KR20000053858A - A process for preparing metal chelates, and stock feed comprising the same - Google Patents

Abstract

PURPOSE: A method of synthesizing organic metallic materials, which is produced from a chelate reaction of metal powder and hydrolyzed animal and plant protein is provided, can be contained in stock feeds preventing environmental pollution. CONSTITUTION: An organic metallic material is synthesized by chelating ph5.5-8.5 of a water solution of an amino acid or hydrolyzed animal protein and hydrolyzed plant protein, and metal powder, an oxide, sodium carbonate or a hydroxide under inert gas, at 60°C or within the limits of a boiling point of the gas.

Description

A process for preparing metal chelates, and stock feed comprising the same}

The present invention provides an aqueous solution of amino acid or hydrolyzed animal protein (HAP) or hydrolyzed plant protein (HPP) and metals (zinc, iron, copper, manganese, cobalt, chromium, molybdenum) to be prepared. Etc ..) to directly react with powders, oxides, carbonates or hydroxides to produce new organometallic compounds produced by chelation bonds and covalent covalent atoms forming heterocyclic structural bonds. It is about how to.

Conventionally, animals have been given inorganic metal substances such as hydrochloride, sulfate, nitrate, phosphate, carbonate, oxide, etc., but these substances are ionized in organs in vivo to show toxicity and bioavailability. This is low, and there was a problem that the substances that are not absorbed as it is excreted to cause environmental pollution.

Accordingly, the present inventors endeavor to develop an organic metal material for feed addition that does not cause the above problems, by using a suitable type of metal (metal or compound) under appropriate conditions, pure amino acid or animal / vegetable protein hydrolyzate (low molecular weight). It was found that the above object can be achieved by chelating the peptide and various amino acid mixtures).

The metal used in the chelation reaction of the present invention is used as a metal powder or in the form of a metal compound.

Metal compounds may be formed in the form of inorganic acid salts such as sulfates, hydrochlorides, nitrates, and phosphates, but metals forming salts of these inorganic acids may be chelate metals in reaction with animal / vegetable protein hydrolysates, peptides or amino acids. It can be formed, but all but one molecule or two molecules of the acid molecule capable of binding in the molecular structure of the chelate metal material is free to form a salt of the inorganic acid and thus remain in the form of an unwanted mixture. Thus, the presence of such inorganic acid salts is ionized in the digestive organs of livestock to promote their transformation into insoluble or toxic substances in combination with other substances, such as phytin, on the surface of the organs.

Therefore, the present invention does not use compounds that are left in the reaction solution such as sulfates, hydrochlorides, nitrates, phosphates, etc., but uses powders of metals themselves, or oxides, carbonates or hydroxides of metals.

When the powder of the metal itself is used, the metal itself can directly cause a chelate reaction. In order to increase the contact area, it is generally preferable to use a powder of about 100 to 300 mesh, and during this reaction, hydrogen Is generated.

As the metal powder, for example, zinc powder, iron powder or manganese powder can be used.

Oxygen is generated when metal oxide is used as a raw material, and carbon dioxide gas is generated when metal carbonate is used. The gas generated during the reaction keeps the temperature of the reaction solution above the boiling point, so that it does not dissolve in the solution but diffuses into the atmosphere, thereby obtaining pure metal chelates.

Examples of the metal oxides include ferrous oxide, ferric oxide, cuprous oxide, cupric oxide, zinc oxide, chromium oxide (CrO ₃ ), and molybdate (MoO ₃ ). Examples of metal carbonates include Ferrous carbonate, copper carbonate (CuCO ₃ Cu (OH) ₂ H ₂ O), zinc carbonate, manganese carbonate, cobalt [xCoCO ₃ · yCo (OH) ₂ · zH ₂ O, x = 2, y = 3, z = 1].

When hydroxide is used as a raw material, water is produced, which is a method in which metals are reacted with animal / vegetable protein hydrolysates, ie, low molecular weight peptides and various amino acid mixtures, or pure amino acids alone. Preferably the hydroxide used is cobalt hydroxide [Co (OH) ₃ ].

Since the powders, oxides, carbonates and hydroxides of the raw metals are not capable of reacting with any metal, these raw materials should be selected according to the reacting materials and the nature of the reaction.

Organic raw materials for forming metal chelates include, firstly, pure amino acids, and secondly, animal protein hydrolyzates or vegetable protein hydrolysates or mixtures thereof.

First, when pure amino acid is used as a raw material, two molecules of amino acid and one metal atom are combined to form one molecule of metal chelate, depending on the type of metal reacted. Taking glycine as an example, the following reaction occurs when a solution of 1 mol of glycine 2 mol metal is reacted under a nitrogen atmosphere.

At this time, the amino group and the carboxyl group of the amino acid combine with the metal to form a chelating bond forming a ring structure, thereby forming a stronger bond than the general ionic bond of the inorganic compound. Until now, highly stable metal chelate materials are produced that do not undergo ionization or decomposition.

Examples of single amino acids that can be used include alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, Barin etc. are mentioned.

Second, when using a raw material of an animal protein hydrolyzate or a hydrolyzate of a vegetable protein or a mixture of both low molecular weight peptides and various amino acids as raw materials, the mixing ratio of peptides and amino acids in the raw material can be unknown. Therefore, their molecular weight or the amount of metal to react quantitatively with them cannot be calculated. However, unlike powders, oxides, carbonates, and hydroxides of metals, their solubility is very low, unlike sulphates, hydrochlorides, nitrates, and phosphates, which are water-soluble and soluble. A slight excess is used in that no gas is generated and the unreacted material is filtered to allow the low molecular weight peptides and amino acids in the solution to react sufficiently with the metal material to form a complete metal chelate.

The organic material used in the present invention, that is, the pH of the amino acid or protein hydrolyzate is adjusted to 5.5 to 8.5 so as to be suitable for the chelation reaction. Therefore, in all the examples below, the pH of the amino acid or protein hydrolyzate solution is adjusted to the above range prior to chelation with the metal or metal oxide.

(Example)

The present invention will be described in more detail with reference to the following examples. These examples are only for illustrating the present invention in more detail, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples.

Example 1

365.5 g of lysine hydrochloride are placed in a 2 liter round bottom flask, 1.5 liters of deionized water is added and stirred at 30 rpm while passing through nitrogen and the temperature is raised to 70 ° C. 70 g of zinc metal powder is slowly added to react until no more hydrogen gas is generated, and the temperature is raised to 100 ° C. and boiled for 1 hour. After cooling to 80 ° C, the unreacted zinc metal powder is filtered off and dried in a vacuum drying apparatus.

Example 2

365.5 g of lysine hydrochloride are placed in a 2 liter round bottom flask, 1.5 liters of deionized water is added and stirred at 40 rpm while passing through nitrogen and the temperature is raised to 70 ° C. 85 g of zinc oxide is slowly added to react until no further oxygen gas is generated, and the temperature is raised to 100 ° C. for 1 hour. After cooling to 80 ° C, unreacted zinc oxide is filtered off and dried in a vacuum drying apparatus.

Example 3

One liter of animal and plant hydrolyzate (about 35%) is placed in a two liter round bottom flask, diluted with 500 milliliters of deionized water, and stirred at 35 rpm while passing nitrogen to raise the temperature to 75 ° C. 65 g of zinc metal powder is slowly added to react until no more hydrogen gas is generated, and the temperature is raised to 100 ° C. for 1 hour. After cooling to 80 ° C, the unreacted zinc metal powder is filtered off and dried in a vacuum drying apparatus.

Example 4

One liter of animal and plant protein hydrolyzate (about 35%) is placed in a two liter round bottom flask, diluted with 500 milliliters of deionized water, and stirred at 40 rpm while passing nitrogen to raise the temperature to 70 ° C. 85 g of zinc oxide is slowly added to react until no further oxygen gas is generated, and the temperature is raised to 100 ° C. for 1 hour. After cooling to 80 ° C, unreacted zinc oxide is filtered off and dried in a vacuum drying apparatus.

Example 5

365.5 g of lysine hydrochloride are placed in a 2 liter round bottom flask, 1.5 liters of deionized water is added and stirred at 35 rpm while passing through nitrogen and the temperature is raised to 70 ° C. 82 g of cupric oxide is gradually added to react until no further oxygen gas is generated, and the temperature is further raised to 100 ° C. for 1 hour. After cooling to 80 ° C, unreacted cupric oxide is filtered off and dried in a vacuum drying apparatus.

Example 6

365.5 g of lysine hydrochloride are placed in a 2 liter round bottom flask, 1.5 liters of deionized water is added and stirred at 40 rpm while passing through nitrogen and the temperature is raised to 70 ° C. 75 g of cuprous oxide is slowly added to react until no further oxygen gas is generated, and the temperature is raised to 100 ° C. for 1 hour. After cooling to 80 ° C, unreacted cuprous oxide is filtered off and dried in a vacuum drying apparatus.

Example 7

One liter of animal and plant protein hydrolyzate (about 35%) is placed in a two liter round bottom flask, diluted with 500 milliliters of deionized water, and stirred at 35 rpm while passing nitrogen to raise the temperature to 70 ° C. 82 g of cupric oxide is gradually added to react until no further oxygen gas is generated, and the temperature is further raised to 100 ° C. for 1 hour. After cooling to 80 ° C, the unreacted cupric oxide is filtered off and dried in a vacuum drying apparatus.

Example 8

1 liter of animal and plant protein hydrolysates (approx. 35%) is placed in a 2-liter round bottom flask, diluted with 500 milliliters of deionized water, stirred at 40 rpm while passing nitrogen under nitrogen, and the temperature is raised to 70 ° C. Up. 75 g of cuprous oxide is slowly added to react until no further oxygen gas is generated, and the temperature is raised to 100 ° C. for 1 hour. After cooling to 80 ° C, the unreacted cuprous oxide is filtered off and dried in a vacuum drying apparatus.

Example 9

366 g of lysine hydrochloride is placed in a 2-liter round bottom flask, 1.5 liters of deionized water is added and stirred at 40 rpm while passing through nitrogen and the temperature is raised to 70 ° C. 58 g of iron powder are added slowly to dissolve to generate hydrogen gas. The temperature is raised to 100 ° C. again, heated until no more hydrogen is generated, and then cooled. When the temperature reaches 80 ° C., the unreacted substance is removed by filtration and then dried in a vacuum drying apparatus.

Example 10

366 g of lysine hydrochloride is placed in a 2 liter round bottom flask, 1.5 liters of deionized water is added and stirred at 35 rpm while passing through nitrogen and the temperature is raised to 70 ° C. 70 g of ferrous oxide powder are added slowly to dissolve. The temperature was raised to 100 ° C. again for 1 hour, and then cooled to 80 ° C., filtered to remove unreacted material, and then dried in a vacuum drying apparatus.

Example 11

One liter of animal and plant hydrolyzate (about 35%) is placed in a two liter round bottom flask, diluted with 500 milliliters of deionized water, and heated with stirring at 40 rpm while passing through nitrogen. Maintain the temperature to 70 ° C. and slowly add 60 g of iron powder. The temperature is raised to 100 ° C. again for 1 hour. After cooling to 80 ° C, the unreacted iron powder is filtered off and dried in a vacuum drying apparatus.

Example 12

1 liter of animal and plant protein hydrolyzate (about 35%) is placed in a 2-liter round bottom flask, diluted with 500 milliliters of deionized water, and then heated to nitrogen and heated to a temperature of 70 ° C. 65 g of powder is slowly added to dissolve. After the generation of oxygen is completed, the temperature is raised to 100 ° C and reacted for another hour. Cool to 80 ° C, filter to remove unreacted ferrous oxide powder, and then dry in a vacuum drying apparatus.

Example 13

366 g of lysine hydrochloride are placed in a 2-liter round bottom flask, dissolved by adding 1.5 liters of deionized water, and heated with nitrogen. The temperature is raised to 70 ° C. and 50 g of metal manganese powder is slowly added while stirring at a speed of 40 rpm. The mixture is stirred until no more hydrogen gas is generated, the temperature is raised to 100 ° C, and further reacted for 1 hour. After cooling to 80 ° C, unreacted manganese powder is filtered off and dried in a vacuum drying apparatus.

Example 14

366 g of lysine hydrochloride are placed in a 2-liter round bottom flask, dissolved by adding 1.5 liters of deionized water, and heated with nitrogen. The temperature is raised to 70 ° C, and 120 g of manganese carbonate is slowly added to dissolve while stirring at a speed of 35 rpm. Carbon dioxide gas is generated during the reaction, and the mixture is stirred until no carbonic acid gas is further generated, and the temperature is raised to 100 ° C. for further reaction for 1 hour. After cooling to 70 ° C, unreacted manganese carbonate is filtered off and dried in a vacuum drying apparatus.

Example 15

One liter of animal and plant protein hydrolyzate (about 35%) is placed in a two liter round bottom flask, diluted with 500 milliliters of deionized water, heated with nitrogen and heated to 75 ° C. While stirring at a speed of 40 rpm, 50 g of metal manganese powder is slowly added to dissolve. Note that hydrogen gas is generated during the reaction, and the temperature is raised to 100 ° C. for 1 hour. After cooling to 80 ° C, the unreacted metal manganese powder is filtered off and dried in a vacuum drying apparatus.

Example 16

One liter of animal and plant protein hydrolyzate (about 35%) is placed in a two liter round bottom flask, diluted with 500 milliliters of deionized water, heated with nitrogen and heated to 70 ° C. Slowly add 120 g of manganese carbonate while stirring at a speed of 30 rpm to dissolve. Note that carbon dioxide gas is generated during the reaction, and the temperature is raised to 100 ° C. again for 1 hour. The reaction solution is cooled to 75 ° C, unreacted manganese carbonate is filtered off and dried in a vacuum drying apparatus.

Example 17

366 g of lysine hydrochloride is placed in a 2-liter round bottom flask and dissolved by adding 1.5 liters of deionized water. The mixture is heated with stirring at a speed of 30 rpm to pass air through nitrogen gas while maintaining the liquid temperature at 70 ° C. Slowly add 100 g of cobalt carbonate, and continue stirring until no more carbonic acid gas is generated during the reaction, and the temperature is raised to 100 ° C. again for 1 hour. The solution is cooled to 75 ° C, unreacted cobalt carbonate is filtered off and dried in a vacuum drying apparatus.

Example 18

366 g of lysine hydrochloride is placed in a 2-liter round bottom flask and dissolved by adding 1.5 liters of deionized water. The mixture is heated with stirring at a speed of 35 rpm to raise the liquid temperature to 70 ° C, and the nitrogen gas is passed to block the air. 70 g of cobalt hydroxide is gradually added to dissolve, and the temperature is raised to 100 ° C. again to further react for 1 hour. The solution is cooled to 70 ° C, unreacted cobalt hydroxide is filtered off and dried in a vacuum drying apparatus.

Example 19

One liter of animal and plant protein hydrolyzate (about 35%) is placed in a two liter round bottom flask, diluted with 500 milliliters of deionized water, heated with nitrogen and heated to 70 ° C. Slowly add 100 g of cobalt carbonate while stirring at a speed of 35 rpm to dissolve. Keep stirring until the carbonic acid gas generated during the reaction no longer occurs, and the temperature is raised to 100 ° C for 1 hour for further reaction. The reaction solution is cooled to about 70 ° C., and unreacted cobalt carbonate is filtered off and dried in a vacuum drying apparatus.

Example 20

One liter of animal and plant protein hydrolyzate (about 35%) is placed in a two liter round bottom flask, diluted with 500 milliliters of deionized water, and heated slowly with nitrogen to maintain the liquid temperature at 70 ° C. Slowly add 70 g of cobalt hydroxide while stirring at 35 rpm to dissolve. The temperature is again heated to 100 ° C. or higher and allowed to react for another hour while boiling. The reaction solution is cooled to about 70 ° C., and unreacted cobalt hydroxide is filtered off and dried in a vacuum drying apparatus.

Example 21

366 g of lysine hydrochloride is placed in a 2-liter round bottom flask and dissolved by adding 1.5 liters of deionized water. The mixture is heated with stirring at a speed of 30 rpm to raise the liquid temperature to 70 ° C, and the nitrogen gas is passed to block the air. 99.5 g of chromic anhydride (CrO) is gradually added to dissolve, and the heating is continued to allow the liquid temperature to reach a boiling point of 100 ° C. or higher, and the reaction is further continued for 1 hour. The solution is cooled to 70 ° C, the impurities are filtered off and dried in a vacuum drying apparatus.

Example 22

366 g of lysine hydrochloride is placed in a 2-liter round bottom flask and dissolved by adding 1.5 liters of deionized water. The mixture is heated with stirring at a speed of 30 rpm to raise the liquid temperature to 75 ° C., and the air is passed through nitrogen gas. 100 g of chromium hydroxide [Cr (OH) ₃ ] is gradually added to dissolve, and the heating is continued to allow the liquid temperature to reach a boiling point of 100 ° C. or higher, and the reaction is further carried out for 1 hour. The solution is cooled to 75 ° C, the unreacted chromium hydroxide is filtered off and dried in a vacuum drying apparatus.

Example 23

One liter of animal or plant hydrolyzate (about 35%) is placed in a two liter round bottom flask, diluted with 500 milliliters of deionized water, and heated slowly with nitrogen to raise the liquid temperature to 70 ° C. Slowly add 100 g of chromium hydroxide while stirring at a speed of 40 rpm to dissolve. The solution is continuously heated to raise the temperature to 100 ° C. or higher for 1 hour. The reaction solution is cooled to 75 ° C., and unreacted chromium hydroxide is filtered off and dried in a vacuum dryer.

Example 24

366 g of lysine hydrochloride is placed in a 2-liter round bottom flask and dissolved by adding 1.5 liters of deionized water. Heat through nitrogen gas to raise the liquid temperature to 75 ° C. 144 g of molybdenum oxide (MoO ₃ , Mo ₂ O ₃ ) is slowly added to the solution while the solution is stirred at a speed of 40 rpm. The solution temperature is raised to 100 ° C. again, and further reacted for 1 hour. After completion of the reaction, the solution is cooled to 70 ° C, unreacted molybdenum oxide and impurities are filtered off, and then dried in a reduced pressure drier.

Example 25

One liter of animal or plant hydrolyzate (about 35%) is placed in a two liter round bottom flask, diluted with 500 milliliters of deionized water, and heated with nitrogen to raise the liquid temperature to 75 ° C. Slowly add 140 g of molybdenum oxide while stirring at a speed of 40 rpm to dissolve. When the amount of oxygen gas generated during the reaction is significantly reduced, the temperature is raised to 100 ° C and allowed to react for another hour. After completion of the reaction, the reaction solution is cooled to 70 ° C, unreacted molybdenum oxide and impurities are filtered off and dried in a vacuum drying apparatus.

As described and demonstrated in detail above, the present invention forms a chelate bond in which both the amino group and the carboxyl group of the amino acid are combined with the metal to form a ring structure, thereby forming a stronger bond than the general ionic bond of the inorganic compound. In addition, highly stable metal chelates are produced that do not undergo ionization or degradation until they are used in cells in vivo. Therefore, when the organic metal material according to the present invention is administered to the livestock as a feed additive, the conventional inorganic metal material is ionized in the organs in vivo to show toxicity, deteriorate in bioavailability, or are not absorbed. It can be discharged outside as it is to contaminate the environment, such as polluting the environment.

Claims (2)

Organic metals produced by chelation of an aqueous solution of pH 5.5 to 8.5 of an amino acid or a hydrolyzate of an animal / vegetable protein with a powder, oxide, carbonate or hydroxide of a metal in an inert gas at a temperature ranging from 60 ° C. to the boiling point of the solution How to synthesize. An organic metal material produced by chelation of an aqueous solution of pH 5.5 to 8.5 of an amino acid or an animal / vegetable protein hydrolyzate with a metal powder, oxide, carbonate or hydroxide in an inert gas at a temperature ranging from 60 ° C. to a boiling point of the solution. Animal feed containing.