KR20190041751A - Composition of supplementary feed comprising chitosan-mineral complex and preparing method thereof - Google Patents

Abstract

The present invention relates to a supplementary feed composition comprising a chitosan-mineral complex. More particularly, the present invention relates to a supplementary feed composition in which a bioabsorption ratio and an immune-enhancing effect of chitosan and minerals are increased by mixing a specific combination of minerals and chitosan having a specific size at a predetermined ratio. The supplementary feed of the present invention maintains constant solubility and stability of high-dose activated minerals without being influenced by a temperature condition as compared with conventional feed, and thus has an excellent effect of increasing an absorption rate in the body twice or more than that of the conventional feed by being added to drinking water and provided to a livestock house.

Description

[0001] The present invention relates to an auxiliary feed composition comprising a chitosan-mineral complex and a preparation method thereof,

The present invention relates to a chitosan-complex mineral complex using a chelate method and a method for producing the same.

Ancillary feed refers to additives used to improve functionalities such as digestive power, physiological activity, growth promotion, and immunity enhancement of livestock products added to compound feeds. Livestock industry generally promotes livestock growth and prevents or treat diseases of livestock (Brücke et al., 2004, pp. 793-797), antibiotics are used as antibiotics (Guo, FC et al. The use of antibiotics is increasingly regulated in that the frequent use of substances increases the resistance of microorganisms and causes the antibiotic efficacy to deteriorate or to remain in the livestock products and adversely affect the human body (Chae, MH et al., 2011, Antimicrobial resistance in Campylobacter jejuni and Campylobacter coli isolated from food animals and raw meats in slaughterhouse in Korea during 2010, T. Publ. Hilth., 35, 239-245).

Physicochemical and biological studies of minerals, one of the five nutrients absolutely necessary for humans and livestock, have been recently studied with a focus on livestock feed research. In the past, minerals and minerals were widely used as animal feed additives, but the utilization rate in the animal body was only 20 ~ 30% and the rest was excreted in the manure, resulting in resource waste and environmental pollution problems. Chelated minerals chelated with organic compounds such as proteins or carbohydrates have been used, and their absorption capacity has been reported to be extremely high (70-80%) (Kratzer and Vohra, 1986). These chelated minerals Various production methods are known (US2877253, US5061815, US5504055, US6458981 B1, US7087775 B2, US7375243 B2, US2008 / 0248583 A1).

On the other hand, chitosan is a linear polysaccharide composed of D-glucosamine and N-acetylglucosamine. It has various functions such as antimicrobial action, lowering of cholesterol in blood, lowering of fat and enhancing action of heavy metal detoxification, . However, since chitosan is insoluble in water, it is insoluble in water, and when used in a powder state, it is not easily absorbed in a living body of an animal or human, and thus there is a problem that the effect on the physiological activity of chitosan is insufficient. Therefore, it is required to use chitosan in water for animal feed or food.

However, most commercial livestock immune enhancers have a powder form such as vitamins, minerals, and probiotics, and are used for feed addition. Therefore, they have a low water absorption rate compared to the drinking water administration. When they are dissolved in water for drinking water administration, they have low solubility and non- Deterioration, nipple clogging, and the like.

In the related art using chitosan and minerals, Patent Document 0001 (KR 10-2001-0066982) discloses a method of synthesizing a chitosan-metal chelate substance by chelating zinc, copper or chromium by adding a solution of low molecular weight chitosan dissolved in an organic acid I am suggesting. However, the solidified preparation prepared according to the above patent document has a disadvantage in that a dispersant, a suspending agent or a stabilizer is additionally required due to low solubility when it is applied by a drinking water administration method.

Patent Document 0002 (KR 10-0814012) discloses a method for producing a chitosan-selenium complex in the form of chitooligosaccharide by binding selenium with chitosan and then decomposing the chitosan with a chitosanase. However, this is not an application to various mineral elements, and the manufacturing process is somewhat complicated and involves a lot of cost and effort.

Accordingly, there is a need for a method of providing a water-soluble chitosan-complex mineral for supplying chitosan and various minerals with a high bioabsorption ratio.

Korean Patent Publication No. 10-2001-0066982 Korean Patent Publication No. 10-0814012

As a result of continuous efforts to develop a livestock enhancer capable of replacing antibiotics, the present inventors have found that when a combination of certain kinds of minerals is activated by chitosan, it has high solubility and stability in an aqueous solution, And accelerates the growth, thereby completing the present invention.

Accordingly, the present invention provides a method for producing a chitosan-mineral complex having an excellent water solubility and long-term storage stability as well as a bioavailability and an effective immune response as an active ingredient of a liquid supplementary feed for drinking water administration .

Another object of the present invention is to provide a liquid feed supplement composition containing the chitosan-mineral complex produced by the above production method as an active ingredient.

In order to achieve the above object, the present invention provides an auxiliary feed composition comprising chitosan chelated with a complex mineral and minerals composed of cobalt, vanadium and selenium.

The present invention also provides a method for producing a chitosan solution, comprising: a first step of preparing a chitosan solution by adding chitosan while stirring purified water; A second step of sequentially introducing vanadium sulfate, cobalt sulfate, and selenium oxide while stirring the chitosan solution obtained in the first step and inducing a metal chelate reaction between the complex ion mineral and chitosan; Adding an organic acid to the solution in the second step; And a fourth step of taking an upper part of the solution in which the third step is carried out.

The auxiliary feed composition comprising the three mineral complex and chitosan according to the present invention has an effect of preventing the disease of the poultry without reducing the cytotoxicity and decreasing the mortality rate.

The present invention shows a remarkably excellent effect of solubility, uniformity and stability by using the solution itself in which metal chelate reaction of a complex ion mineral and chitosan proceeds at a specific ratio as a liquid preparation.

Further, by selectively using chitosan having a specific molecular weight, it is possible to maximize the reactivity of the chelate in the aqueous solution and maximize the immune enhancing effect.

In addition, since the solubility and homogeneity of the chitosan-mineral complex remain constant regardless of the pH and temperature conditions, it can be conveniently applied to the house without the clogging of the nipple even when added to the drinking water. There is an excellent effect that the absorptivity in the body is increased.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows an automatic dosing device required for application of the composition of the present invention to drinking water in addition to drinking water.
Figure 2 shows the solubility and stability of chitosan-complex mineral chelates upon addition of various organic acids.
FIG. 3 shows the synthesis process of the chitosan-complex mineral chelate of the present invention.
4 is a graph comparing cytotoxicity of the supplementary feed composition of the present invention and the composition of the comparative example.

The present invention overcomes the conventional conjecture that solid formulations such as vitamins, minerals, plant extracts, and probiotics are used for the purpose of feed addition, and adds a highly concentrated liquid preparation in which organically activated complex minerals are stably and uniformly dissolved to the drinking water Thereby providing a new concept of an auxiliary feed composition for immune augmentation that shows a water absorption rate twice as high as that of water through conventional feeds and has a high stability (solubility, uniformity, etc.) and can maximize application convenience and disease defense efficacy will be.

Further, the present invention is characterized by using the chelate method. When inorganic mineral minerals are surrounded by polymer organic materials and chelated, cells recognize inorganic minerals as organic and increase the absorption rate in the body. The present inventors have developed a novel feed supplement composition which is capable of supplying a uniform minerals in vivo as a drinking water preparation by containing a complex micro-minerals in a polymer, unlike the prior art which chelates a low molecular buffer and a single metal.

However, the polymer buffer should take into consideration the solubility for cytotoxicity and chelating reaction and the problem of bioabsorbability after the reaction, in particular the solubility and absorbency depending on the ratio of mineral and buffer. Therefore, the present inventors selected chitosan, a natural substance, as a polymer buffer for chelating reaction.

As used herein, "chitosan" is a polyglucosamine obtained by deacetylation of chitin present in crab shells and the like, which does not cause rejection in the body, and is effective in growth promotion, immunity enhancement, physiological activity, inhibition of pathogenic bacteria growth, It is possible to solve the problem of cytotoxicity of polymer because it has properties of digestive function and detoxification, and can be used together with minerals to synergistically induce the immune enhancement effect.

Generally, the effect of chitosan varies greatly depending on the molecular weight, degree of deacetylation, and degree of water solubilization. In the case of chitosan oligosaccharides whose molecular weight is not so large, it is known that immunosuppression is lower than that of high molecular weight chitosan.

In the present invention, the chitosan has a molecular weight of 5,000 to 50,000 Kda. When the molecular weight is small, the immunostimulating effect is lowered and the chelate reactivity with the mineral is lowered. When the molecular weight is too low, the water solubility is limited even when the chitosan is too high. Most preferably, the case of having a molecular weight of 5,000 to 10,000 maximizes the absorption rate and utilization rate in the body.

The chitosan of the present invention preferably has a degree of deacetylation of 60 to 80% and most preferably 70% of deacetylation.

On the other hand, the auxiliary feed composition of the present invention is in the form of a liquid and is an aqueous solution. In order to dissolve chitosan in an aqueous solution in water, a charge or a polar functional group is required. Specifically, in the case of chitosan, the number of functional groups capable of chelating with minerals is about 30-40. Therefore, it is necessary to control the solubility in water and the absorbability of water by setting a suitable ratio without using all functional groups in consideration of water solubility and fat solubility.

Therefore, in order to select minerals that can enhance the immunity enhancing effect of chitosan in consideration of the solubility and the absorbability of chitosan, zinc, copper, selenium, iron, magnesium, manganese, phosphorus, potassium, calcium, sodium, Molybdenum, cobalt, and so on, in order to search for and select immunopotentiating substances.

To synthesize water-soluble chitosan-complex mineral chelates, a method of selecting a combination of minerals and determining the ratio of mineral to chitosan is as follows.

In the first step, the solubility differences, mineral content and mineral / buffer ratio should be determined. The differences in solubility of minerals were as follows. VOSO ₄ , CuSO ₄ (5H ₂ O) > MnSO ₄ > _{NiSO 4 (7H 2 O)>} CoSO 4 (7H 2 O)> ZnSO 4 (7H 2 O)> SeO 2> CrSO 4 (5H 2 O)> MoO 3. Therefore, in order to prevent precipitation of low-solubility minerals, it reacts with the polymer buffer sequentially from low-solubility minerals. The contents of mineral minerals were Zn (12mg), Mn (2mg), Cu (1.5mg), Se (0.05mg), Mo (0.025mg), V (0.015mg) and Co After selecting the complex mineral preparation selected according to the ratio, the synthesis is started from the ratio of the complex mineral to the polymer buffer (mineral: chitosan = 0.3-0.5: 1).

In step 2, the degree of chelation should be measured according to reaction temperature and reaction time to find the appropriate reaction conditions. First, measure the reaction time and time at room temperature. If the temperature needs to be increased, increase the reaction rate by 15 ^° C to determine the degree of reaction. When the amount of inorganic minerals remaining in the aqueous solution is high, the amount of the mineral is measured by ICP-AES (inductively coupled plasma atomic emission spectrometer) through an aqueous solution containing no polymer buffer through filtration or dialysis. The amount of inorganic minerals in the aqueous solution is too small to measure the polymer buffer and the amount of minerals chelated. If solids are precipitated, the ratio of complex mineral / polymer buffer should be adjusted again, and vice versa, if there is no solid residue, the reaction should be carried out with a higher ratio of complex mineral / polymer buffer.

 When the reaction was completed in three steps, the remaining inorganic minerals were removed by filtration or dialysis to confirm the presence of minerals. The amounts of minerals were measured by ICP-AES and confirmed by several experiments under the same conditions.

Through the above process, the auxiliary feed composition of the present invention is characterized in that it contains chitosan chelated with complex minerals composed of selenium, cobalt and vanadium and minerals as an active ingredient.

According to a preferred embodiment of the present invention, the auxiliary feed composition of the present invention preferably contains 0.05 to 1.5 parts by weight of chitosan, 0.1 to 0.3 parts by weight of cobalt, 0.05 to 0.15 parts by weight of vanadium, and 0.1 to 0.35 parts by weight of selenium.

When the amount of chitosan is excessive, the absorption rate of chitosan is decreased. When the amount of chitosan is too small, the amount of activated minerals is decreased and the bioavailability of minerals is decreased. Further, if the content of any component in the complex minerals is out of the above range, there is a problem that the efficiency of the auxiliary feed is deteriorated by precipitation into crystals without being chelated with chitosan.

According to a preferred embodiment of the present invention, the supplementary feed composition of the present invention preferably further comprises citric acid. To completely dissolve chitosan in an aqueous solution, it is necessary to maintain the liquidity at pH 4 or less. For this purpose, organic acids such as acetic acid, oxalic acid and citric acid can be used. In general, it is known that acetic acid is the most stable when chitosan is dissolved. However, according to Experimental Example 1 of the present invention, acetic acid is excessively required to completely dissolve chitosan. When the solution is in a clear aqueous solution, . In addition, since oxalic acid does not produce a clear aqueous solution even when it is used in excess, it is preferable to use citric acid in order to completely dissolve chitosan.

According to a preferred embodiment of the present invention, the content of citric acid is preferably 0.2 to 0.6% by weight based on the total weight of the composition. If the content of citric acid is too small, the chitosan-complex mineral chelate does not sufficiently dissolve in the aqueous solution to form a precipitate, resulting in deterioration of the efficiency of the liquid feed. If the content of citric acid is excessively large, the liposoluble property of chitosan becomes small, There is a problem that the water absorption rate is lowered.

The present invention relates to a chitosan solution comprising a first step of preparing a chitosan solution by adding chitosan while stirring purified water; A second step of sequentially introducing vanadium sulfate, cobalt sulfate, and selenium oxide while stirring the chitosan solution obtained in the first step and inducing a metal chelate reaction between the complex ion mineral and chitosan; Adding an organic acid to the solution in the second step; And a fourth step of taking an upper part of the solution in which the third step has been carried out.

According to a preferred embodiment of the present invention, the organic acid is preferably citric acid. In the present invention, the organic acid is added to the second step solution in which the chelating reaction proceeds, instead of the first step of preparing the chitosan solution.

As described above, the reason for adding the organic acid is to completely dissolve chitosan. In the present invention, the chitosan solution to which the organic acid is not added and the mineral are first subjected to the chelate reaction so that the chitosan can react with the mineral at 20 to 30 The solubility in water and the absorption capacity of the body can be controlled by controlling the ratio of the complex mineral and the buffer by using only a moderate degree of the functional groups of the functional groups.

According to a preferred embodiment of the present invention, the chitosan solution of the first step is preferably prepared at a temperature of 24 ± 1 ° C. When the temperature of the chelate reaction is not maintained at room temperature, the chelate reaction may be reversed or a precipitate may be formed when the liquid composition is applied to drinking water at room temperature.

According to the present invention, the supplementary feed composition of the present invention can be used for immunization enhancement of livestock in the livestock industry.

In the present invention, chitosan, which is a pure natural substance showing a synergistic effect by mixing with minerals, is known to have excellent antibacterial and immunostimulating effects. The effects of vanadium, cobalt and selenium selectively activated through the chelate reaction with chitosan in the present invention are as follows.

Vanadium (V) promotes hematopoietic function, stimulates iron regeneration, acts on the muscle of the cardiac glycoside, and strengthens myocardial contractility. Therefore, vanadium deficiency affects high cholesterol disease, metabolic abnormalities of serum lipids, anemia, arteriosclerosis and angina pectoris.

Cobalt (Co) is a component of vitamin B12, and it is essential for the normal function of skeletal, nervous, and gastrointestinal cells, preventing hemorrhage and anemia. Cobalt deficiency causes malaise, anemia, anorexia, dyspepsia, loss of limbs and nervousness.

Selenium (Se) is a toxic substance such as a component of peroxidase enzyme of glutathione, GSH-RH activity enhancement, lipid and oxidation cell protection, antioxidant activity, anti-aging minerals, beauty minerals, carcinogens and arsenic, cadmium, It is known that the harmful effects of this organism on resistance and anticancer effects are known. The diseases of 40 kinds such as cancer, heart disease, diabetes, extreme acidosis and infertility are all related to selenium deficiency, and selenium deficiency causes myocardial necrosis, Increase in cholesterol, decrease in strength, decrease in strength, decline in strength, decrease in strength, decrease in strength, increase in cholesterol, increase in cholesterol, increase in cholesterol .

In the present invention, chitosan having a low cytotoxicity and excellent immunity enhancing effect by itself is used as a buffer to maximize the bioavailability of minerals (FIG. 4).

In addition, chelate reaction of chitosan and complex minerals composed of vanadium, cobalt and selenium at a specific weight ratio can harmonize the reactivity of chitosan and minerals and the bioabsorption of chitosan, thereby synergistically inducing the immune enhancement effect of minerals and chitosan.

In addition, the minerals dissolved in the liquid composition of the present invention are organicized by the buffering action of chitosan, dissolved in the active water uniformly in the active state, and continuously supplied to the poultry, thereby being effectively used for enhancing the immunity of the livestock .

According to a preferred embodiment of the present invention, the liquid feed supplement composition containing the chitosan-mineral complex to the poultry can be added to the feed water, and it is preferable that the feed composition is added at a rate of 30,000 to 60,000: 1 And the like.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Production example. Preparation of drinking water with minerals

Using the automatic dosing apparatus shown in FIG. 1, drinking water was prepared by adding the composition of Example 1 per 1 ton of feed water in a ratio of 60: 1, and for comparison, drinking water mixed with conventional powder type minerals was prepared After each drinking water was directly applied to the house, the results were compared and evaluated, and the results are shown in Table 1 below.

division Mineral or solidified chelating agents Activated mineral-containing liquid formulation Depending on the type of benefit
Absorption rate - The majority of feed diets
- Low Absorption Rate  - Maximization of absorption rate by applying drinking water Ease of Use and Persistence - Intermittent drinking water administration
- Nipple clogging, low persistence -365 days continuous administration
- Pay in proportion to water usage
- Easy and quick convenience of applying whole house For water
Solubility - low solubility in water
- Cause excessive use  - Excellent solubility and homogeneity at room temperature using liquid formulations in which activated minerals are dissolved.
Activation - Mostly deposited on the walls and floors to be treated.
- Jonny phenomenon occurred  - High solubility and storage stability in water and high activity of minerals Uniformity  Minute uniformity  Maintain uniformity regardless of -pH and temperature conditions

Bioabsorption rate - In the case of inorganic minerals, the bioavailability is low due to absorption method, absorption site, intestinal pH, and binding with anion materials
- Organic form of minerals has low solubility in water and low bioavailability - active absorption, diffusion absorption, absorption rate is high
- After passing through the stomach without extra ionization process, it is absorbed in the small intestine and absorbed into the plasma through the cell membrane.
- Less affected by intestinal pH or other obstructing substances

Based on the above results, it has been found that the composition for immune enhancement, which is prepared from activated minerals in a liquid form, exhibits a water absorption rate 2 times higher than the water absorption rate through the feed of drinking water and has a higher water solubility and uniformity than conventional mineral powders , Bioabsorbability, convenience of application, and the like.

Example .

The chitosan-complex mineral chelate was prepared by dissolving chitosan in the formulation shown in Table 2 and adding a small amount of metal salt to prepare an aqueous solution in which the chitosan-complex mineral chelate was dissolved, followed by the addition of citric acid. To prepare a completely dissolved aqueous solution. The properties of the compositions of Examples 1 to 5 prepared are shown in Table 3 below.

Example
One Example
2 Example
3 Example
4 Example
5 Comparative Example
One Comparative Example
2 Chitosan (chitooligosaccharide) 0.05 1.0 1.0 1.5 1.5 0.05 1.5 Cobalt sulfate (CoSO ₄ .7H ₂ O) 0.1 0.2 0.2 0.3 0.3 0.1 0.3 Vanadium sulfate (VOSO ₄ .H ₂ O) 0.05 0.1 0.1 0.15 0.15 0.05 0.15 Selenium oxide (Na ₂ SeO ₃₎ 0.1 0.2 0.2 0.35 0.35 0.1 0.35 Citric acid 0.2 0.3 0.4 0.4 0.5 0.1 0.6 Purified water Remainder Remainder Remainder Remainder Remainder Remainder Remainder Sum 100 100 100 100 100 100 100

(Unit: parts by weight)

Chitosan - Mineral Chelate Temperature p H importance Stability 23.2 4.5 1.01 Clear brown liquid

Experimental Example 1. Confirmation of chelate reactivity and solubility according to kinds of organic acids (Fig. 2)

The chitosan-mineral aqueous solution was prepared by adding minerals at a weight of 50% or more to the weight of chitosan and chitosan in purified water. However, since it is not completely chelated and is opaque and precipitates are formed, various organic acids were added as shown in Table 4 to improve solubility in a clear aqueous solution state.

division Chitosan +3 minerals + organic acid Aqueous solution state Remarks One Chitosan (10g) +3 minerals + citric acid O Addition of citric acid 3.8g -> Clear state -> Result of dialysis Clear aqueous solution 2 Chitosan (10g) +3 minerals + acetic acid O -> X Addition of acetic acid 13.84 ml-> clear state-> dialysis result solid formation 3 Chitosan (10g) +3 minerals + oxalic acid X Add 39 g of oxalic acid -> Not in perfect aqueous solution

As a result, the citric acid-added experimental group was improved to a clear aqueous solution state in a small amount, and the best result was obtained (FIG. 2).

Experimental Example  2. Solubility and stability test (Figure 3)

Examples 1 to 5 and Comparative Examples 1 and 2 were visually inspected for their properties. As a result, Examples 1 to 5 maintained the aqueous phase continuously at room temperature without precipitation immediately after the preparation and after the elapse of time, 1 and 2 were precipitated.

Example
One Example
2 Example
3 Example
4 Example
5 Comparative Example
One Comparative Example
2  color clear
Brown clear
Brown clear
Brown clear
Brown clear
Brown opacity
Ocher opacity
Ocher  Appearance Liquid phase Liquid phase Liquid phase Liquid phase Liquid phase Liquid phase Liquid phase  Presence or absence of crystal formation radish radish radish radish radish U U

Experimental Example  3. Cytotoxicity test (Fig. 4)

Cell viability was measured to determine the effect of the composition of the present invention on the PBMC proliferative capacity and cell (cytotoxicity) of chicken. Compared with the chitosan and the sample having the mineral content of the comparative example 5, In order to establish experimental conditions, Concanavalin A (con A), which is a T cell activator, was used for control. Cone A was 20 μg in dose dependent, time dependent treatment and 3days The highest growth rate (A, B) was observed and the best cell number was 1 × 10 ⁶ (C). Example 5 and Comparative Examples 3 and 4 were treated under the same conditions from 1 x 10 ^-2 to 5 x 10 ^-5 to determine the cell viability and to perform the MTT assay.

ingredient Example
5 Comparative Example
3 Comparative Example
4 Chitosan (chitooligosaccharide) 1.5 - - Sulfuric acid - 0.2 0.2 Cobalt sulfate (CoSO ₄ .7H ₂ O) 0.3 0.1 0.3 Vanadium sulfate (VOSO ₄ .H ₂ O) 0.15 0.05 0.15 Selenium oxide (Na ₂ SeO ₃₎ 0.35 0.1 0.35 Citric acid 0.5 0.5 0.5 Purified water Remainder Remainder Remainder Sum 100 100 100

As a result, Comparative Examples 3 and 4 is 1x10 ^-2 ~ 1x10 ^- showed cytotoxicity at the concentration of ^3, Example 5 was not greater toxicity. Overall, good results were obtained when diluted to above 1x10 < ^-4 >

Comparative Example  5. Identification of solubility by searching for the concentration of chitosan and complex minerals

Chitosan (2mM) was found to be a suitable concentration for the chelation reaction. Chitosan was prepared by dissolving chitosan in purified water. Table 8 shows the result of dissolving various minerals in an aqueous solution and slowly injecting them and reacting as shown in Table 7 so that the chelate bonds are well formed.

division Molecular formula Molecular Weight Mineral atomic weight One Polymer chitosan 10,000 - 2 Low molecular weight chitosan 5,000 - 3 CrCl ₃ 6H ₂ O 266.45 51.99 4 MgCl ₂ 6H ₂ O 203.3 24.3 5 FeC4H ₂ O ₄ 169.9 55.84 6 FeCl ₂ 4H ₂ O 198.81 55.84 7 Na ₂ MoO ₄ 2H ₂ O 241.95 95.94 8 ZnSO ₄ 7H ₂ O 287.56 65.38 9 ZnO 81.38 65.38 10 CuSO ₄ 5H ₂ O 249.18 63.54 11 MnSO ₄ H ₂ O 169.01 54.9 12 CoSO ₄ 7H ₂ O 281.12 58.93 13 Na ₂ SeO ₃ 172.94 78.96 14 VOSO ₄ H ₂ O 181 50.94 15 MgO 40.3 24.3

division Chitosan mineral Presence or absence of aqueous solution Remarks One 1g  Cu (640 ppm) O  Aqueous solution state 2 1g  Cu (892 ppm) X  Solid generation 3 1g  Cu (1,274 ppm) X  Solid generation 4 1g  Cu (1,530 ppm) X  -> 100 ml of purified water added (510 ppm) 5 1g  Cu (2,549 ppm) X  Solid generation 6 1g  Se (1,369 ppm) O Se (1,369ppm) is clear (injected into aqueous solution)
The addition of 0.2 g of selenium (powder) (2,282 ppm) 7 10g  Se (4,150 ppm) O  Aqueous solution state 8 1g  Zn (128 ppm), Mn (53 ppm), Cu (46 ppm), Se (12 ppm), Mo (13 ppm) O  Solid production -> 500 ml of purified water (6 ppm) -> Solid production 9 1g  Zn (341 ppm), Se (70 ppm), Cu (97 ppm) O  Aqueous solution state 10 10g  Cu (13,000 ppm) X  After adding 7 ml of 3N H2SO4, 11 10g  V (2,500 ppm), Co (4,000 ppm), Se (10,000 ppm) O Addition of purified water addition
V (250 ppm), Co (400 ppm), Se (1,000 ppm) 12 13g  V (500 ppm), Co (800 ppm), Se (2,000 ppm) X  Experiment with 13 g of chitosan, solid formation when adding Se, addition of 0.6 g of Methionine -> not clear, filtration 1.5 g 13 10g  Mo (956 ppm), Se (789 ppm) O  Aqueous solution state 14 1g  V (28 ppm), Co (40 ppm), Se (100 ppm) X 60 ℃ heat, added purified water
V (14 ppm), Co (20 ppm), Se (50 ppm) -> Solid 15 10g  V (25 ppm), Co (40 ppm), Se (100 ppm) X  Stirring at room temperature for 24 hours, metering pump for 8 hours, filtration 1 g 16 10g  V (25 ppm), Co (40 ppm) X  Stirring at room temperature for 24 hours, metering pump for 8 hours, filtration 0.2 g

As a result of the experiment, it was found that in the case of Cu (640ppm, 1mM) and Se (1,369ppm, 1mM) which are 50% of the chitosan 2mM, 2,282ppm 2.8mM, and Zn 1.5mM) was added to the solution, it was confirmed that the solution solidified substantially. In order to improve this, it was confirmed that the change of solidified state into aqueous solution state was confirmed by changing the temperature, amino acid (Methionine) and pH (H ₂ SO ₄ ). Since the content of minerals that can be reacted with chitosan was low, vanadium, cobalt and selenium were chelated with chitosan in an amount of 1 ppm or less in vivo, and the remaining minerals decided to further investigate the chelate reactivity with amino acids.

Claims (10)

A complex mineral consisting of selenium, cobalt and vanadium, and chitosan chelated to minerals. The auxiliary feed composition according to claim 1, wherein the composition is liquid. The supplementary feed composition according to claim 1, wherein the chitosan has a size of 5000 to 10,000 Kda. The auxiliary feed composition according to claim 1, comprising 0.05 to 1.5 parts by weight of chitosan, 0.1 to 0.3 parts by weight of cobalt, 0.05 to 0.15 parts by weight of vanadium, and 0.1 to 0.35 parts by weight of selenium. The supplementary feed composition of claim 1, further comprising citric acid. 6. The supplemental feed composition according to claim 5, wherein the content of citric acid is 0.2 to 0.6% by weight based on the total weight of the composition. The supplementary feed composition according to claim 1, wherein said supplementary feed composition is for immunization of livestock. A first step of preparing a chitosan solution by adding chitosan while stirring the purified water;
A second step of sequentially introducing vanadium sulfate, cobalt sulfate, and selenium oxide while stirring the chitosan solution obtained in the first step and inducing a metal chelate reaction between the complex ion mineral and chitosan;
Adding the organic acid to the solution in which the second step has been performed, and
And a fourth step of taking the upper part of the solution in the third step. 9. The process according to claim 8, wherein the organic acid is citric acid. 9. The method according to claim 8, wherein the chitosan solution of the first step is prepared at room temperature of 24 占 폚.

Images