipsite was formed to the depth of the pores. The cation exchange capacity of this zeolite composition was 350 cmol (+) kg ^-1 . Next, 500 g of the above zeolite composition was washed with water and air-dried, placed in 1,000 ml of a 0.5 mol aqueous calcium chloride solution, and shaken with a reciprocating shaker for 2 hours.

This treatment was repeated five times to saturate with calcium ions, and excess salts were washed off with water by centrifugation and dried at 150 ° C. to obtain a calcium-substituted artificial zeolite composition. Next, a mixture of the above calcium-substituted zeolite composition, ordinary portland cement and water at a weight ratio of 4: 3: 3, and a calcium-substituted zeolite composition, portland cement, shirasu balloon and water were mixed. A mixture prepared by mixing at a weight ratio of 4: 2: 1: 3 was prepared. Each of the above-mentioned mixtures was separately kneaded, molded by a granulator, and dried by heating at about 100 ° C. for 3 hours. A 2.3 mm calcium-substituted soil conditioner having no pores and a calcium-substituted soil conditioner having pores were obtained.

Example 2 An ultrasonic transmitter (MODEL US-600T, manufactured by Nippon Seiki Seisaku-sho, Ltd.) was installed in a 1-liter autoclave with a stirrer (manufactured by Toyo Koatsu Co., Ltd.). 20 g of rice husk incineration ash and 20 g of aluminum chloride crystal powder obtained from the Kyun Yangon thermal power plant (using rice hulls as fuel) in Myanmar with a content of reactive silica of 93% and an alumina content of 0.1% 200ml of 3N potassium hydroxide aqueous solution was poured from above, the lid was closed, and then pressurized with saturated vapor pressure while transmitting 25kHz ultrasonic wave at 600W, and the internal temperature became 120 °. Heated until C was reached.

After maintaining this state for 3 hours, the vapor was evacuated and returned to the atmospheric pressure, and the internal reaction products were taken out. The reaction product was washed with water, air-dried, and the crystal structure was confirmed by X-ray diffraction. As a result, it was confirmed that a zeolite composition mainly composed of philipsite was formed to the depth of the pores. The cation exchange capacity of this zeolite composition was 410 cmol (+) kg ^-1 . Next, 500 g of the above zeolite composition was washed with water and air-dried, placed in 1000 ml of a 0.5M magnesium chloride aqueous solution, and shaken with a reciprocating shaker for 2 hours.

This treatment was repeated five times to saturate with magnesium ions, and the excess salt was washed off with water by centrifugation and then dried at 150 ° C. to obtain a magnesium-substituted artificial zeolite composition. Next, a mixture of the magnesium-substituted zeolite composition, bentonite, and water at a weight ratio of 4: 3: 3, and a magnesium-substituted zeolite composition, bentonite, shirasu balloon, and water were used in a weight ratio. And a mixture of 4: 2: 1: 3 was prepared, and the above-mentioned mixtures were separately kneaded, molded by a granulator, and dried by heating at about 100 ° C. for 3 hours. A magnesium-substituted soil improver having no pores of 0 mm and a magnesium-substituted granular soil improver having pores were obtained.

Example 3 Alkaline concentration of about 6 N (aqueous sodium hydroxide solution), aluminum concentration of about 10 g / liter, 20 liters of waste liquid of an aluminum sash form, and 1.8 kg of water glass were mixed together (aluminum ratio: about 3). Using a pressure-resistant reaction vessel having a concentration (aqueous sodium hydroxide solution) of 4.5 N, the pressure-resistant reaction vessel was heated at a reaction temperature of 120 ° C. for 5 hours while applying ultrasonic oscillation to perform a zeolite reaction. Was.

After completion of the reaction, the dried white reaction product was taken out, and identified by X-ray diffraction. As a result, it was confirmed that the product was a philipsite. The ion exchange capacity of this philipsite was 480 cmol (+) kg ^-1 . Next, 500 g of the above zeolite composition was washed with water and air-dried, placed in 1000 ml of a 0.5 mol aqueous ammonium chloride solution, and shaken with a reciprocating shaker for 2 hours. This treatment was repeated five times to saturate with ammonium ions, and the excess salt was washed off with water by centrifugation and then dried at 150 ° C. to obtain a magnesium-substituted artificial zeolite composition. Next, a mixture of the above-mentioned ammonium ion-substituted zeolite composition, methylcellulose and water at a weight ratio of 4: 3: 3, and a mixture of ammonium ion-substituted zeolite composition, methylcellulose, shirasu balloon and water were prepared. Prepared by mixing at a weight ratio of 4: 2: 1: 3, kneading each of the above mixtures separately, molding with a granulator, and drying by heating at about 100 ° C. for 3 hours. Diameter 10. An ammonium-substituted soil conditioner having no pores of 0 mm and an ammonium ion-substituted soil conditioner having pores were obtained.

[0033]

[Effect of the invention]

 The granular zeolite-based soil conditioner of the present invention starting from waste containing a silicic acid component and / or an aluminum component has a high cation exchange capacity and has an effect of forming the aggregate structure of the soil. By exchanging with cations, cations necessary for the growth of crops are gradually released, so that fertilizer retention is better than that of conventional natural soil conditioners. In addition, since the soil conditioner of the present invention is granular, it is possible to provide the soil with air permeability and water permeability. Living microorganisms settle in the voids of the soil conditioner, allowing various types of microorganisms to coexist, decomposing harmful substances such as crop waste in the soil, and producing useful substances for crops. Therefore, it is possible to create soil suitable for growing crops. It is also possible to use a combination of the above-mentioned various cation-substituted granular zeolite soil conditioners.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing the shape of a soil conditioner of the present invention.

FIG. 2 is an explanatory view showing a shape of a soil conditioner having a void according to the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 granular soil improver 2 base material 3 cation-substituted zeolite composition 4 granular soil improver 5 base material 6 cation-substituted zeolite composition 7 shirasu balloon

Claims (4)

[Utility model registration claims] 1. A reaction product obtained by mixing a waste containing a silicic acid component and / or an aluminum component and an aqueous alkali solution and subjecting the reaction product obtained by performing hydrothermal synthesis at a predetermined silane ratio to a cation. A zeolite starting from a waste containing a silicate component and / or an aluminum component, which is obtained by kneading a molding material and water, forming the granules into predetermined granules with a granulator, and heating and drying the granules. Granular soil conditioner. 2. A reaction product obtained by mixing a waste containing a silicic acid component and / or an aluminum component with an aqueous alkali solution and subjecting the reaction product obtained by hydrothermal synthesis at a predetermined silane ratio to cation substitution. Starting from a waste containing a silicate component and / or an aluminum component, which is kneaded with a molding material, a shirasu balloon, and water, formed into predetermined granules by a granulator, and then heated and dried to obtain granules. A granular zeolite-based soil conditioner used as a substance. 3. The zeolite granular soil improver according to claim 2, wherein the granular material has a porous structure, and the starting material is a waste containing a silicate component and / or an aluminum component. 4. A soil improvement of granular zeolite starting from a waste containing a silicate component and / or an aluminum component according to claim 1, wherein the granular material has a spherical shape with a diameter of 2.3 to 10 mm. Agent.