KR20020039702A - Calcium drug from star fish and extraction method of same - Google Patents

Abstract

PURPOSE: Provided is a method for extracting calcium from starfish by fermentation and chemical treatment. The calcium extract is used for liquid fertilizers improving growth of crops. CONSTITUTION: The calcium extract is prepared by the following steps of: grinding starfish to 50mesh in size; heating a mixture of ground starfish and water at 100deg.C; fermenting by inoculating the mixture with lactobacillus to produce fermented materials of pH 3-4; mixing the fermented materials with an acidic compound, Ca(NO3)2 to be pH 1.5-2.5; adding a basic compound, Mg(OH)2, to be a neutral calcium extract(pH 5-6). The prepared calcium extract contains 17-18.12% of Ca, Mg, P, protein, and trace elements.

Description

Calcium preparation derived from starfish and its manufacturing method {CALCIUM DRUG FROM STAR FISH AND EXTRACTION METHOD OF SAME}

The present invention relates to a calcium preparation derived from starfish and a method for preparing the same, and more particularly, to a method for extracting calcium ions from starfish lysate through fermentation and chemical treatment.

Starfish belong to the echinoderm and live in various parts of the seabed. Starfish prey mainly on shellfish and shellfish such as abalone, shellfish, oysters, scallops and mussels. Starfish are also creatures that inflict enormous damage to fishermen by spawning in large quantities and rapidly breeding, destroying fish farming and fisheries ecosystems.

As a way to solve the damage to the starfish, there are lime spraying, trap installation, submerged harvesting methods, and more effective ways to rescue the starfish are being developed.

On the other hand, the damage caused by starfish is not limited to the fisheries sector. Starfish captured or collected in various ways are treated as waste due to lack of proper utilization on land, causing odor and environmental pollution accompanied by secondary decay, and cost and time for waste disposal.

Recycling starfish, mixing and processing starfish and sardines of Republic of Korea No. 1982-3469, manufacturing method of fish meal for livestock feed, manufacturing method of artificial feed for high-density culture of barley shrimp of Republic of Korea No. 1983-3223, fertilizer of Republic of Korea 1993-3957 There is a manufacturing method. The Republic of Korea No. 1993-3957 provides a method of manufacturing a fertilizer by drying and grinding fish and shellfish and then simply mixing calcium carbonate.

It is therefore an object of the present invention to provide a method for extracting calcium from starfish.

Another object of the present invention is to provide a method for producing a fertilizer using calcium extracted from starfish.

1 is a graph showing that the amount of calcium extracted from the starfish of the present invention increases as the pH of the extract is lowered.

The present invention to achieve the above object

(a) crushing starfish;

(b) heating the lysate;

(c) fermenting the heated product to produce fermented products having a pH of 3 to 4; And

(d) it provides a calcium extraction method comprising the step of titrating the pH to 1.5 to 2.5 by mixing a compound containing an acid group to the fermented product.

In addition, the present invention

(a) crushing starfish;

(b) heating the lysate;

(c) fermenting the heated product to prepare fermented products having a pH of 3 to 4;

(d) mixing a compound containing an acid group with the fermentation product to prepare a strong fermentation acid solution having a pH of 1.5 to 2.5; And

(e) It provides a calcium preparation method comprising the step of preparing a neutral solution by adding a basic substance to the strong fermentation acidic solution to titrate the pH to 5 to 6.

It also provides a fertilizer prepared by the above calcium preparation method.

Hereinafter, the present invention will be described in detail.

Starfish contains a large amount of organic and inorganic components. One of the useful ingredients is calcium.

The calcium preparation of the present invention is preferably extracted from starfish, more preferably Asterias amurensis, Starfish (Asterias pectini fera), Sunstar starfish (Solaster borealis), Rod starfish (Solaster paxillatus), Spiny starfish (Astropecten polycantbus), the spiny starfish (Marthasterias glacilis).

The present invention provides a method for extracting calcium from starfish. The calcium extraction method may be carried out by applying to fish and other marine animal organisms other than starfish. The method for extracting calcium ions is characterized in that it is carried out by heating the pulverized product of fish waste and then adjusting the pH of the heated water. In other words, by lowering the pH to ionize the calcium compound contained in the fish and fish, at the same time to dissolve the remaining fine fish waste crushed to extract all the calcium in the crushed calcium ions. The pH control method is preferably a biological treatment or chemical treatment, two treatments may be performed sequentially. The biological treatment is preferably made by fermentation using a fermentation strain, and the chemical treatment is preferably carried out by adding a substance containing an acid group. Acid groups are ions that react with hydrogen to form a strongly acidic substance, and NO ₃ ⁻ , SO ₄ ^2- , CH ₃ COO ⁻ , and PO ₄ ^3- are preferred, and the acid-containing substance may be Ca (NO ₃ ) ₂ , MgSO ₄ , CH ₃ COOH, H ₃ PO ₄ and the like are preferred. It is preferable to further include neutralizing the pH by extracting the calcium ions by the above-described method and mixing the basic substance.

In addition, the calcium preparation of the present invention includes the steps of crushing starfish, heating, biological treatment of the heating, chemical treatment of the biological treatment, and neutralizing the pH of the chemical treatment It characterized in that the manufacturing.

In order to extract the calcium contained in the starfish, the present invention is characterized by using a calcium ion release method by pH. Calcium is present in the form of calcium carbonate in the starfish. Since the calcium carbonate is ionized in the acid, the calcium ion extraction method of the present invention is characterized by changing the pH of the starfish heating material. The calcium contained in the starfish is bound in the protein, which first breaks down the protein in order to extract it. 1 is a graph showing the calcium or protein content extracted from the starfish according to pH, when the protein is completely decomposed into the amino acid form using 6 N hydrochloric acid and then the protein content and calcium content is 100% The amounts of free protein and calcium at each pH were shown. As shown in Figure 1, the calcium content of calcium and protein increase as the pH of the reactant is lowered to obtain a calcium of about 60% when the pH is 2 to 3. Therefore, the calcium extraction method of the present invention is characterized by the acidification of the pH of the reactants.

The method of lowering the pH of the calcium extraction reactant of the present invention is preferably a chemical method and a biological method, and most preferably, the chemical method is performed after the biological method. The biological method is to inoculate the fermentation strain with the starfish heating, acidifying the pH of the starfish heating with the organic acid produced by the fermentation strain. The fermented starfish heating preferably has a pH of 3-4.

In addition, the chemical method is to prepare a strong fermentation acidic liquid by mixing the chemicals in the fermented starfish heating water. The chemical is preferably a compound containing an acid group, most preferably calcium nitrate (Ca (NO ₃ ) ₂ ). Calcium nitrate is added to the fermented starfish heating and then ionized with nitrate ions (NO ₃ ⁻ ) and calcium ions (Ca ²⁺ ), and the nitrate ions react with hydrogen ions on the fermented starfish heating to nitrate (HNO ₃ ). Becomes In the strong fermentation acidic liquid of the present invention, the pH is lowered by the nitric acid, so that the pH is 1.5 to 2.5. The content of the compound containing an acid group to be added is preferably adjusted according to pH, and most preferably, it is added so that the pH of the strong fermentation acid solution is 2. The strong fermented acidic liquid can decompose the remaining starfish microstructure and extract all remaining calcium components.

(1) Broken Starfish

The shell of the starfish is a very hard and tough tissue, which is then crushed to extract organic or inorganic substances contained in the starfish tissue. The starfish is frozen and then crushed using a Hammer crusher. The shredded starfish fragment is preferably 50 mesh passes.

(2) heating

Starfish shreds are mixed with water and heated at 100 ° C. During the heating process, the mineral contained in the starfish is released. The leaving minerals are calcium, phosphorus, potassium, magnesium and other trace elements. The heated heating comprises calcium carbonate leached from the starfish tissue.

(3) biological treatment

The calcium carbonate contained in the heating is decomposed into carbon dioxide and calcium ions to obtain useful calcium (Ca ²⁺ ). The biological treatment is preferably performed by inoculating the fermentation process by inoculating fermentation strains on the starfish heating water. The fermentation strain for the fermentation process of the present invention is preferably a fermentation strain producing an organic acid, more preferably Lactobacillus strains, and most preferably Lactobacillus confusa ( Lactobacillus confusa ).

In the fermentation process of the present invention, fermented strains are cultured at 3.5 x 10 ⁹ to 3.5 x 10 ¹² cfu / ml, and 3 L of the starfish heated in step (2) is mixed. The fermentation is preferably made of 35 ℃, 18 to 24 hours in aerobic anaerobic phase, the fermentation product is preferably pH 3 to 4 after the fermentation process.

(4) chemical treatment

The compound containing an acidic radical is mixed with the fermentation product obtained by said (3). Preferably calcium nitrate (Ca (NO ₃ ) ₂ ). Calcium nitrate is added to the fermentation at 0.7 g / ml and stirred. The chemical reaction generated by the addition of the calcium nitrate is shown in Scheme 1 below.

Scheme 1

_{Ca (NO 3) 2 → Ca} 2+ + NO 3 -

H ⁺ (hydrogen ions present in the fermentation liquid) + NO ₃ ^- → HNO ₃

A compound containing an acid group is mixed with a fermentation product to prepare a strong fermentation acidic solution, and the upper limit fermentation acidic solution decomposes calcium ions by decomposing the microstructure of the starfish.

(5) pH adjustment

A basic preparation is added to the strong fermented acidic solution prepared in step (4) to titrate the pH to neutral to prepare a calcium preparation. The basic substance is preferably a conventional basic substance, most preferably magnesium hydroxide (Mg (OH) ₂ ). Magnesium hydroxide is a very preferred substance in the present invention because it is a basic substance and magnesium is directly involved in the growth of crops. The magnesium hydroxide is preferably added to the strong fermentation acidic acid to titrate the pH to 6 to 7, and the amount of magnesium hydroxide is adjusted to the pH titration.

The present invention also provides a calcium preparation. The calcium preparation of the present invention is preferably in the form of a solid, a gel, a powder or a liquid, and most preferably a liquid. The calcium preparation of the present invention was commissioned by the Rural Development Administration to analyze the content of water-soluble calcium in the calcium preparation. As a result, it was confirmed that water soluble calcium was more than 17% and 18.12% according to the provision of Article 8 of the RDA Testing, Analysis and Certification Request Rules. In addition, the calcium preparation of the present invention includes magnesium, phosphorus, potassium, and other trace elements and proteins.

The calcium preparation of the present invention is preferably used as an agricultural fertilizer, it is preferable to fertilize foliar fertilization or irrigation in the crop. When used as an agricultural fertilizer, the calcium preparation of the present invention is effective in strengthening the stems of crops and maintaining fruit deletion and growth and coloring freshness. The calcium preparation of the present invention is preferably fertilized in crops such as fruit trees, vegetables, leafy vegetables, and special crops, and the fertilizing time is before fruiting, fruit boiling, after coloring, before flowering, before summer rainy season, during the rainy season, during high-temperature disorders. Therefore, it is desirable to control crops properly in view of the ecology of crops. More specifically, it is preferable to fertilize foliar fertilization and irrigation during cultivation of fruits and vegetables, fruit vegetables, fruits, and fruits during planting. In order to prevent it is preferable to soak foliar fertilization at intervals of 7 to 10 days in advance. In addition, when fertilizing calcium preparations in fruit trees, it is preferable to dilute 1L of calcium preparations in 10 pieces of water before planting new roots before flowering and consequently to fertilize them once per week and dry them little by little. Fertilization time and the amount of fertilization of calcium preparations according to crops are shown in Table 1 below.

TABLE 1

Crop name Processing time How to use and usage effect Melon, watermelon, tomato, melon Before play Foliar fertilization: 500 cc to 1000 pyeong for 10 days Spray tube fertilization: 150 pyeong 1L irrigation fertilization for 15 days Prevent coating, supplement nutrient deficiency, root development, organ calcium Fruit waiting Leaf surface fertilization: 2 weeks interval tube fertilization application: 150 pyeong 1L 15 days interval Prevents rot and foot, strengthens shelf life, reduces heat and heat Before and after colorator Leaf application: 500 cc sprayed at 1200 pyeong every 10 days Color Enhancement pepper Around 1 month before the official meal (after the end of May) Foliar fertilization: Spray drenching (800x) every 10 days Anthrax prevention, rot and prevention, foliar strengthening High temperature disorder, severe rainy calcium deficiency disorder, anthrax is severe Foliar application: Drenched (800-fold dilution) every 7-10 days Anthrax Prevention, Calcium Deficiency Prevention Leafy vegetables 10 days after the meal Foliar fertilization: Drenched in 10-day intervals (800x) Preventing and eliminating cabbage rot and lettuce bruising Strawberry 15 days after the meal Cross fertilization: 150 pyeong 1L once Strengthen rooting, root development 1 month after the meal Foliar fertilization: 500 cc to 1000 pyeong, 10-day intervals Promotes germination differentiation, supplements nutrient deficiency, prevents tip and prevention, uniform initiation of crown, and enhances shelf life of fruit Fruit tree 3-4 months before flowering Root irrigation: dilute 1L in 10 horses of water and soak each horse in a week. Preventing Headache Summer (before the rainy season) Foliar fertilization: 800 times diluted dipping Falling prevention, browning prevention September-October Foliar fertilization: 800-1000 times diluted to soak Coloring, enhanced storage

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are provided only to more easily understand the present invention, and the present invention is not limited to the following examples.

Example 1

100 kg of the captured and frozen starfish were crushed with a Hemer grinder equipped with a 1 hp motor to prepare a 50-mesh pass starfish crushed product. 50 kg of the starfish shreds were mixed with 50 L of water and heated in a reactor at 100 ° C. for 1 hour. The heating was placed at room temperature to lower the temperature.

The fermented strain Lactobacillus confuza was obtained from a sloped medium, followed by primary culture in Lactobacillus MRS medium (Difco), followed by secondary culture of 3 L, 3.5 x 10 ¹⁰ cfu / ml. When the heating was 35 ° C, 3 L of Lactobacillus confusas were added and stirred incubation at 35 ° C for 18 hours to 24 hours. 35 Kg of commercial calcium nitrate was mixed with the fermented product, and stirred for 2 hours to prepare a strong fermented acidic liquid. A calcium formulation having a pH of 5 to 6 was prepared by mixing 500 g of magnesium hydroxide with the prepared strong fermented acidic solution.

Experimental Example

Calcium preparation prepared by the method of Example 1 was used as a liquid fertilizer to investigate the effect on the growth of melon, tomato, ginseng.

Tomato and melon were divided into a group treated with untreated, chemical fertilizer (Namhae Chemicals; 21% nitrogen, 17% phosphoric acid, 17% potassium), and a group treated with Example 1. Example 1 was sprayed on the front by diluting 100 cc 200 times. The melon and the tomatoes were examined at 3 weeks intervals after the planting, and the maximum leaf length, fruit weight, and fruit tree were listed in Table 2 below.

TABLE 2

division Overweight (g) Fruit Tree () Leaves () First investigation (May 25) No treatment 0 0 6 Chemical fertilizer 0 0 8 Example 1 0 0 7 Second investigation (July 20) No treatment 23 12 11 Chemical fertilizer 28 11 13 Example 1 30 15 16 Third investigation (August 15) No treatment 280 26 14 Chemical fertilizer 330 38 15 Example 1 410 44 15

As can be seen in Table 2, the melon and the tomato treated in the embodiment 1 was increased by about 30% compared to the untreated fruit in the third irradiation, the fruit fruit was grown without any defect due to the growth of the fruit and stable growth Indicated.

Ginseng was fertilized with 10 L foliar fertilizer and no other fertilizer in one control, and the other one cultivated with 100 cc of Example 1 diluted in 10 L water. Thereafter, the same treatment was examined three times per two weeks after the fertilization changes.

TABLE 3

division Leaf weight (g) Root weight (g) Length (cm) First investigation (May 20) No treatment 8 23 11 Example 1 8 22 11.5 Second investigation (June 5) No treatment 14 23.5 11.5 Example 1 15 23.5 11.7 Third investigation (June 25) No treatment 18 24 11.6 Example 1 20 24 11.8

The leaf weights in Table 3 were calculated from the weight of the ground leaf surface, the root weight of ginseng root, and the root length of ginseng root. In the case of ginseng, there was no significant difference in muscle weight and root length when Example 1 was treated, but the increase in leaf weight promoted assimilation and absorption of nutrients through foliar surface, resulting in hypertrophy of ginseng root and root length after high temperature.

As mentioned above, the present invention can extract calcium from fish and shellfish as well as prepare calcium preparations. The calcium preparation of the present invention is used as a fertilizer to improve the growth of crops.

Claims (9)

(a) crushing starfish; (b) heating the lysate; (c) fermenting the heated product to produce fermented products having a pH of 3 to 4; And (d) a method of titrating the pH to 1.5 to 2.5 by mixing a compound containing an acid group with the fermentation product Calcium extraction method comprising a. The method of extracting calcium according to claim 1, further comprising the step of (d) mixing the basic substance with a strong fermented acidic solution to titrate the pH to 5-6. The method of claim 1, wherein the crushed calcium extraction method, characterized in that the passage through 50 mesh. The method of claim 1, wherein the fermentation is calcium extraction method, characterized in that carried out by inoculating Lactobacillus (Lactobacillus) system. The method of extracting calcium according to claim 1, wherein the compound containing an acid group is calcium nitrate. 3. The method of extracting calcium according to claim 2, wherein the basic substance is magnesium hydroxide. (a) crushing starfish; (b) heating the lysate; (c) fermenting the heated product to prepare fermented products having a pH of 3 to 4; (d) mixing a compound containing an acid group with the fermentation product to prepare a strong fermentation acid solution having a pH of 1.5 to 2.5; And (e) preparing a neutral solution by adding a basic substance to the strong fermented acidic solution and titrating the pH to 5 to 6 Calcium preparations manufacturing method comprising a. Fertilizer prepared by the method for producing a calcium preparation of claim 7. 9. The fertilizer according to claim 8, wherein the fertilizer is a liquid.