KR20230046567A - Method for preparing mineral amino acid complex and method for preparing feed composition comprising the same - Google Patents

Abstract

The present invention relates to a method of producing mineral amino acid crystals, comprising the steps of: (a) simultaneously adding a mineral precursor and an amino acid to heated water, and dissolving and reacting the same to produce a solution containing a mineral amino acid complex; (b) making the solution containing the mineral amino acid complex to a saturated state by controlling temperature and then slowly cooling the same to induce crystallization to produce a solution containing mineral amino acid complex crystals; and (c) filtering and drying the solution containing the mineral amino acid complex crystals to remove moisture and obtain the mineral amino acid complex crystals. Accordingly, the yield is increased and the process time can be significantly shortened compared to the production of mineral amino acid crystals using a conventional concentration process.

Description

Method for preparing mineral amino acid complex crystals and method for preparing feed composition comprising the same {Method for preparing mineral amino acid complex and method for preparing feed composition comprising the same}

The present invention relates to a method for producing crystals of a mineral amino acid complex and a method for producing a feed composition comprising the same, and more particularly, to a method for producing a crystal of a mineral amino acid complex using induction of crystallization and a method for producing a feed composition comprising the same .

The advantage of amino acid-mineral complexes in mineral nutrition is that they are readily absorbed by mucosal cells and plant cells by active transport or other mechanisms. That is, when minerals are absorbed using amino acids as carrier molecules, there is an advantage in avoiding problems related to competition for active sites for absorption and absorption inhibition of special trace elements between minerals.

A mineral amino acid complex is generally produced by a reaction between an alpha-amino acid and a metal ion, and a metal ion having a valency of 2 or more is required to have a ring structure. In this reaction, the positive charge of the metal ion is neutralized by reacting with the negative charge of the amino or carboxyl group of the alpha-amino acid.

Literature on the structure and chemical formula and bioavailability of mineral amino acid complexes is very diverse. Representatively, Ashmead et al., Chelated Mineral Nutrition, (1982), Chas. C. Thomas Publishers, Springfield, Ill. ), Ashmead et al., Intestinal Absorption of Metal Ions, (1985), Ashmead et al., Foliar Feeding of Plants with Amino Acid Chelates, (1986) and U.S. Patent No. 4,020,158 , 4,167,564, 4,216,143, 4,721,644, 4,599,152, 4,774,089, 4,830,716, 4,863,898, 4,725,427 and the like.

Conventional method for producing mineral amino acid complex is to perform a concentration process after the reaction to form the complex. In this concentration process, the viscosity of the sample increases, so that it frequently sticks to the container during the filtration and drying steps, and vacuum-drying. In the process, there is a problem in that the yield of the product decreases due to loss of sample due to bubbles generated as moisture evaporates, and a separate grinding process is required to make the mineral amino acid complex generated in the concentration process into particles, so the process time is shortened. It was a long and costly problem.

U.S. Patent No. 4,020,158 U.S. Patent No. 4,167,564

Ashmead et al., Chelated Mineral Nutrition, (1982), Chas. C. Thomas Publishers, Springfield, Ill. Chas. C. Thomas Publishers, Springfield, Ill. Ashmead et al., Intestinal Absorption of Metal Ions, (1985) Ashmead et al., Foliar Feeding of Plants with Amino Acid Chelates, (1986)

An object of the present invention is to solve the problems occurring in the conventional mineral amino acid complex manufacturing method including a concentration process, and to provide a novel mineral amino acid complex manufacturing method capable of shortening the process time and improving the yield. .

In addition, another object of the present invention is to provide a method for producing a functional feed composition including a method for producing a novel mineral amino acid complex having the above advantages.

According to one aspect of the invention,

(a) preparing a solution containing a mineral amino acid complex by simultaneously adding a mineral precursor and an amino acid to heated water, dissolving and reacting;

(b) preparing a solution containing mineral amino acid complex crystals by saturating the solution containing the mineral amino acid complex by controlling the temperature and then slowly cooling the solution to induce crystallization; and

(c) filtering and drying the solution containing the mineral amino acid complex crystals to remove moisture and obtaining mineral amino acid complex crystals; provided.

The mineral precursor may be a metal oxide or metal salt containing any one metal selected from zinc (Zn), magnesium (Mg), manganese (Mn), copper (Cu), and chromium (Cr).

The amino acid may be aspartic acid or glutamic acid.

In step (a), the dissolution and reaction may be performed in water heated to 60 to 90 °C.

In step (a), the mineral precursor and amino acid may be mixed at a molar ratio of 1:1 to 1:3.

In step (b), the saturation state may be formed at a temperature of 60 to 90 °C.

In step (b), the crystallization induction may be performed by cooling to a temperature of 10 to 30 °C.

In step (c), the drying may be performed at a temperature of 60 to 80 °C.

In step (c), the drying may be performed according to vacuum drying.

The mineral amino acid complex has a molecular formula of C ₄ H ₉ NO ₇ Zn, and may be zinc aspartic acid hydrate represented by Formula 1 below.

[Formula 1]

.

.

The mineral amino acid complex may be an orthorhombic crystal.

According to another aspect of the present invention,

A method for producing a feed composition comprising the method for producing the crystal of the mineral amino acid complex is provided.

The manufacturing method of the mineral amino acid complex of the present invention, unlike the conventional manufacturing method of the mineral amino acid complex, uses crystallization induction through cooling instead of the concentration process, thereby improving the yield by preventing the yield reduction due to the generation of bubbles during concentration and reducing the process time to 6 There is an effect that can significantly shorten the time or more.

In addition, the manufacturing method of the functional feed composition of the present invention can shorten the process time and reduce the cost by including the mineral amino acid complex manufacturing method introducing the crystallization induction.

1 shows a saturation curve related to the induction of supersaturation for inducing crystallization in the method for preparing mineral amino acid crystals of the present invention.
Figure 2 is a flow chart showing the manufacturing process of Comparative Example 1 (a) and Example 1 (b).
FIG. 3 is a schematic diagram of a coordinate bond between zinc aspartic acid hydrate of Chemical Formula 1 and an aspartic acid (second aspartic acid) of an adjacent zinc aspartic acid hydrate.
4 is an infrared spectroscopic analysis result according to Experimental Example 3 of the present invention.

Since the present invention can apply various transformations and have various embodiments, specific embodiments will be illustrated in the drawings and described in detail in the detailed description. However, it should be understood that this is not intended to limit the present invention to specific embodiments, and includes all transformations, equivalents, and substitutes included in the spirit and scope of the present invention. In describing the present invention, if it is determined that a detailed description of related known technologies may obscure the gist of the present invention, the detailed description will be omitted.

Hereinafter, the manufacturing method of the mineral amino acid crystals of the present invention will be described.

First, a mineral precursor and an amino acid are simultaneously added to heated water, dissolved and reacted to prepare a solution containing a mineral amino acid complex (step a).

The mineral precursor may be a metal oxide or metal salt containing any one metal selected from zinc (Zn), magnesium (Mg), manganese (Mn), copper (Cu) and chromium (Cr), and preferably the metal. The oxide or metal salt may be any one selected from zinc (Zn) and magnesium (Mg). More preferably, it may be zinc oxide or zinc sulfate, and even more preferably, it may be zinc oxide. Most preferably, zinc oxide can be used. In the prior art, water-soluble zinc salts that are well soluble in water were mainly used for the preparation of zinc aspartic acid complexes, but when heated over a certain temperature and time while using water-insoluble zinc oxide, a more effective zinc amino acid complex can be formed. there is.

The amino acid is preferably aspartic acid or glutamic acid, and more preferably may be aspartic acid.

That is, the mineral amino acid complex is preferably a zinc aspartic acid complex.

The dissolution and reaction may be carried out in water heated to 60 to 90 ° C, more preferably in water heated to 60 to 80 ° C, even more preferably 60 to 70 ° C. In the above temperature range, reactions required for the formation of the mineral amino acid complex along with dissolution may occur most actively.

The mineral precursor and amino acid may be mixed in a molar ratio of 1:1 to 1:3, and more preferably in a molar ratio of 1:1.5 to 1:2.5.

The theoretical molar ratio of zinc to aspartic acid in zinc aspartic acid complex hydrate is 1:1, but when an excess amount of aspartic acid is added compared to the zinc precursor, insoluble zinc oxide is reduced and water-soluble zinc aspartic acid hydrate is more easily prepared. can

A step of removing insoluble matters from the product of this step may be further included. The step of removing insolubles may be further required when zinc oxide is used as a zinc precursor. The step of removing the insolubles may be performed by filtering with a filter paper or filter cloth of several μm or less, for example, 0.2 μm, and the insolubles may be removed before the filtration or separately from the filtration by centrifugation.

Thereafter, the solution containing the mineral amino acid complex is saturated by temperature control and then slowly cooled to induce crystallization, thereby preparing a solution containing the mineral amino acid complex crystals (step b).

1 is a saturation curve related to crystallization induction, and this step will be described with reference to this.

The saturation state is preferably formed at a temperature of 60 to 90 °C, more preferably 60 to 80 °C, and even more preferably at a temperature of 60 to 70 °C.

When the saturated state is formed, it is preferable to induce crystallization by making the supersaturated state while gradually cooling to a temperature of 30 ° C or less, and more preferably, crystallization can be induced at a temperature of 10 to 30 ° C. Such crystallization has an advantage in that since a crystalline sample having particles is prepared in a crystallization tank, only water needs to be removed thereafter, and there is no need to go through a separate pulverization process as in the conventional preparation by concentration.

Next, the solution containing the mineral amino acid complex crystals is filtered and dried to remove moisture to obtain mineral amino acid complex crystals (step c).

The drying is preferably performed at a temperature of 60 to 80°C, and more preferably at 65 to 75°C.

The drying is preferably performed according to vacuum drying.

The mineral amino acid complex thus prepared may be zinc aspartic acid hydrate represented by the following Chemical Formula 1 and having a molecular formula of C ₄ H ₉ NO ₇ Zn.

[Formula 1]

.

.

The zinc aspartic acid hydrate is characterized in that it has a water solubility that dissolves in 1 to 30 ml of water at 25 ° C. per 1 g, and is an orthorhombic crystal.

[Formula 1]

The present invention provides a method for preparing a feed composition comprising the method for preparing the above-described mineral amino acid complex.

The mineral amino acid complex crystals of the present invention can be used for feed additives.

The feed additive may be added and mixed at 0.01-1% by weight based on the solid content of the feed composition of livestock such as pigs, chickens, ducks, cows, sheep, goats, dogs, and may be applied by administering to various animals, more preferably It is used as an additive in pig feed.

The feed composition of the present invention may be prepared as a feed composition in the form of fermented feed, formulated feed, pellet form and silage, but is not limited thereto, and may be modified and prepared as necessary.

Preparation of the mineral amino acid complex using the conventional concentration process may take about 12 hours or more from reaction, concentration, vacuum drying, and grinding. It is not necessary to perform the grinding process, and since the concentration process is omitted, the process time can be reduced by 6 hours or more compared to the prior art.

Hereinafter, preferred embodiments are presented to aid understanding of the present invention, but the following examples are merely illustrative of the present invention, and various changes and modifications are possible within the scope and spirit of the present invention. It is obvious to those skilled in the art, It goes without saying that these variations and modifications fall within the scope of the appended claims.

[Example]

Example 1: Preparation of zinc aspartic acid complex by crystallization process

After putting 1,300ℓ of purified water in a stirrer and heating it to 60℃, the mixture of 61.5kg of zinc oxide and 163.5kg of aspartic acid was added to the heated purified water and stirred (35hz, 80rpm or less) for 6 hours to perform dissolution and reaction at the same time. . When the reaction is completed, the solution containing the zinc aspartic acid complex produced by the reaction is transferred to a crystallization tank, saturated at a temperature of 60 to 90 ° C, and then slowly cooled below 30 ° C to form a supersaturated state, thereby inducing crystallization Thus, zinc aspartic acid complex crystals were prepared. Thereafter, the zinc-aspartic acid complex crystals and the supernatant (water) were fractionated through filtration, and vacuum-dried at 70° C. in a dryer to obtain aspartic acid complex crystals.

Comparative Example 1: Preparation of Zinc Aspartic Acid Complex by Concentration Process

1,300 ℓ of purified water was put into a stirrer, 61.5 kg of zinc oxide was stirred to dissolve, and 163.5 kg of aspartic acid was added and reacted by stirring at a temperature of 90 ° C. for 6 hours to prepare a zinc aspartic acid complex. When the reaction was completed, the solution containing the zinc aspartic acid complex was concentrated under reduced pressure. The concentrated solution was filtered using a 200 μm filter to remove the solvent, dried in a vacuum at 70° C. in a dryer, and pulverized.

[Experimental Example]

Experimental Example 1: Confirmation of structure of zinc aspartic acid complex

The structure of the zinc aspartic acid complex prepared according to Example 1 and Comparative Example 1 was confirmed using Bruker SMART APEX II X-ray Crystallograph (XRC) and Bruker SHELXTL Structure Analysis Program.

crystallographic data

Molecular Formula C ₄ H ₉ NO ₇ Zn

Molecular Weight 248.49

crystal system orthorhombic system

space group P2(1)2(1)2(1)

Z 4

unit cell dimension a=7.8012(15) Å α=90°

b=9.3435(17)Å β=90°

c=11.576(2)Å γ=90°

Volume 843.8(3) / Å ³

Calculated density 1.956 Mg/m ³

temperature 296(1)K

absolute structural parameters 0.00

Crystal size 0.18 x 0.12 x 0.08 mm ³

F(000) 504

Absorption coefficient 2.920 mm ^-1

Table 1 shows atomic coordinates (x10 ⁴ ) and equivalent isotropic displacement parameters (Å ² x10 ³ ). U(eq) is defined as 1/3 of the trace of the orthogonalized Uij tensor.

Table 2 shows the bond length (Å) and angle (°).

Symmetry transformations were used to create equivalent atoms. #1 -x, y-1/2, -z+3/2; #2 - x, y+1/2, -z+3/2.

Table 3 shows the anisotropic displacement parameters (Å ² x10 ³ ). The exponent of the anisotropic displacement factor is of the form -2π ² [h ² a ^*2 U ¹¹ +...+2hka ^* b ^* U ¹² ].

Table 4 shows hydrogen coordinates (x10 ⁴ ) and equivalent isotropic displacement parameters (Å ² x10 ³ ).

Table 5 shows torsion angles (°).

Based on the above results, the water-soluble zinc aspartic acid complexes of Example 1 and Comparative Example 1 have a molecular formula of C ₄ H ₉ NO ₇ Zn, and are confirmed to be zinc aspartic acid hydrates of the following formula 1. Examples in which the crystallization process of the present invention is introduced It was confirmed that the zinc aspartic acid complex of No. 1 and the zinc aspartic acid complex of Comparative Example 1 using the conventional concentration process had the same molecular structure and molecular weight, and thus produced the same product.

[Formula 1]

In the zinc aspartic acid hydrate of Formula 1, two water molecules are coordinated with zinc, two oxygen atoms are coordinated with two hydroxyl groups of the first aspartic acid and one nitrogen atom is coordinated with one amino group, and the second Zinc aspartic acid hydrate is a 1:1 molar ratio of zinc and aspartic acid, which have a total of six coordination bonds by coordinating with one oxygen atom of aspartic acid.

FIG. 3 shows a schematic diagram in which the zinc aspartic acid hydrate of Chemical Formula 1 coordinates with the aspartic acid (second aspartic acid) of the adjacent zinc aspartic acid hydrate.

Experimental Example 2: Comparison of Production Yield of Zinc Aspartic Acid Complexes According to Manufacturing Methods

The preparation of the zinc aspartic acid complex of Example 1 and Comparative Example 1 was performed three times each, and the results of comparing yields are shown in Table 6 below.

Comparative Example 1 (including concentration process) Example 1 (including crystallization process) Sample transference number(%) Sample transference number(%) One 84.5 One 95.18 2 84.8 2 95.71 3 84.6 3 96.0 average 84.63 average 95.63

According to this, it can be confirmed that the production yield of the zinc aspartic acid complex of Example 1 including the crystallization process of the present invention is increased by 10% or more compared to the production yield of the zinc aspartic acid complex of Comparative Example 1 including the conventional concentration process. can

Experimental Example 3: Infrared spectroscopic analysis

For the zinc aspartic acid complex prepared in Example 1 and Comparative Example 1, the Korea Research Institute of Chemical Technology was commissioned to perform infrared spectroscopy analysis (Bruker ALPHA-T Infrared Spectrometer (IR)), and the results are shown in FIG. was Here, (a) shows the result of infrared spectroscopy analysis of the zinc aspartic acid complex of Example 1 and (b) the zinc aspartic acid complex of Comparative Example 1.

According to this, the peak values of the zinc aspartic acid complex of Comparative Example 1 including the conventional concentration process and the zinc aspartic acid complex of Example 1 including the crystallization process of the present invention were similar.

Experimental Example 4: Induction Plasma Spectroscopic Analysis

For the zinc aspartic acid complex prepared in Example 1 and Comparative Example 1, the Korea Research Institute of Chemical Technology was requested to perform inductive plasma spectroscopy (by Thermo Scientific iCAP 7400 duo Inductively Coupled Plasma-Atomic Emission Spectrometer (ICP-AES)). It was performed and the results are shown in Tables 7 and 8 below.

Here, Table 7 shows the results of 5 samples of the zinc-aspartic acid complex of Example 1, and Table 8 shows the results of induction plasma spectroscopy of 6 samples of the zinc-aspartic acid complex of Comparative Example 1.

According to this, it was found that the zinc content of the zinc aspartic acid complex of Example 1 including the crystallization process of the present invention was increased compared to the zinc aspartic acid complex of Comparative Example 1 including the conventional concentration process. It is considered that the zinc content increased due to the complete reaction between aspartic acid and zinc.

Examples of formulation of the composition containing the mineral amino acid complex crystals of the present invention will be described below, but the present invention is not intended to be limited, but only specifically described.

[Formulation example]

Formulation Example 1: Preparation of powder

Zinc aspartic acid complex crystals of Example 1 500 mg

Lactose 100 mg

Talc 10 mg

The above ingredients are mixed and filled into an airtight bag to prepare a powder.

Formulation Example 2: Preparation of tablets

Zinc aspartic acid complex crystals of Example 1 300 mg

Corn Starch 100 mg

Lactose 100 mg

Magnesium stearate 2 mg

After mixing the above ingredients, tablets are prepared by tableting according to a conventional tablet manufacturing method.

Formulation Example 3: Preparation of capsule formulation

200 mg of crystals of the zinc aspartic acid complex of Example 1

3 mg of crystalline cellulose

Lactose 14.8 mg

Magnesium stearate 0.2 mg

Capsules are prepared by mixing the above ingredients and filling them into gelatin capsules according to a conventional capsule preparation method.

Formulation Example 4: Preparation of injection

Zinc aspartic acid complex crystals of Example 1 600 mg

Mannitol 180 mg

Sterile Distilled Water for Injection 2974 mg

Na ₂ HPO _4, 12H ₂ O 26 mg

It is prepared with the above component content per 1 ampoule according to the conventional method for preparing injections.

Formulation Example 5: Preparation of liquid formulation

4 g of crystals of the zinc aspartic acid complex of Example 1

Isomerized sugar 10 g

5 g mannitol

Appropriate amount of purified water

According to the conventional liquid formulation manufacturing method, each component is dissolved in purified water, lemon flavor is added in an appropriate amount, the above components are mixed, and then purified water is added to adjust the total amount to 100g, and then filled into a brown bottle for sterilization. to prepare a liquid.

Formulation Example 6: Preparation of granules

1,000 mg of crystals of the zinc aspartic acid complex of Example 1

Appropriate amount of vitamin mixture

Vitamin A Acetate 70 μg

Vitamin E 1.0 mg

Vitamin B1 0.13 mg

Vitamin B2 0.15 mg

Vitamin B6 0.5 mg

Vitamin B12 0.2 μg

Vitamin C 10 mg

10 μg of biotin

Nicotinamide 1.7 mg

Folic acid 50 μg

Calcium Pantothenate 0.5 mg

Appropriate amount of mineral mixture

Ferrous sulfate 1.75 mg

Zinc Oxide 0.82 mg

Magnesium Carbonate 25.3 mg

Potassium Phosphate Monobasic 15 mg

Dibasic Calcium Phosphate 55 mg

Potassium citrate 90 mg

Calcium Carbonate 100 mg

Magnesium Chloride 24.8 mg

Although the composition ratio of the above vitamin and mineral mixture was prepared by mixing ingredients suitable for granules in a preferred embodiment, the mixing ratio may be arbitrarily modified, and after mixing the above ingredients according to a conventional granule manufacturing method, It can be prepared and used for preparing a health functional food composition according to a conventional method.

Formulation Example 7: Preparation of feed composition

0.1 kg of the zinc aspartic acid complex crystal of Example 1, 25.5 kg of corn, 15.04 kg of wheat, 8.15 kg of wheat flour, 7.4 kg of rice bran, 18 kg of soybean meal, 1 kg of jade gluten, 14 kg of chicken by-products, 9 kg of animal fat and oil, 0.3 kg of processed salt , 0.3 kg of tricalcium phosphate, 1 kg of limestone, 0.01 kg of choline chloride, 0.05 kg of vitamins, 0.05 kg of minerals, and 0.1 kg of digestive enzymes were mixed to prepare an animal (dog, pet dog) feed composition.

Claims (12)

(a) preparing a solution containing a mineral amino acid complex by simultaneously adding a mineral precursor and an amino acid to heated water, dissolving and reacting;
(b) preparing a solution containing mineral amino acid complex crystals by saturating the solution containing the mineral amino acid complex by controlling the temperature and then slowly cooling the solution to induce crystallization; and
(c) filtering and drying the solution containing the mineral amino acid complex crystals to remove water and obtaining mineral amino acid complex crystals. According to claim 1,
The mineral precursor is a metal oxide or metal salt containing any one metal selected from zinc (Zn), magnesium (Mg), manganese (Mn), copper (Cu) and chromium (Cr). manufacturing method. According to claim 1,
The method of producing a mineral amino acid crystal, characterized in that the amino acid is aspartic acid (aspartic acid) or glutamic acid (glutamic acid). According to claim 1,
In step (a), the dissolution and reaction are performed in water heated to 60 to 90 ° C. According to claim 1,
In step (a), the mineral precursor and the amino acid are mixed in a molar ratio of 1:1 to 1:3. According to claim 1,
In step (b), the saturated state is a method for producing a mineral amino acid complex crystal, characterized in that formed at a temperature of 60 to 90 ℃. According to claim 1,
In step (b), the induction of crystallization is performed by cooling at a temperature of 10 to 30 ° C. According to claim 1,
In step (c), the drying is a method for producing a mineral amino acid complex crystal, characterized in that carried out at a temperature of 60 to 80 ℃. According to claim 1,
In step (c), the method for producing a mineral amino acid complex crystal, characterized in that the drying is carried out according to vacuum drying. According to claim 1,
The method for preparing a mineral amino acid crystal, wherein the mineral amino acid complex has a molecular formula of C ₄ H ₉ NO ₇ Zn and is a zinc aspartic acid hydrate represented by the following formula (1).
[Formula 1]

. According to claim 10,
The method for producing a mineral amino acid complex crystal, characterized in that the mineral amino acid complex is an orthorhombic crystal. A method for producing a feed composition comprising a method for producing a crystal of the mineral amino acid complex of any one of claims 1 to 11.

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