KR102549945B1 - Manaufacturing method for zeolite for potassium fertilizer - Google Patents

Abstract

The present invention relates to a method for producing zeolite for potassium fertilizer. In one embodiment, the manufacturing method of the zeolite for potassium fertilizer includes the steps of firstly treating the zeolite with an ammonium compound; Heating the primary treated zeolite; Secondary treatment of the heated zeolite with an aqueous solution of potassium hydroxide; Forming a coating layer by applying a coating agent containing 100 parts by weight of a silicic acid-based binder, 5 to 40 parts by weight of a viscosity modifier, and 1 to 10 parts by weight of germanium oxide on the surface of the secondary treated zeolite; and heat-treating the zeolite on which the coating layer is formed.

Description

Manufacturing method of zeolite for potassium fertilizer {MANAUFACTURING METHOD FOR ZEOLITE FOR POTASSIUM FERTILIZER}

The present invention relates to a method for producing zeolite for potassium fertilizer.

For the growth of plants, carbon is absorbed in the form of carbon dioxide in the air, hydrogen and oxygen are absorbed in the form of water through the roots of plants, and other forms of inorganic salts or inorganic ions are absorbed from the soil.

On the other hand, in the process of harvesting plants such as crops from the soil every year, the soil becomes short of nutrients and must be supplied artificially. Therefore, fertilizers (fertilizer) should be sprayed on the soil so that plants such as crops can grow well and increase productivity.

In particular, since a large amount of nitrogen, phosphorus, and potassium are required for plant growth, the soil tends to lack these nutrients, so an appropriate type of fertilizer should be supplied to the soil. These types of fertilizers include subsistence fertilizers, organic fertilizers, nitrogen fertilizers, phosphate fertilizers, potash fertilizers, and compound fertilizers.

Among them, potassium fertilizer is advantageous for plant growth and root development. Conventionally, as a potassium source, ashes from burned plants or natural minerals containing potassium were used, and chemically, potassium chloride or potassium sulfate was supplied. However, chemically prepared potassium chloride and potassium sulfate fertilizers have a problem in soil acidification during long-term fertilization. In addition, in the prior art, potassium was supported on natural bentonite, zeolite or diatomaceous earth to prepare and use fertilizer.

Natural zeolites are used as soil improvers for agriculture. Since the zeolite is composed of a porous clay mineral having a large cation exchange capacity, it has effects of increasing retention capacity, adsorbing harmful components and supplying special components, thereby increasing productivity by increasing the effect of preventing nutrient leaching.

About 40 or more types of such natural zeolites have been discovered, but mordenite, clinoptilolite, and the like are known as zeolites mainly found in Korea.

However, since all zeolites such as mordenite and crinoptirolite contain a large amount of sodium (Na), when applied to soil for a long time, there is a concern about side effects on plants due to excessive sodium (Na). When potassium (K) ions are supported on zeolite with high purity, the sodium (Na) ions supported on the natural zeolite described above become an obstacle. ) ions remain, and the sodium (Na) ions remaining in this way tend to alkalize the soil excessively when a certain amount or more of the zeolite made in this way is applied to the soil due to the common ion effect with potassium (K) ions.

Background art related to the present invention is disclosed in Republic of Korea Patent Registration No. 10-1992526 (2019.10.01. Announcement, title of the invention: organic slow-acting fertilizer using psyllium hull and manufacturing method thereof).

One object of the present invention is to provide a method for producing zeolite for potassium fertilizer, which is excellent in improving soil fertility, preventing soil acidification, and preventing sodium accumulation.

Another object of the present invention is to provide a method for producing zeolite for potash fertilizer with excellent plant growth promoting effect and crop yield increasing effect.

Another object of the present invention is to provide a method for producing zeolite for potash fertilizer with excellent soil fertility improvement effect.

Another object of the present invention is to provide a method for producing a zeolite for potassium fertilizer having excellent durability of the coating layer and bonding strength between the coating layer and the zeolite.

One aspect of the present invention relates to a method for producing a zeolite for potassium fertilizer. In one embodiment, the manufacturing method of the zeolite for potassium fertilizer includes the steps of firstly treating the zeolite with an ammonium compound; Heating the primary treated zeolite; Secondary treatment of the heated zeolite with an aqueous solution of potassium hydroxide; Forming a coating layer by applying a coating agent containing 100 parts by weight of a silicic acid-based binder, 5 to 40 parts by weight of a viscosity modifier, and 1 to 10 parts by weight of germanium oxide on the surface of the secondary treated zeolite; and heat-treating the zeolite on which the coating layer is formed.

In one embodiment, the zeolite may include at least one of mordenite and clinoptilolite.

In one embodiment, the zeolite may have an average size of 0.05 to 5 mm.

In one embodiment, the heat treatment may be performed at 120 to 250 °C.

Prior to the step of forming the coating layer in one embodiment, the step of heating the secondary treated zeolite at 120 ~ 650 ℃; may further include.

The method for producing zeolite for potassium fertilizer according to the present invention and the zeolite for potassium fertilizer produced thereby are excellent in the effect of improving soil fertility, buffering soil pH, preventing sodium accumulation and preventing acidification, and exhibiting excellent plant growth promoting effect And, the effect of improving the fertility of the soil is excellent, and the durability of the coating layer formed on the zeolite for potassium fertilizer and the bonding strength between the coating layer and the zeolite may be excellent.

1 shows a method for producing a zeolite for potassium fertilizer according to one embodiment of the present invention.

In describing the present invention, if it is determined that a detailed description of a related known technology or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted.

In addition, the terms to be described below are terms defined in consideration of functions in the present invention, which may vary according to the intention or custom of the user or operator, so the definitions should be made based on the content throughout this specification describing the present invention.

Manufacturing method of zeolite for potassium fertilizer

One aspect of the present invention relates to a method for producing a zeolite for potassium fertilizer. 1 shows a method for producing a zeolite for potassium fertilizer according to one embodiment of the present invention. Referring to FIG. 1, the method for producing zeolite for potassium fertilizer includes (S10) a primary treatment step; (S20) heating step; (S30) a second processing step; (S40) coating layer forming step; and (S50) heat treatment step.

More specifically, a method for producing a zeolite for sexual potash fertilizer includes (S10) firstly treating the zeolite with an ammonium compound; (S20) heating the primary treated zeolite; (S30) secondarily treating the heated zeolite with an aqueous solution of potassium hydroxide; (S40) forming a coating layer by applying a coating agent containing 100 parts by weight of a silicic acid-based binder, 5 to 40 parts by weight of a viscosity modifier, and 1 to 5 parts by weight of germanium oxide on the surface of the secondary treated zeolite; and (S50) heat-treating the zeolite on which the coating layer is formed.

Hereinafter, a method for preparing a zeolite for potassium fertilizer according to the present invention will be described in detail step by step.

(S10) 1st processing step

This step is a step of first treating the zeolite with an ammonium compound.

In one embodiment, the first treatment step is to remove sodium (Na) ions supported on natural zeolite by contacting (mixing) the zeolite and an ammonium compound containing ammonium ions having a greater ionization tendency than sodium. It may be a step of replacing sodium ions with ammonium ions.

In one embodiment, the ammonium compound may include at least one of an ammonium salt and an ammonium ion (NH ₄ ⁺ ). For example, the ammonium compound may include at least one of ammonium chloride (NH ₄ Cl) and ammonium sulfate ((NH ₄ ) ₂ SO ₄ ) aqueous solution.

The zeolite may include natural zeolite. For example, the zeolite may include at least one of mordenite and clinoptilolite.

In one embodiment, the zeolite is porous, and may have an average pore size of 0.5 nm to 1 μm and a specific surface area of 150 to 1000 m ² /g. Under the above conditions, the effect of increasing the fertility of the zeolite for potassium fertilizer of the present invention, adsorbing harmful components, and transferring useful components to crops may be excellent.

In one embodiment, the zeolite may have a cation exchange capacity (CEC) of 80 to 200 meq/100g. Under the above conditions, the effect of increasing the fertility of the zeolite for potassium fertilizer of the present invention, adsorbing harmful components, and transferring useful components to crops may be excellent.

In one embodiment, the zeolite may have an average size of 0.05 to 5 mm. The average size may be the particle diameter or maximum length of the zeolite. Productivity and workability may be excellent under the condition of the average size of the zeolite. For example, zeolite having the above average size condition may be used by pulverizing natural zeolite and then screening and separating using a sieve.

(S20) Heating step

This step is a step of heating the zeolite that has been subjected to the primary treatment. In this step, by heating the zeolite substituted with ammonium ions, hydrogen ions (H ⁺ ) may be supported on the zeolite.

In one embodiment, the heating may be performed at 550 to 750 °C. When heated in the above range, the hydrogen ions can be easily supported.

(S30) 2nd processing step

This step is a step of secondarily treating the heated zeolite with an aqueous solution of potassium hydroxide (KOH). In this step, the hydrogen ions are replaced with potassium ions (K ⁺ ) by contacting and treating the hydrogen ion-supported zeolite with an aqueous solution in which potassium hydroxide is dissolved.

In one embodiment, the potassium hydroxide may be treated in contact with 1 to 15 parts by weight based on 100 parts by weight of the zeolite. During the secondary treatment under the above conditions, hydrogen ions in the zeolite can be easily replaced with potassium ions.

In one embodiment, the potassium hydroxide aqueous solution may be prepared by mixing 100 parts by weight of a solvent and 1 to 15 parts by weight of potassium hydroxide. Under these conditions, reactivity with the zeolite may be excellent. In one embodiment, the solvent may include water.

In one embodiment, before performing the coating layer forming step (S50), the step of heating the secondary treated zeolite at 120 ~ 650 ℃ may be further included. When heated under the above conditions, water and volatile components of the zeolite can be easily volatilized and removed, thereby improving the purity of potassium in the zeolite.

(S40) coating layer formation step

The step is a step of forming a coating layer by applying a coating agent containing 100 parts by weight of a silicic acid-based binder, 5 to 40 parts by weight of a viscosity modifier, and 1 to 5 parts by weight of germanium oxide on the surface of the secondarily treated zeolite.

In one embodiment, the coating agent may penetrate the surface and pores of the zeolite to form a coating layer.

The silicic acid-based binder may be included to secure mechanical strength and adhesion of the coating agent. In one embodiment, the silicic acid-based binder may include potassium silicate (K ₂ SiO ₃ ). When the potassium silicate is included, the mechanical strength of the coating layer and the adhesion between zeolites are excellent, and the effect of supplying silicon (Si) and potassium (K) components to the soil may be excellent.

The viscosity modifier may be included for the purpose of securing workability by adjusting the viscosity of the coating agent. In one embodiment, the viscosity modifier may include at least one of starch, cellulose, guar gum, and polyvinyl alcohol. The starch may include at least one of wheat starch and corn starch.

In one embodiment, the cellulose may include at least one of methyl cellulose, ethyl cellulose, carboxy methyl cellulose, and carboxy ethyl cellulose.

In one embodiment, the viscosity modifier may be included in an amount of 5 to 40 parts by weight based on 100 parts by weight of the silicic acid-based binder. When the viscosity modifier is included in an amount of less than 5 parts by weight, the viscosity control effect is insignificant and workability is deteriorated, and when included in an amount exceeding 40 parts by weight, the workability may be rather deteriorated.

The germanium oxide (GeO ₂ ) may be included to improve adhesion between the coating layer and the zeolite while supplying nutrients to plants such as crops.

In one embodiment, the germanium oxide is included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the silicic acid-based binder. When the germanium oxide is included in an amount of less than 1 part by weight, the adhesion between the coating layer and the zeolite is reduced, and the plant growth effect is insignificant. this may increase

In one embodiment, the coating agent may further include 0.1 to 1 part by weight of molybdenum oxide (MoO ₂ ) based on 100 parts by weight of the silicic acid-based binder. When included in the above weight range, the durability and adhesion of the coating layer are excellent, and the plant growth effect can be further improved.

In one embodiment, the germanium oxide and molybdenum oxide may be included in a weight ratio of 3:1 to 8:1. When included in the weight ratio range, the durability and adhesion of the coating layer are excellent, and the plant growth effect can be further improved.

In one embodiment, the coating agent may further include a solvent. For example, the solvent may include one or more of water, ethanol, methanol, butanol, isobutanol, and isopropyl alcohol. In one embodiment, the solvent may be included in an amount of 50 to 300 parts by weight based on 100 parts by weight of the silicic acid-based binder. When included in the above content range, mixing and dispersibility of the components of the coating agent may be excellent, and workability may be excellent when applying the coating agent.

In one embodiment, the zeolite and the coating agent may be included in a weight ratio of 1:0.1 to 1:3. While the durability of the coating layer is excellent under the above conditions, the potassium component supported on the zeolite can be easily eluted when fertilizing the soil.

(S50) heat treatment step

This step is a step of heat-treating the zeolite on which the coating layer is formed.

The heat treatment is performed to improve the bonding force between the zeolite and the coating layer while curing the formed coating layer.

In one embodiment, the heat treatment may be performed at 120 to 250 °C. When heat-treated under the above conditions, durability of the coating layer and bonding strength between the zeolite and the coating layer may be excellent.

Zeolite for potassium fertilizer prepared by the method for producing zeolite for potassium fertilizer

Another object of the present invention relates to a zeolite for potassium fertilizer prepared by the method for producing a zeolite for potassium fertilizer.

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this is presented as a preferred example of the present invention and cannot be construed as limiting the present invention by this in any sense. Contents not described herein can be technically inferred by those skilled in the art, so descriptions thereof will be omitted.

Examples and Comparative Examples

Example 1

Natural zeolite (crinoptilolite) having a cation exchange capacity (CEC) of 100 to 150 meq/100 g was pulverized to an average size of 0.1 to 1 mm to prepare a pulverized product. Then, the pulverized product was first treated by contacting an ammonium compound (including an ammonium salt) to replace sodium ions contained in natural zeolite with ammonium ions. Then, the zeolite subjected to the primary treatment was heated at 550 to 750° C. to support hydrogen ions on the zeolite.

In addition, 100 parts by weight of the heated zeolite was added to 100 parts by weight of a potassium hydroxide (KOH) aqueous solution (including 3.9% by weight of potassium hydroxide), and stirred for 1 hour at room temperature (15 to 35 ° C.) to perform secondary treatment, and the zeolite The hydrogen ion of was replaced with a potassium ion. In addition, the secondly treated zeolite was heated in a temperature range of 120 to 650 ° C. to remove moisture to increase the purity of potassium ions. Then, 100 parts by weight of a silicic acid-based binder (potassium silicate), 30 parts by weight of a viscosity modifier (carboxymethylcellulose), 3 parts by weight of germanium oxide, 0.5 parts by weight of molybdenum oxide, and 100 parts by weight of a solvent (water) are included on the surface of the zeolite. A coating layer was formed by applying a coating agent (zeolite: coating agent = 1:0.5 to 1:3 weight ratio) and drying. The zeolite on which the coating layer was formed was heat treated at 120 to 250° C. to prepare a spherical zeolite for potassium fertilizer having an average particle diameter of 1 to 5 mm.

Examples 2-3

A zeolite for potassium fertilizer was prepared in the same manner as in Example 1, except that a coating agent containing the ingredients and contents shown in Table 1 was applied.

Comparative Examples 1 to 4

A zeolite for potassium fertilizer was prepared in the same manner as in Example 1, except that a coating agent containing the components and contents shown in Table 1 was applied.

Comparative Example 5

A natural zeolite having a cation exchange capacity (CEC) of 100 to 150 meq/100g was prepared.

Experimental example

(1) Measurement of soil pH change: 50 to 150 kg/10a of the zeolites for potassium fertilizer of Examples 1 to 3 and Comparative Examples 1 to 5 were applied to the acidified soil (pH = 4.5), respectively. After 1 year, the pH of the soil fertilized with the zeolite for potassium fertilizer of Examples 1 to 3 and Comparative Examples 1 to 5 was measured, respectively, and the results are shown in Table 2 below. In addition, whether or not the coating layer formed on the surface of the zeolite for potassium fertilizer of Examples 1 to 3 and Comparative Examples 1 to 4 was confirmed with an optical microscope, it was determined to be good or bad, and the results are shown in Table 2.

Referring to the results of Table 2, it was found that Examples 1 to 3 according to the present invention had an excellent effect of improving alkaline soil of acidified soil compared to Comparative Examples 1 to 5. In addition, it was found that the comparative examples out of the range of the coating agent content of the present invention were easily separated due to poor adhesion of the coating layer compared to Examples 1 to 3.

(2) Crop cultivation test (turf): A lawn cultivation test was conducted in a conventional manner using Examples and Comparative Examples. Specifically, after fertilizing 50 to 150 kg/10a of zeolite for potassium fertilizer of Examples 1 to 3 and Comparative Examples 1 to 5, soil 3 months had elapsed was collected and mixed with rice hull to prepare cultured soil. 100 wild grass ( zoysia japonica ) seeds were sowed and cultivated in the culture soil using the above Examples and Comparative Examples, respectively, and then the complex fertilizer was sprayed at intervals of 15 days and cultivated in the usual way for 6 months. Next, with respect to the turfgrass grown using the above examples and comparative examples, plant height and weight were measured and average values were calculated, respectively, and the results are shown in Table 3 below.

Referring to the results of Table 3, it was found that the turfgrass cultivated using Examples 1 to 3 had an excellent growth promoting effect than Comparative Examples 1 to 5.

So far, the present invention has been looked at mainly through embodiments. Those skilled in the art to which the present invention pertains will be able to understand that the present invention may be implemented in a modified form without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments should be considered from an illustrative rather than a limiting point of view. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the equivalent scope will be construed as being included in the present invention.

Claims (5)

First treating the zeolite with an ammonium compound;
Heating the primary treated zeolite;
Secondary treatment of the heated zeolite with an aqueous solution of potassium hydroxide;
Heating the secondary treated zeolite at 120 to 650 ° C;
Forming a coating layer by applying a coating agent containing 100 parts by weight of a silicic acid binder, 5 to 40 parts by weight of a viscosity modifier, 0.5 to 1 part by weight of molybdenum oxide, and 1.5 to 8 parts by weight of germanium oxide on the surface of the secondary treated zeolite; and
It is a method for producing zeolite for potassium fertilizer comprising; heat-treating the zeolite on which the coating layer is formed at 120 to 250 ° C.
The method for producing a zeolite for potassium fertilizer, characterized in that the molybdenum oxide and germanium oxide are included in a weight ratio of 1: 3 to 1: 8.
The method of claim 1, wherein the zeolite comprises at least one of mordenite and clinoptilolite.
The method of claim 1, wherein the zeolite has an average size of 0.05 to 5 mm.
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