KR20060102373A - Manufacturing method of calcium binding amino acid - Google Patents

Abstract

The present invention simultaneously extracts peptide (peptide), an amino acid conjugate, calcium (Ca) and phosphorus (P) from animal bone tissue (especially bone frame) to induce phosphorylation of amino acid peptides. The present invention relates to a method for producing an amino acid calcium, characterized by combining the resulting phosphorylated amino acid peptide and the extracted calcium, more specifically, the bone frame, organic acid and protein in a bioreactor composed of a temperature and pH controller and a stirrer. Adding a hydrolase, and reacting the mixture by stirring at 35 to 45 ° C. for 4 to 10 hours; A separation process of filtering and separating only those having a predetermined molecular weight or less using an ultra-filtering system; And the drying process, while the extraction of calcium and phosphorus and hydrolysis of the protein is carried out simultaneously in the reaction process, the phosphorylation of amino acid peptides and the process of binding calcium at the same time by the process of producing excellent amino acid calcium absorption in the human body Economic efficiency was achieved.

Fish bone frame, calcium, phosphorus, phosphorylated, amino acid peptide

Description

Manufacturing method of calcium binding amino acid

1 is a schematic process diagram for the preparation of the calcium calcium amino acid according to the present invention.

Figure 2 is a comparison of the recovery rate of separation of the amino acid calcium by the filtration system.

The present invention relates to a method for producing amino acid calcium which is a water-soluble natural calcium binder from animal bone tissue, in particular a bone frame.

Calcium is the most abundant mineral element in the human body, and the average adult has about 1000% to 1200g, about 2% of the body weight. 99% of the body's calcium forms bones and teeth, and only 1% of the body's calcium is responsible for regulating physiological activities such as muscle contraction and relaxation, regular heartbeat, blood coagulation, enzyme activation, intracellular stimulation and excitement delivery. Doing.

In particular, calcium plays an important role in reducing the incidence of chronic diseases such as osteoporosis, hypercholesterolemia, arteriosclerosis, hyperlipidemia, hypertension, and therefore proper calcium nutrition should be maintained at all times. The daily recommended amount of calcium is about 700mg. It is very important to consume calcium through food, but in fact, even if you eat food containing calcium, the absorption rate of calcium in the body is very low. Only 45% of the situation is eating.

In order for calcium to be absorbed in the body, it must be present in soluble form when passing through mucosal cells in the small intestine where calcium is absorbed. However, since the small intestine is weakly alkaline, it is impossible for calcium, an essential mineral, to exist in an ionic state. Therefore, calcium cannot maintain the state of ions in the mucosa without relying on special structures.

In other words, when water-soluble mineral ions produced in the stomach are not protected by a compound having a special structure, they are combined with excess phosphoric acid during the duodenum to form calcium phosphate, which is a non-absorbent mineral, and is released into the powder.

On the other hand, efforts have been made to improve the absorption rate of a commercial calcium agent in the human body in connection with the related art. As a result, oligopeptides obtained by decomposing proteins with specific enzymes and phosphorylated proteins chemically modified with specific proteins or peptides Or attempts have been made to use peptides. The most well-known technique is CPP (casein phospho peptide) made by hydrolyzing casein protein in milk with enzyme trypsin, which is phosphorylated with serine residue of casein, which is combined with soluble calcium in the small intestine to facilitate the absorption of the body. Naito et al .: Agricultural and Biological chemistry, 36: 409-, 1972.

In addition, trypsin decomposition of milk protein, casein, has been shown to be effective in preventing the formation of insoluble substances such as calcium phosphate, which is combined with metal ions such as calcium and iron, forms soluble complexes, and excreted outside the body (Reeves et al.). : Science, 128: 474-. 1958).

As the above-mentioned prior art, for example, a method of manufacturing fish bone meal obtained by separating bones from fish and drying them is known (Japanese Patent Application Laid-Open No. 2-231059, Japanese Patent Application Laid-open No. 4-121166). It takes a lot of energy to dry. In addition, after washing the fish bones in high pressure water to decompose the remaining protein with hydrolase, washing and removing the dried bones by vacuum heating evaporation method and then pulverized to produce fish bone meal (Japanese Patent Laid-Open) 2-231059) is known, but the low calcium content of the product thus produced is a disadvantage. On the other hand, in order to solve the additional problem, Japanese Patent Laid-Open No. 6-319487 discloses a method for producing water-soluble calcium by softening by dipping fish bones in acetic acid, but the process is complicated and liquid beverage Since it cannot be used other than this, its use is limited and it is not widely used.

As related prior patents in Korea, Patent Nos. 10-0403284 and 10-0399722 disclose methods for producing fish bone meal, water-soluble calcium, and calcium absorption promoting peptides from fish bones. The process of extracting tuna from the intestine is complicated, and in the case of water-soluble calcium, there is a problem that it is difficult to be widely used from an economic point of view.

In addition, the prior art for producing a casein phospho peptide (CPP), a calcium absorption accelerator that is widely used all over the world, there is a U.S. Patent No. 4,358,465 (1982) and Japanese Patent Publication (Heb. 2-7616, 1990) and the like. The technology differs only in the kind of enzyme used in the decomposition of sodium casein, separation, and purification methods, but the principles and processes are the same. Therefore, the hydrolysis process, the separation and purification process, and the artificially added calcium, a chemical synthesis product, It consists of a series of processes combined with CPP and dried, and the process is designed as a separate independent system.

In order to solve the above problems, an object of the present invention, by putting the organic acid and the hydrolase at the same time in the fresh fish bone frame secured to the safe fish species and reacts, calcium (Ca) and phosphorus (P) which is a natural mineral component By decomposing and extracting amino acid peptides, phosphorylating the decomposed amino acid peptides, and combining the extracted calcium, it provides a method for producing amino acid calcium, which is water-soluble and has excellent product safety and absorption in the human body.

In addition, the extraction, phosphorylation and calcium binding process of each active ingredient can be carried out under a single process, and it is composed of a recycling process for recycling the hydrolase which occupies a substantial part of the raw material cost in the hydrolysis and extraction stages. The present invention provides a method for producing amino acid calcium having high economic efficiency in manufacturing process through cost reduction effect.

The present invention relates to the extraction of inorganic calcium, phosphorus and amino acid peptides from a bone frame (with muscle proteins attached to the bone), ii) phosphorylation of amino acid peptides, and iii) amino acid by binding of phosphorylated peptides and calcium. Reaction steps for forming a composition containing calcium, i) separation of calcium amino acid, and i) drying step for drying the calcium amino acid composition are the centers.

In particular, by carrying out the process of i) ii) iii) i) under a single process (single system), the economic efficiency in the manufacturing method was achieved.

In order to achieve the above object, the present invention provides a method for preparing calcium calcium amino acid, a protein frame in a bioreactor composed of a temperature controller and a stirrer (fish bone frame (with muscle protein coupled to the bone)) and organic acid and protein hydrolase When the reaction was carried out by stirring at 35-45 ° C. for 4-10 hours, the fish bone frame was decomposed into calcium, phosphorus and amino acid peptide, and ii) the decomposed amino acid peptide was phosphorylated by binding with phosphoric acid. Iii) a reaction process in which the phosphorylated amino acid peptide reacts with calcium; A separation step of filtering and separating only those having a predetermined molecular weight or less using an ultrafiltration system to separate the reactants passed through the reaction step; And a drying step of spray drying to deodorize and dry the separated reactant.

In addition, 1% (based on dry weight) of the fish bone frame is preferably added based on the organic acid 1 ~ 10% solution.

In addition, it is preferable that only the molecular weight is filtered at 5,000 Da or less in the separation process.

In addition, the reaction product which is not filtered after the separation process is recycled from the reaction process, wherein the proteolytic enzyme having a high molecular weight is preferably not filtered and recycled.

In addition, the drying process is made by using a spray drier (Spray Drier), it is preferable that the spray drying at a high temperature of injection temperature 200 ~ 230 ℃, exhaust temperature 150 ~ 180 ℃.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the Examples to be described below.

The method for preparing amino acid calcium according to the present invention comprises a reaction step (100), a separation step (200), and a drying step (300) for reacting a fishbone frame with an organic acid and a protein hydrolase in a bioreactor.

* Extraction of calcium (Ca), phosphorus (P) and amino acid peptides by simultaneous treatment of organic acids and proteolytic enzymes using a bio-reactor, phosphorylation of amino acid peptides and calcium binding of phosphorylated amino acid peptides Reaction Process of Amino Acid Calcium (100)

Fish Bone Frame wet-crushed with 10% acetic acid solution (pH: 2.0-2.2) among edible organic acids in Bio-Reactor equipped with temperature and pH controller and stirrer. 1% (based on dry weight) and 1% (based on bone frame) of enzyme were added.

After stirring for 4-10 hours at 40 degreeC with gentle stirring, the amino acid calcium composition was obtained by taking the supernatant which passed through the bioreactor and the attached filter.

In the bioreactor, calcium (Ca), phosphorus (P) and amino acid peptides are extracted by the action of organic acids and proteolytic enzymes, and phosphorylated amino acid peptides are formed by the action of the extracted phosphorus (P) and degraded amino acid peptides. At the same time, the amino acid calcium composition was formed by adsorbing calcium.

* Continuous Circulation Production and Separation Process of Amino Acid Calcium by Combination of Bioreactor and Ultrafiltration System (200)

The combination of the bioreactor and the ultrafiltration system allows the entire process of decomposition, extraction and separation and recovery of amino acid calcium into a single process system. In this process, the decomposition reaction is not completed and the ultrafiltration membrane (Membrane Filter: cutoff) Reactants that do not pass -5000 Da) are reintroduced into the bioreactor with proteolytic enzymes (molecular weight 20,000-30,000 Da) to extend the reaction time to the end of the desired degradation.

In this process, the first hydrolase is put through a recycling process, and the production cost can be reduced by participating in the reaction with the newly added bone frame to the bioreactor.

The amino acid calcium composition produced as a result of the reaction in the bioreactor is subjected to an ultrafiltration system by a transfer pump. As shown in FIG. 2, the amino acid calcium is recovered more than 85% from the fraction having a molecular weight of 5000 Da or less.

* Spray drying process for deodorization and drying of separated amino acid calcium composition (300)

Deodorization and drying of the separated amino acid calcium are carried out using a spray drier, with an injection temperature of 200 ° C. or higher, preferably 200-230 ° C., and an exhaust temperature of 150 ° C. or higher, preferably 150-180. It is set at a relatively high temperature at 占 폚, whereby excess edible organic acid (especially acetic acid) is evaporated off and at the same time odor (fishy) of the amino acid calcium composition is halved, and the preferred direction for the amino acid calcium is achieved by the roasting effect under the spraying conditions. Is given, and palatability is increased.

As described above, the amino acid calcium produced through the drying process may be packed in appropriate amounts for a long time guarantee.

As described above, the amino acid calcium according to the present invention simultaneously performs the extraction of minerals from animal bone tissues, especially fish bones and hydrolysis of proteins, inducing interactions between the extracted useful substances, and at the same time performing phosphorylation of amino acid peptides Economical efficiency is achieved by combining calcium in a single process.

In addition, the amino acid calcium produced by the production method of the present invention does not require the use of calcium absorption accelerators in combination, and as such, the absorption rate in the human body is very high, and product quality stability and safety are ensured.

In addition, the manufacturing method according to the present invention is a process combining a bioreactor and an ultrafiltration system, and constitutes a circulation system for recycling the hydrolase which occupies a substantial portion of raw material costs in the hydrolysis and extraction stages, resulting in continuous production and cost reduction. Will have an effect.

Claims (6)

In a bio-reactor consisting of a temperature and pH controller and a stirrer, a fish bone frame (muscle protein bound to the fish bone), an organic acid and a protein hydrolase are added and stirred at 35 to 45 ° C. for 4 to 10 hours. A reaction step of reacting the mixture by reaction; A separation step of filtering and separating only those having a predetermined molecular weight or less using an ultra-filtering system to separate the reactants that have undergone the reaction process; And Calcium amino acid calcium production method characterized in that consisting of a drying step of spray drying to deodorize and dry the separated reactants. The method of claim 1, The amino acid calcium production method characterized in that the 1% (based on the dry weight) of the bone frame based on the 1-10% solution of the organic acid. The method according to claim 1 or 2, During the reaction process, the golgol frame is decomposed into calcium, phosphorus and amino acid peptides, and ii) the decomposed amino acid peptide is phosphorylated by binding to phosphoric acid, and iii) the phosphorylated amino acid peptide is bound to calcium. Amino acid calcium production method characterized in that. The method of claim 1, In the separation step, the amino acid calcium production method characterized in that the molecular weight is filtered to 5,000 Da or less. The method of claim 4, wherein the unfiltered reactant after the separation step is recycled from the reaction step, wherein the protein hydrolase having a high molecular weight is not filtered and recycled. The method of claim 1, wherein the drying step is performed using a spray drier (Spray Drier), calcium amino acid calcium production method characterized in that the spray drying at a high temperature of 200 ~ 230 ℃, exhaust temperature 150 ~ 180 ℃.

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