KR100741441B1 - Nitrate-nitrogen diminishing agent - Google Patents

Abstract

Provided is a nitrate-nitrogen diminishing agent to substantially reduce nitrate-nitrogen contained in farm products simply by spraying once or twice a year and thus, to grow toxic-free, safe farm products including vegetables and green tea. The nitrate-nitrogen diminishing agent contains a complex essential mineral hydroxide in which a large amount of essential minerals Ca and/or Mg is mixed with a very small amount of other essential minerals such as Fe, Mn, Zn and Cu that are dispersed in an atom state at a proper ratio. The nitrate-nitrogen diminishing agent is represented by chemical formula [(M1^2+)1-x(M2^2+)x]1-z(M^3+)z(OH)2(An-)z/n mH2O or (M1^2+)1-x(M2^2+)x(OH)2, where M12+ indicates Ca and/or Mg, and M2^2+ indicates an essential mineral selected from the group consisting of Fe, Mn, Zn, Cu, Ni and Co.

Description

Nitric Acid Nitrogen Reducing Agent {NITRATE-NITROGEN DIMINISHING AGENT}

The present invention relates to a nitrate-nitrogen reducing agent of crops such as vegetables and green tea.

With the use of nitrogen fertilizers for a long time, the concentration of nitrate nitrogen in crops has been raised to a level that adversely affects the health of the human body, causing problems. The higher the nitrate nitrogen, the higher the risk of developing methemoglobinemia (the risk of death in infants). Therefore, the more vegetables or green teas that are known to be healthy in nature, the worse the health against the purpose. However, a method for reducing nitrate nitrogen in crops has not been found yet, and there is no effective solution.

An object of the present invention is to provide an agent in which nitrate nitrogen in the crops grown therein is greatly reduced only by adding to the soil. Furthermore, it is a simple operation, for example, to provide a soil improving agent capable of reducing the target nitrate nitrogen by spraying or mixing the soil once or twice a year.

The present inventors thought that the cause of the problem of nitrate nitrogen was the deterioration of the soil caused by the use of chemical fertilizers for a long time. Since only chemical fertilizers have been used mainly in the soil, most of the essential minerals that must be present in the soil are depleted or deviated from an appropriate ratio between the minerals, and it is thought that the crops grow unhealthy, so to speak. Therefore, if the soil can provide almost all of the essential minerals in proper proportions and concentrations, the crops grown there will be replenished by replenishing the minerals that are the active centers of the enzymes, thereby restoring the enzyme's original function and restoring health. . As a result, it is thought that nitrate nitrogen can be greatly reduced to a safe level.

Based on the above design, a compound capable of dispersing most of the essential minerals at an appropriate ratio in an atomic state, and capable of being gradually released at an appropriate concentration (hereinafter, simply referred to as 'western') It has been devised, and as a result of repeated experiments, the effect of the present invention was found and realized.

The present invention is the following formula (1) and / or (2)

[Formula 1]

[(M ₁ ^{2 +} ) _1-x (M ₂ ^{2 +} ) _x ] _1-z (M ^{3 +} ) _z (OH) ₂ (A ^n- ) _{z /} nmH ₂ O

[Formula 2]

(M ₁ ²⁺ ) _1-x (M ₂ ²⁺ ) _x (OH) ₂

( ^Wherein M ₁ ²⁺ represents Ca and / or Mg, M ₂ ²⁺ represents at least one or more of the essential minerals Mn, Fe, Cu, Zn, Ni and Co, and M ³⁺ represents 3 1 or more types of valent metals are represented, Preferably at least 1 or more types of Fe, Mn, Cr, and Co are represented, and A ^n- is anion of n (n is an integer of 1 or more). ; represents at least one kind of anion), preferably from _{^{I -, Cl -, NO 3}} -, SO 4 2-, HPO 4 2-, HBO 3 2-, MoO 4 2-, H (Mo) 7 O 24 ^5- , HVO ₄ ^2- , SeO ₄ ^2- , and x, m and z satisfy the following ranges, respectively, 0 <x <0.5, 0 ≦ m <10, 0 <z <0.4. By adding the hydroxide solid solution of the essential mineral represented by zero or positive number), the nitrate nitrogen of the crops grown there can be significantly reduced.

Moreover, the addition of the nitrate-nitrogen reducing agent according to the present invention may be applied once or twice a year because it is sustained release, and thus, once a week or 10 days. Compared with the general medicine which needs to be sprayed, the amount of work can be extremely reduced. By watering or by rainwater, the hydroxide solid solution represented by the formulas (1) and / or (2) gradually dissolves and releases mineral ions in water in an order of ppm or less. For this reason, when the mineral becomes high in excess of an appropriate concentration, it does not cause harm to the crops.

Best Mode for Carrying Out the Invention

The nitrate nitrogen reducing agent of the present invention is represented by the following formula (1) and / or (2)

[Formula 1]

[(M ₁ ^{2 +} ) _1-x (M ₂ ^{2 +} ) _x ] _1-z (M ^{3 +} ) _z (OH) ₂ (A ^n- ) _{z /} nmH ₂ O

[Formula 2]

(M ₁ ²⁺ ) _1-x (M ₂ ²⁺ ) _x (OH) ₂

( ^Wherein M ₁ ²⁺ represents Ca and / or Mg, and M ₂ ²⁺ represents at least one or more of the essential minerals Fe, Mn, Zn, Cu, Ni and Co, preferably Fe, Mn, Zn and Cu, M ³⁺ represents at least one of trivalent metals, preferably at least one of Fe, Mn, Cr, Al, and Co, particularly preferably Fe, Mn, and A ^n- is at least one of n-valent anions, preferably Cl ⁻ , I ⁻ , NO ₃ ⁻ , oxygenates of sulfur, phosphorus, molybdenum, vanadium and selenium which are essential minerals, for example _{^{SO 4 2 -, HPO 4 2}} -, MoO 4 2 -, H (Mo) 7 O 24 5 -, HVO 4 2 -, SeO ₄ represents a ^2-, x, m and z are each in the following range 0 < x <0.5, preferably 0.05≤x≤0.3, particularly preferably 0.1≤x≤0.25, 0≤m <10, 0 <z <0.4, preferably 0.01≤z≤0.3, particularly preferably 0.05≤ hydroxide solid solution of essential mineral represented by 0 or positive number satisfying z≤0.2) It is characterized by containing as an active ingredient.

Of the essential minerals Ca and Mg, which are required in relatively large amounts, alone or in complex hydroxide crystals, trace minerals, Fe, Mn, Zn and Cu, which are required in trace amounts, and essential minerals Mo, which are required in small amounts, Calcium hydroxide or by dissolving at least one or more kinds of minerals selected from Se, Ni, Cr, Co, and V, preferably Fe, Mn, Zn, and Cu in an appropriate ratio (dispersed and dissolved in atomic state) Solubility in water at a level close to magnesium hydroxide, that is, slowly (slowly) dissolution of trace minerals, in other words, sustained release can be achieved.

And by making the hydrotalcite structure shown by Formula (1), the trace minerals Mo, Se, I, and V which are insufficient (deficient) and therefore hard to enter a metal part in a metal hydroxide structure are the anion forms, For example, the oxygen acid salt is anion A ^n- of ion exchangeable formula (1), and is incorporated into one crystal in a molecular state together with other minerals. You can do it.

Examples of such anions include MoO ₄ ^2- , H (Mo) ₇ O ₂₄ ^5- , SeO ₄ ^2- , I-, and HVO ₄ ^2- .

As, for containing essential minerals that require a large amount of anion, eg Cl ^{- -} it is _{^{An, NO 3 -, SO 4}} 2-, SO 3 2-, HPO 4 2-, H 2 PO 4 -, PO 4 3 ^- it can also be incorporated. In addition, it is also possible to chemisorb by using the anionic chemical form of the essential mineral on the surface of the metal hydroxide crystals that are positively charged in the formulas (1) and / or (2). Do. Equation (1) An ^- anion, which does not contain, as well as essential minerals for example, CO ₃ ^2-, CH ₃ COO ^- may be an organic acid ion and the like.

Since essential minerals have an adverse effect even if they are excessive, they are preferably dispersed and present in Ca and / or Mg which requires a large amount at an appropriate ratio and concentration. To do so, the amount (量) x M ₂ ²⁺ in the range of about ^{_{M 1 2+ 0 <x <0.5}} , preferably 0.05≤x≤0.3, particularly preferably 0.1≤x≤0.25. In addition, M ^{+ 2} is preferably contained in the order (順) of Fe>Zn≥Mn> Cu "Mo, Se, Co, Ni. Moreover, the bivalent state which is easy to absorb minerals, such as Fe and Mn, is preferable. Therefore, the range of z is 0 <z <0.4, preferably 0.01≤z≤0.3, particularly preferably 0.05≤z≤0.2.

The preferred ratio of the main minerals occupied in the nitrate-nitrogen reducing agent of the present invention is expressed in mol%, Ca = 64-75%, Mg = 12-33%, Mn = 1-5%, Fe = 5-12% , Cu = 0.2-1%, Zn = 2-5%.

The amount of the nitrate-based nitrogen reducing agent of the present invention added to the soil is 0.1 to 1,000 g, preferably 1 to 200 g, particularly preferably 5 to 100 g per m 2.

When the nitrate-nitrogen reducing agent of the present invention is to improve the carbonization resistance, or to reduce the sedimentation resistance in the case of being dispersed and used in water, to further improve the sustained release property, etc. For this purpose, it may be used by surface treatment with anionic surfactants such as higher fatty acids, alkali metal salts of higher fatty acids or nonionic (nonionic) surfactants. The amount of the surface treating agent is 0.1 to 20%, preferably 0.5 to 10% by weight of the nitrate nitrogen reducing agent according to the present invention. The surface treatment can be carried out by any known wet or dry method, but is preferably anionic or noni dissolved in water or emulsified in water after stirring the agent of the present invention dispersed in water. It can carry out by the wet method of adding and mixing a warm surfactant.

The preparation of the agent of the present invention can be carried out by a coprecipitation method. For example, the aqueous solution of the water-soluble salt of M ₁ ²⁺ and / or M ³⁺ can be co-precipitated by adding an equivalent or equivalent aqueous solution of alkali or more.

Examples of the water-soluble M ₁ ²⁺ , M ₂ ²⁺ and / or M ³⁺ used herein include chlorides such as Ca, Mg, Fe, Mn, Cu, and Zn, nitrates, sulfates, acetates, and the like. Examples of alkali include sodium hydroxide, potassium hydroxide, calcium hydroxide and the like.

Examples of co-precipitation methods other than the above include water-soluble salts such as Mg, Fe, Mn, Cu, Zn, etc., which are less than equivalents, for example, under stirring of slurry-shaped dispersions of calcium hydroxide and / or magnesium hydroxide. It is a method of adding a mixed aqueous solution and making it react.

Calcium hydroxide used as a raw material is calcined lime obtained by calcining limestone and then hydrated. As a mixture of calcium hydroxide and magnesium hydroxide, hydrated product of dolomite (Dolomite)和 物) can be used separately.

The use form of the agent of the present invention is a powder, a slurry, a granulated product, and the like, and granules are preferable when the handling and scattering properties are emphasized. The size of the granulated material is, for example, 5 to 10 mm, preferably 1 to 3 mm, and the shape is spherical, cylindrical, or the like. Moreover, when using for hydroponic cultivation etc., it is preferable to use the slurry with little settling property.

The agent of the present invention is mixed with known agricultural subsidiary materials such as activated clay, diatomaceous earth, mica, zeolite, bent knight, fish meal, activated carbon, bamboo charcoal, prarlite, vermiculite, charcoal, and diluted and / or the like. Or neutralized or adjusted to pH.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on an Example.

[Example 1], [Example 2] and [Comparative Example 1]

Mixed aqueous solution of calcium chloride, magnesium chloride, manganese chloride, ferrous chloride, zinc chloride, cupric nitrate (Ca = 0.7M / L, Mg = 0.15M / L, Mn = 0.02M / L, Fe After stirring 5 liters (about 30 degreeC) of 0.10 M / L, Zn = 0.025 M / L, Cu = 0.005 M / L to 3 liters of 4 M / L sodium hydroxide (about 30 degreeC), it adds for about 1 minute and reacts Let's do it.

The reaction product was filtered under reduced pressure, washed with water, dried at about 100 ° C. for 20 hours, and then pulverized with a hot air drier. The X-ray diffraction pattern of the obtained powder was a mixture of hydrotalcites and calcium hydroxide.

Analysis of the total amount of each element of the pulverized product is performed by ICP, Fe ²⁺ is determined by absorbance photometry (1, 10-phenanthroline method), Mn ²⁺ is determined by chelate titration method, and the amount of crystals is determined. Thermal analysis was carried out and determined by weight reduction of 100 ° C to 200 ° C. The chemical composition was approximately as follows.

(Ca _0.70 Mg _0.15 ) _0.84 Fe ²⁺ _0.04 Mn ²⁺ _0.01 Zn _0.025 Cu _0.005 ) (Fe ³⁺ _0.06 Mn ³⁺ _0.01 ) _0.07 (OH) ₂ Cl _0.07 H ₂ O _0.28

After mixing the powder and the acidic clay in a ratio of 10:90, adding water (in addition), kneading the kneader, and using a extruder, a cylindrical pellet having a diameter of 1.5 mm was produced. After that, the resultant was dried at about 70 ° C. for 5 hours for use in testing crops.

Test setting (g / pot) of seedling topdressing

TABLE 1

0.08% [(Example 1)] and 0.4% [(Example 2)] of the nitrate-nitrogen reducing agent of the present invention obtained by the above method in seedling seeding only (Comparative Example 1) and seedling seeding shown in Table 1 3 litters were prepared for 1 pot after germination for 1 week after germination, and for 3 weeks per pot, nitrate nitrogen, sugar content, chlorophyll and Growth status was measured. Nitrate nitrogen was measured by RQ flex, sugar content by sugar meter, and chlorophyll by chlorophyll tester. The results are shown in [Table 2].

Ingredient contents and growth investigation result

TABLE 2

Nitric acid nitrogen is reduced to less than half by adding 0.08% of the agent of the present invention to the clay, and satisfies 2,000 ppm or less, which is said to be safe. In addition, in the agent of the present invention, the root growth (underground part of the live weight) was improved, and the stems and leaves were strong. This also contributes to the fall prevention. Taste-related sweetness is also improving. Therefore, the agent of the present invention contributes to the remarkable improvement of nitrate nitrogen and to the growth and quality of plants.

The nitrate nitrogen reducing agent of the present invention can reduce nitrate nitrogen to about half or less in crops such as vegetables and green tea, suppress the occurrence of methemoglobinemia, and provide safe crops. In addition, by developing the roots of the crop, the growth of stems and leaves is improved, and the yield is increased. In addition, since the absorption efficiency of the fertilizer is improved, the fertilizer can be reduced, and the stems, leaves, and roots are strengthened, and the fall due to the wind can be improved. In addition, taste and nutrients such as sugar content and chlorophyll are also improved.

Claims (4)

Equation (1) or (2) below on soil [Formula 1] [(M ₁ ²⁺ ) _1-x (M ₂ ²⁺ ) _x ] _1-z (M ³⁺ ) _z (OH) ₂ (A ^n- ) _{z /} nmH ₂ O [Formula 2] (M ₁ ²⁺ ) _1-x (M ₂ ²⁺ ) _x (OH) ₂ ( ^Wherein M ₁ ²⁺ represents Ca and / or Mg, M ₂ ²⁺ represents at least one or more of the essential minerals Fe, Mn, Zn, Cu, Ni and Co, and M ³⁺ represents 3 Represents one or more kinds of valent metals, An ⁻ represents an anion of n (n = 1 to 10), x, m and z are in the following ranges, respectively, 0 <x <0.5, 0 ≦ m <10,0 A nitrate-nitrogen reducing agent for a crop, characterized by adding a hydroxide solid solution represented by &lt; 0 or positive number satisfying &quot; z &lt; 0.4. The method of claim 1, M ₂ ²⁺ in the formulas (1) and (2) are Fe, Mn, Cu and Zn, and M ³⁺ is Mn and / or Fe. The method of claim 1, In the above formulas (1) and (2), x and z are in the ranges of 0.05 ≦ x ≦ 0.3 and 0.01 <z <0.2, respectively. The method of claim 1, The amount of the nitrate nitrogen reducing agent added to the soil is 1 g to 200 g per m 2, wherein the nitrate nitrogen reducing agent of the crop.