KR100964749B1 - Compound nano fertilizer of amino acid material using nano-sheet of layered clay minerals and manufacturing method thereof - Google Patents

Abstract

PURPOSE: A nano compound fertilizer is provided to prevent sediment and eduction when adding salt and to ensure high efficiency with improved storage and stability. CONSTITUTION: An amino acid nano compound fertilizer using nano-sheet of layered clay mineral comprises layered clay mineral and amino acid material which is introduced on the surface and layer of clay mineral. The introduced amino acid material separates layer of partial clay mineral by three dimensional structure of the amino acid material and interaction with surface charge of the clay mineral. A method for manufacturing the amino acid nano compound fertilizer using nano-sheet of layered clay mineral comprises: a step of swelling clay mineral in solution containing urea or aluminum salt and a step of mixing the clay mineral with amino acid.

Description

Compound nano fertilizer of amino acid material using nano-sheet of layered clay minerals and manufacturing method

The present invention relates to a fertilizer and a method for manufacturing the same, and more particularly, to a nano-composite fertilizer of the amino acid material with improved stability and uniformity, fast-acting and slow-release using a layered clay mineral nanosheets and a method for producing the same. .

Fermentation of molasses or raw sugar produces alcohol, yeast, glutamic acid, organic acid, etc., and a large amount of byproduct amino acid substances are generated in the separation and purification of amino acids and proteins.

These amino acids not only contain various amino acids, peptides and proteins, but also inorganic components such as sulfur and phosphorus, which are necessary for growing crops, and thus are recognized for their useful value as feed additives and organic fertilizers.

However, the method of utilizing such an amino acid substance as an organic fertilizer is still at the level of technology in which CMS (condensed molasses solubles) or the like is simply or mixed with various fertilizer components, and thus, decomposition by various biochemical reactions during storage, The problem of deterioration of the merchandise such as precipitate formation of added salts and precipitation of proteinaceous substances by salts occurs. In addition, the absorption efficiency is very low due to rapid decomposition when applied to soil or plants has become a serious problem.

In other words, the amino acid substance exhibits decomposition problems due to various biochemical reactions during storage, and is poor in uniformity of quality as a plant nutrient feeder, and exhibits agglomeration in the presence of salts due to amphoteric charge. The absorption efficiency when applied to soil and plants is low, NOx gas generated during decomposition and nitrogen nitrogen leachate has a problem causing air and water pollution.

Therefore, the development of technology that can solve the above-mentioned problems is very urgent in agricultural and environmental aspects.

The present invention has been made to solve the above-mentioned problems, mainly by using the by-product amino acid material generated in a solution or slurry (slurry) to improve the stability during storage and to prevent precipitation and precipitation during salt addition, An object of the present invention is to provide a high efficiency nano-composite fertilizer having a fast-acting effect.

It is another object of the present invention to provide a manufacturing method capable of efficiently producing the above-mentioned nanocomposite fertilizer.

The object of the present invention is to increase the product uniformity and shelf life of amino acid fertilizers by introducing amino acids into the surface and interlayers of the nanosheets of swellable layered clay minerals to maximize uniformity and stability in solution and solid phase. And at the same time improve the nutrient absorption efficiency and effect persistence as a fertilizer.

Therefore, the amino acid nanocomposite fertilizer according to the present invention comprises a swellable layered clay mineral and prepared amino acid material introduced into the surface and between the layers of the clay mineral, wherein the amino acid material is the surface of the clay mineral and Introduced between the layers to interact with the surface charge of clay minerals and the three-dimensional structural properties of amino acids to uneven the distance between layers of clay minerals or to strip plates to form fully or partially peeled nanosheets. It is characterized by.

Nanocomposite fertilizer using the amino acid material according to the present invention, as the by-product amino acid material is introduced into the surface and the interlayer of the nano-sheet of the clay mineral and exist in a nanonized state, as well as preventing decomposition and precipitation during storage, Sedimentation problems due to protein precipitation during salt addition or insolubilization of added salts are solved, which improves storage stability during compounding, and the amino acid material is combined with clay minerals to exhibit both efficacy and sustainability. There is.

In particular, the composite fertilizer in which the amino acid material is introduced into the swellable layered clay mineral according to the present invention is uniformly adsorbed by the amino acid material is uniformly adsorbed to the nano-sized clay mineral, the stability of the suspension is increased, the product uniformity is high, Proteolytic degradation is inhibited by amino acid protection of the layered clay mineral particles, which may have sustained release.

In addition, in the case of general amino acid fertilizers, the outflow of water is easy, whereas the amino acid component introduced into the layered clay mineral can reduce the loss rate of fertilizer components due to rainfall, thereby increasing the efficiency of the fertilizer, and thus, There is an effect that can be reduced.

In addition, the fertilizer component is slowly eluted using the clay mineral nanosheets, so that the absorption into the plant is uniformly controlled during the entire growth period, thereby maximizing the ineffectiveness and minimizing the environmental pollution caused by the loss of the fertilizer component. Can contribute to maximization.

In the present invention, the amino acid nanocomposite is prepared through complete and partial exfoliation of swellable layered clay minerals utilizing amino acid substances, solution stabilization of various ions through selective adsorption and ion dispersing, and enhancement of decomposition resistance of amino acid substances. A fertilizer and its manufacturing method are provided.

Therefore, according to the present invention, it comprises a swellable layered clay mineral comprising a nanosheet phase completely or partially peeled off by swelling and an amino acid material prepared, wherein the amino acid material is the surface of the nanosheet of the clay mineral and An amino acid nano-composite fertilizer is provided, which is introduced between the layers and exists in a nanonized state.

Figure 1 is a schematic diagram showing the process of changing the introduction of the amino acid material to the swellable layered clay mineral during the preparation of the amino acid nano-composite fertilizer according to the present invention.

Referring to the amino acid nano-composite fertilizer and the manufacturing process according to the present invention in detail with reference to the drawings, the principle of producing the amino acid nano-composite fertilizer according to the present invention is a swellable layered clay mineral that is easily expanded in water Or sufficiently expanded in a solution containing a salt such as an ammonium salt, and then reacted with the amino acid material so that the amino acid material is partially or completely intercalated between the layers of the clay mineral, depending on the chargeability of the amino acid material. do. The intercalated amino acid material causes uneven distance between layers of clay minerals or layers of some clay minerals.

That is, the charge on the surface of clay minerals interacts with cations or anions of amino acid substances. (A positive amino acid substance has a repulsive force on one side of the amino acid when the charge is the same as the surface of the clay mineral.) Depending on the three-dimensional structure of the amino acid and the degree of folding (chain folding) of the non-uniform distance between the layers or peeling some layers.

The outer surface of the fully or partially exfoliated clay mineral layer secondaryly combines with the amino acid material in the solution to prevent recombination of the clay mineral, and also blocks the aggregation and precipitation of the amino acid material by salts. Among the dissolving salts added while improving the stability and decomposition resistance of solid materials, that is, proteins and clay minerals, cations are selectively adsorbed to anionic clay minerals and anions are selectively adsorbed to cationic clay minerals. Formation of insoluble salts, such as hydroxide, can be prevented.

Therefore, not only the biochemical degradation of the amino acid material is delayed, but also the delayed absorption and the absorption efficiency of nutrients can be increased while adsorbing amino acids, which are primary degradation products by clay minerals, and preventing precipitation of inorganic ions.

In the preparation of the amino acid nanocomposite fertilizer using the nanosheet of the layered clay mineral according to the present invention, preferably, the layered clay mineral and the amino acid material are mixed in a ratio of 1: 1 to 9 by weight. . When the weight ratio is mixed at a ratio of about 1: 1, a gel-like substance capable of producing a solid fertilizer is obtained, and when the weight ratio of the liquid amino acid is increased, a liquid fertilizer can be prepared. It is preferable to obtain a stable nano composite fertilizer while increasing the content of the amino acid substance having a weight ratio of about 1: 8 to 9 as much as possible. The effect is not enough.

In this case, the layered clay mineral may be selected from a smectite clay mineral or a layered double hydroxide, and the amino acid material may be obtained from an amino acid-based by-product containing CMS (condensed Molasses Soluble) or animal amino acid. use. At this time, the amino acid material is a fertilizer component containing materials such as urea, ammonium sulfate, phosphoric acid, and the like to adjust the pH to close to the isoelectric point of the amino acid to have an amphoteric charge, and hydrogen bonding to minimize the folding of the peptide chain Interfering salts are added to adjust the ionic strength (IS) to near 0.1-5 molar concentrations.

In addition, in order to partially or completely insert three-dimensional materials having various zwitterionic charges and sizes into the layered clay minerals, the layers between the layered clay minerals should be expanded as much as possible. The swelling of layered clay minerals for this purpose is achieved by saturating the layers with ammonium ions by a solution (1.0-2.0 molar concentration) prepared with ammonium salt or urea.

When the swollen clay mineral and the amino acid substance with controlled solution properties are mixed, the rearrangement of the disordered crystals through the partial adsorption or complete exfoliation of the crystals through surface adsorption and ion exchange reaction proceeds very rapidly and the fertilizer within 2 hours. The preparation of is completed. As the reaction proceeds, the fluidity of the reactants in the gel state is lowered and may show a very high viscosity depending on the moisture content and the ionic strength, or may be prepared in a solid phase.

That is, in the preparation of the solid amino acid nanocomposite fertilizer, the mixture of the swellable layered clay mineral powder and the amino acid material such as CMS in the liquid phase of which pH and ionic strength are adjusted as described above is stirred, intercalation and A semi-dry solid is obtained by a hygroscopic reaction, and dried to prepare a powder or granule.

On the other hand, in the case of the liquid fertilizer is prepared by adjusting the pH and ionic strength of the amino acid solution and the swelled clay mineral suspension is adjusted, the pH is adjusted to about acidic to neutral near the isoelectric point of the amino acid material.

When the liquid and solid anoic acid nano-composite thus prepared is exposed to the environment when applied to soil or crops, amino acid components intercalated are easily released and decomposed and absorbed into the crop by ion exchange and diffusion mechanisms.

Moreover, the released amino acid components are easily degraded in the environment, while the components adsorbed on the nanosheets of the layered clay minerals, which are inorganic carriers, can minimize the decomposition and loss, thus providing the effect of fast-acting and sustained-release effects, thus providing continuous nutrients to crops. have.

Hereinafter, embodiments of the present invention will be described.

Example 1

Urea was added to the CMS solution so as to have a molar concentration of 5.0, and then the pH was adjusted to 5, and mixed with the swellable layered clay mineral bentonite, stirred, and dried to prepare a solid amino acid nanocomposite fertilizer.

The X-ray diffraction patterns of the solid amino acid nanocomposite fertilizer and bentonite as swellable layered clay minerals were investigated. The results are shown in FIG. 2.

As shown in FIG. 2, bentonite, an inorganic carrier material not mixed with an amino acid material, exhibited a strong main peak at around 14.25 nm, and appeared in a hydrated form.

However, in the solid amino acid nanocomposite fertilizer prepared in the present embodiment, it can be seen that the amino acid is inserted into the bentonite, and the main peak is widened and the strength is lowered at the same time. It suggests that partial peeling of the layer and rearrangement of the disordered crystals occurred.

Example 2

After the ammonium sulfate was added to the CMS solution to 0.5 molar concentration, bentonite saturated with ammonium was mixed to 1 v / w%, and the pH was adjusted to 5 to prepare a liquid amino acid nanocomposite fertilizer according to the present invention. It was.

Test 1

The liquid amino acid nanocomposite fertilizer stock solution prepared in Example 2 and the diluted solution diluted 500-fold for 3 hours in order to dilute it to the concentration level used when fertilizing the actual crop was confirmed by dispersion stability.

In addition, the stock solution prepared by simply mixing the bentonite and CMS solution stock solution used in Example 2 and the diluted solution diluted 500-fold was prepared, and left standing for 3 hours to compare the dispersion stability with the amino acid nanocomposite fertilizer prepared in Example 2 It was.

As a result, as shown in FIG. 3, the precipitate of the simple mixture and its dilution occurred, but in the case of the liquid and the dilution of the amino acid nanocomposite fertilizer prepared in Example 2, the precipitate did not occur, resulting in uniform and stable stability. It can be confirmed that the dispersion is made.

Test 2

In order to confirm the degree of conversion of the amino acid nanocomposite fertilizer and the simple amino acid material to the ammonia-pacific nitrogen in accordance with the present invention, the liquid amino acid nanocomposite fertilizer prepared in Example 2 and the CMS solution which is an amino acid material (comparative example) ) Is converted into the same amount of nitrogen and applied to the soil, and the substitutional ammonia nitrogen content was examined for each time period, and the change is shown in FIG. 4.

As shown in Figure 4, in the case of the amino acid nano-composite fertilizer prepared according to the present invention, compared to the case of using a simple CMS solution, the content of ammonia nitrogen eluted initially was lower, which was initially This is because the ammonia nitrogen generated is adsorbed to the clay mineral.

On the other hand, after 10 days, the ammonia nitrogen was gradually decreased in the CMS solution application of the comparative example, while the compound fertilizer of Example 2 was continuously increasing. This result is due to the rapid conversion to NOx in the comparative example, while the conversion of protein or amino acid to ammonia nitrogen in the compound fertilizer of Example 2 is a result of the ammonia is adsorbed to the clay minerals and the conversion to NOx is inhibited. Judging.

This fact also appears as a result of measuring the change amount of the nitrogenous nitrate shown in FIG. 5.

That is, as shown in FIG. 5, in the case of the compound fertilizer of Example 2, the amount of nitrogen nitrate was generally lower than that of the comparative example, and increased more rapidly after 10 days.

From the above results, the amino acid nanocomposite fertilizer according to the present invention was confirmed that the conversion to nitrogen nitrate is slower than the simple amino acid fertilizer and the generation of NOx is significantly suppressed as a whole.

1 is a schematic diagram showing the change in the manufacturing process of the amino acid nano-fertilizer.

2 is a graph showing an X-ray diffraction pattern of bentonite, an amino acid nanocomposite fertilizer and a swellable layered clay mineral;

Figure 3 is a photograph showing the comparison test results of the dispersion stability and the simple mixed solution and amino acid nano fertilizer;

4 is a graph showing the change of the substitutional ammonia nitrogen content after the application of the amino acid substance and amino acid nanocomposite fertilizer;

5 is a graph showing the amount of change in nitrate nitrogen after application of the amino acid material and amino acid nano-fertilizer.

Claims (7)

It comprises a swellable layered clay mineral and prepared amino acid material introduced into the surface and between the layers of the clay mineral, the amino acid material is introduced into the surface and interlayer of the clay mineral to interact with the surface charge of the clay mineral And the nanosheets of the layered clay minerals characterized in that the distance between layers of the clay minerals is uneven or the plate is peeled off to form a fully or partially peeled nanosheet shape by the three-dimensional structural characteristics of the amino acid material. Amino Acid Nanocomposite Fertilizer. The amino acid nano-composite fertilizer according to claim 1, wherein the layered clay mineral is selected from smectite clay mineral or layered double hydroxide. The method of claim 1, wherein the amino acid material is one or more fertilizer component-containing material is obtained from the amino acid-based by-product containing a condensed Molasses Soluble (CMS) or animal amino acid adjusted to the pH of the solution close to the isoelectric point of the amino acid Amino acid nanocomposite fertilizer. The amino acid nano-composite fertilizer according to claim 1, wherein the layered clay mineral is saturated with ammonium ions by ammonium or urea solution. A nanosheet of layered clay minerals comprising the step of expanding the swellable layered clay mineral in a solution containing urea or ammonium salts and then mixing the expanded layered clay mineral with an amino acid to react the mixture. Amino acid nanocomposite fertilizer manufacturing method using. After mixing a liquid amino acid substance using a suspension of swellable layered clay mineral and at least one fertilizer component selected from urea, ammonium salt or phosphoric acid, the pH is adjusted to the isoelectric point of the amino acid substance. Method for preparing liquid amino acid nanocomposite fertilizer using nanosheets of clay minerals. By mixing and stirring the powder of the swellable layered clay mineral and the liquid amino acid material, the amino acid material is introduced into the surface and the layers of the clay mineral through intercalation and hygroscopic reaction, and interacts with the surface charge of the clay mineral. Due to the three-dimensional structural characteristics of the amino acid material, the semi-dried solid material of the amino acid nano-composite fertilizer in the form of uneven interlayer distance of clay minerals or peeling of the plate to form a fully or partially peeled nano sheet form A method for producing a solid amino acid nanocomposite fertilizer using a nanosheet of a layered clay mineral, which is obtained, and dried to prepare a powder or granules.

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