KR20060028441A - Calcium get to extract from the husk of an echinoderm processing with an organic acid and method for per paring the same - Google Patents

Abstract

The present invention relates to a method for preparing the same, including a pretreatment process for increasing the calcium component extraction and solubilization rate of the sea urchin portion.

The method for preparing calcium was prepared by washing and dehydrating the sea urchin portion of the first sea urchin, followed by freezing (-25 ° C.), grinding, hot air drying, sieving, firing, organic acid treatment, and heavy metal removal.

In the present invention, the keratin portion of the sea urchin is washed and processed to have a calcination temperature of 700-900 ° C. during the calcination process, and the calcination time is 2 hours or more, and the organic acid treatment and heavy metal removal through the separator are treated. In particular, calcium compositions can be prepared in food and pharmaceutical supplements. The calcium-containing composition has excellent calcium absorption rate in the digestive tract, is easy to process, and has a good texture and white appearance.

 It can be mixed with other food and pharmaceutical supplements to produce a superior product.

Solubilization rate, skin, firing, organic acid treatment, water absorption

Description

Calcium extraction from organic acid-treated sea urchin skin and method for manufacturing thereof {CALCIUM GET TO EXTRACT FROM THE HUSK OF AN ECHINODERM PROCESSING WITH AN ORGANIC ACID AND METHOD FOR PER PARING THE SAME}

1 of the present invention is a view showing a calcium manufacturing process.

The sea urchin is extracted from the sea urchin, washed and dehydrated, and freeze-dried to remove moisture. Grind in a state where water is removed to remove foreign substances (over 60 mesh) and dry with hot air. After drying, sieve and grind again if it is 60mesh or more and grind it to 60mesh or less. After pulverizing, firing at high temperature and regrinding to remove heavy metals through organic acid treatment and separation membrane, and then the resultant is dried and prepared in the form of salt to increase the solubility of the final calcium powder.

An object of the present invention is currently commercially available calcium is used in pharmaceutical supplements and food additives, health supplements and the like. Based on the existing sources of calcium, natural minerals such as limestone, calcium phosphate and calcium carbonate, and animal bones and egg shells, oysters, shellfish, scallop shells, marine animals and plants such as seaweed and kelp are manufactured as raw materials. have. Calcium extracted and processed from these raw materials is taken as a meal or exhibits absorption in different digestive tracts, respectively. In addition, most of the calcium in these raw materials are present in the form of calcium carbonate or calcium phosphate or converted into organic acid calcium salts such as citric acid, lactic acid, gluconic acid and maleic acid in order to increase the absorption rate in the digestive tract. However, calcium obtained from these raw materials has the disadvantage that the absorption rate in the digestive tract is not sufficient or the absorption rate in the digestive tract is not bad but the solubilization rate is low. In addition, there are problems such as high cost in order to make the above calcium, which is inconsistent as a food material for calcium supplementation.

Therefore, what is intended in the present invention is to make through the process of extracting calcium having high purity and solubility of calcium from the natural marine material in order to supplement the disadvantages of the existing calcium.

The present invention relates to the recycling of the sea urchin skin part, which is a marine organism, and to the extraction of calcium from the skin and its preparation. More specifically, take the epidermal part of the sea urchin.

After washing and dehydrating in the first step, freeze (-10 ~ -25 ℃) and dry.

In the secondary process, the dry skin part is ground (less than 60 mesh).

In the third process, hot air drying (25 ~ 60 ℃, 24 hours) and sifting (less than 60mesh) are performed.

In the fourth process, to increase the purity by removing solubilization rate and organic impurities

    It undergoes firing process at 700 ~ 900 ℃.

In the 5th process, organic acid (acetic acid) is prepared in a volume percent ratio and a separator is used.

    Solubilization rate by removing heavy metals

    Maximized.

It is prepared including the above process.

In general, calcium refers to the origin of calcium (Calcium), which is derived from Latin called lime calx.

It is the first pure metal separated from lime by the British chemist Debut in 1808. It is the element that makes up the human body. It is the fifth most abundant element after organic compounds made of oxygen, carbon, hydrogen and nitrogen. to be.

It is present in the highest amount of minerals in the human body. Although it varies depending on the person, about 1.5 to 2.2% of the weight is made of calcium. This Ca is 99% of the bone and teeth are stored mainly in the form of calcium phosphate, the remaining 1% is spread in the blood and cells are used to activate the human function. The backbone consists of 65-70% minerals and 30% collagen. The ratio of calcium in bone, blood and cells is about 10,000: 1 in bone and blood.

Calcium's actions include heart palpitation, muscle and nerve activity, blood coagulation, enzyme activity, and cell membrane permeation. The active calcium is about 10M more than the intracellular fluid in the extracellular fluid, especially in soft tissues (SOFT TISSUE), it seems that the importance of the active calcium can be guessed.

The calcium that makes up bone is released into body fluids by the action of parathyroid hormone (PTH) and hydroxide D (activated vitamin D), and maintains a constant level of serum calcium (Ca2-) with calcium absorbed from the outside. Serum calcium increases the excitability of nerves and muscles, causing stiffness (TETANY). Conversely, hypercalcemia is accompanied by general boredom and consciousness disorders. However, a sufficient concentration of serum calcium calcifies the bones to promote bone growth and to activate the coagulation factor. Meanwhile, INTRACELLULAR CALCIUM promotes hormone and neurotransmission, promotes secretion of digestive enzymes such as amylase, protease and lipase secreted into gastric juice and duodenum, metabolic processes such as collagen, and muscle contraction and cell proliferation. It is involved in function regulation.

Calcium is very low absorption and high when protein, lactose, vitamin D, C, etc. together, so it is important to eat food as well as calcium sources. In modern times, calcium is deficient due to irregular and unbalanced eating habits and lack of milk intake, and calcium demand is increasing due to various stresses. It seems to be getting worse. In particular, postmenopausal women who have decreased female hormones (estrogen) and lower calcium absorption rate are directly linked to serious problems. Therefore, in order to solve this problem, continuous calcium intake of at least nutritional recommendation (700mg) is important. Calcium is a mineral with a very low absorption rate of 20 ~ 30%, and the absorption rate is lower due to lack of exercise, excessive drinking, smoking, high-fat diet, intake of caffeine, excessive intake of salt, stress, etc. Increasing the absorption rate in the body to the maximum has become an important concern.

Koreans recommend calcium for infants (300mg / day, females: 300mg / day), children (males: 700mg / day, females: 700mg / day), adolescents (men: 900mg / day, females: 800mg / day), Adults (male: 700 mg / day, female: 700 mg / day; pregnant women 1,000 mg / day; lactation 1,100 mg / day).

As mentioned above, the calcium intake of Koreans should be made naturally, but this is not the case.

Therefore, it is intended to extract calcium from natural ingredients that can not be naturally ingested in modern people to be used in more stable supplements and medicines.

In general, the method of making calcium is produced industrially mainly by fusion salt electrolysis and heat reduction.

In the electrolysis method, calcium chloride anhydride is used as a raw material, and calcium fluoride or potassium chloride is mixed therein to lower the melting point and electrolyze at about 800 ° C. A steel electrolytic cell coated with graphite is used as the anode, and the water-cooled iron electrode is used as the cathode.

In the thermal reduction method, lime obtained by baking high-purity limestone is used as a raw material and reduced to aluminum.

6CaO + 2Al → 3Ca + Ca ₃ Al ₂ O ₆

In this case, a crystal is obtained by using a reaction tube made of stainless steel and heating to 1200 ° C. under vacuum to cool the generated calcium vapor. Since it is crystallized from steam, purity is about 98%.

The crystal has a face-centered cubic structure below 300 ° C. In addition, there are several crystal transformations, for example, hexagonal packed structure (六 方 密集 充 塡 構造) above 450 ℃. Lighter than alkali metal, it is malleable and malleable. It has an orange flame reaction. It has a chemical property very similar to its cognate strontium and barium, and has similar properties and structures, but generally decreases in order of Ba> Sr> Ca in terms of reaction activity. It reacts slowly with oxygen, nitrogen and water in the air at room temperature, so that the surface is covered with a yellowish gray film composed of oxides, nitrides and hydroxides. When heated in oxygen (or air), it burns with flame and becomes oxide CaO but does not produce peroxides or superoxides like alkali metals below potassium.

Heating in pure nitrogen produces nitride Ca ₃ N ₂ . It reacts slowly with hydrogen at 400 degreeC or more, and becomes calcium hydride, but when hydrogen pressure is high, it reacts even at low temperature.

In addition, it reacts with halogen, phosphorus, sulfur, selenium at high temperature, and directly with carbon, silicon, and boron.

It reacts slowly with water at room temperature and reacts violently with hot water to generate hydrogen and leave hydroxide. It reacts violently with alcohol violently, and produces | generates hydrogen and produces | generates an alkoxide (alcoholate: the compound which substituted the hydrogen of the hydroxyl group of alcohol with metal), or a salt. It dissolves in liquid ammonia to form a dark blue solution. After ammonia evaporates, hexaammine calcium complex [Ca (NH ₃ ) ₆ ] is left behind.

Heating in gaseous ammonia causes the following reactions:

Ca + 2NH ₃ → 3CaH ₂ + Ca ₃ N ₂

Mercury produces amalgams and reduces many organic compounds. High-purity calcium is stable in air for a while and can be stored for long periods when stored in the presence of inert gas or in a vacuum.

The compounds of calcium are very similar to those of strontium and barium, but their solubility in water is usually slightly higher.

The limestone and limestone market, which is produced from limestone, is showing strong demand over the ages.

Therefore, development and application are being promoted as high value-added products mainly in the food additive market, mainly in major grades.

Domestic limestone production amounted to 7.76 million tons in 2003, an increase of 1.8 times in four years compared to 4.12 million tons in 2000. In addition, existing limestone accounted for less than 5% of domestic demand, but import imports have doubled in 2004, accounting for about 10% of total demand.

Limestone imports increased 47.7% in 2001 (25,1375 tons) and 2002 (37,1160 tons), and increased only 7.2% in 2003 (39,7698 tons) to 2004 (86,8585 tons). That's up 118.4%. The surge in limestone imports is attributable to increased demand for high grade grades in the limestone processing market. Among slaked lime, etc. for food additives and pharmaceutical belonging to an advanced grade showed that while high, but relies on imports for much of the past localize the reaction of calcium hydroxide reported a significant import substitution effect of calcium hydroxide and calcium hydroxide chemistry class (Ca (OH) ₂₎ Are similar to each other, but are classified according to the purpose of use or purification. It is used for bleaching of color. On the other hand, calcium hydroxide for food has been applied for the purpose of strengthening functionalities in baking, milk, etc. for the purpose of ingesting calcium ions in the body. Made in China is about 30% cheaper than domestic, but the quality is not uniform, so demand companies are reluctant to use it.

In Korea, the company completed the development of high-reaction, high-reactive calcium hydroxide in 1998, and in 2001, it began full-scale business of PCC (hard calcium carbonate) and high-reaction calcium hydroxide for the purpose of diversifying its business. Highly reactive calcium hydroxide is mainly used as a food additive, industrial and pharmaceutical additives. In addition, in developed countries, calcium hydroxide is applied as a feed additive for calcium enhancement of animals, and thus the possibility of market development is increasing.

Conventional methods of calcium are manufactured chemically and naturally.

Chemically, it is extracted from hydrated lime and quicklime as described above, and in nature, calcium extracted from seaweed, cuttlefish shell, shellfish, starfish and the like is used. However, the calcium extracted from the above natural products is low in solubilization rate and the processing method is a situation that causes the above problems due to mass production without complementing the complex points. In addition, since the solubilization rate is low, the use is relatively comprehensive.

Therefore, the present invention aims to invent a product which is more stable than the presently demanded problems and which can optimally match product characteristics with high absorption rate and solubility and excellent price competitiveness.

It is an object of the present invention to provide calcium that is more stable and soluble in water from the viewpoint of being available to the human body. More specifically, to provide a method for producing calcium that is safe for the human body and soluble in water.

In order to achieve the above object in the present invention, the classification according to each process step.

This is because the solubilization rate is different according to each process step, and the calcium content is markedly different according to each process step.

Therefore, the process steps in the present invention will be described in detail.

After washing and dehydrating in the first step, the product is freeze-dried (-10 to -25 ° C) to remove moisture and odor for at least 24 hours.

In the second process, the dry skin part is pulverized (less than 60 mesh) to remove the suspended matter remaining in the skin part of the sea urchin.

In the third process, the pulverized particles are hot-air dried (25-60 ° C. for 24 hours) to remove residual water and sieved (less than 60 mesh) to evenly distribute the particle size of the pulverized powder.

In the fourth process, in order to increase the solubilization rate, heat is applied to the electric furnace at 700 to 900 ° C., followed by calcination, followed by regrinding to equalize particle size.

In the fifth process, the organic acid (acetic acid) is treated and prepared in the form of a salt and dried to maximize the solubilization rate and remove heavy metals.

 In the above method, after measuring the calcium content, the calcium content was confirmed by measuring with an ICP (Inductivel coupled plasma spectrophotometer, Atomscan 25, TJA).

The reference data of the present invention is the analysis of all the components based on the data appearing when the pure calcium to 100.

Test example

Example 1

In the first step prepared by the above method, the skin part of the sea urchin was taken, washed with water and dehydrated, and then freeze-dried (-10 to -25 ° C) for easy grinding.

Allow enough drying time (more than 24 hours) to remove moisture and odor present in the dermis.

 In the second step, the dried dermis in the first process was pulverized (less than 60 to 200 mesh) to remove suspended matters remaining in the dermis of the sea urchin.

In the third process, the crushed particles are hot-air dried (25 ~ 60 ℃, 24 hours) to remove the remaining water, and then sieved (less than 60 mesh) to uniformly distribute the particle size of the pulverized powder. have.

In the fourth step, in order to increase the solubilization rate, heat was applied to the electric furnace at 700 to 900 ° C., followed by calcining, and regrind to equalize particle sizes.

Calcium prepared by the above method, that is, the process step of calcium prepared by using the sea urchin skin, that is, the component analysis of the calcium produced in the first step and the fourth step is made as follows.

Example 1 ANALYSIS-1  AA Ca Mg Na Sr 92.93 5.15 1.14 0.78

ANALYSIS-1: CONCENTRATION (Unit: wt%)

AA: after firing

As shown in Table 1, the calcium content after firing was measured by inorganic decomposition of the sample organic matter by ICP (Inductivel coupled plasma spectrophotometer, Atomscan 25, TJA) using Tsutagawa et al, (1984). .

As a result, the calcium content reached 92.93%.

PH was measured at 11-12.

Calcium prepared by the above method is capable of component analysis and PH measurement, but cannot measure solubilization rate. In other words, there is no value as a product.

In the heavy metal test, minerals were measured by ICP (Inductivel coupled plasma spectrophotometer, Atomscan 25, TJA) after wet decomposition of the organic material of the sample by the method of Tsutagawa et al, (1984).

As a result, no harmful components such as cadmium, copper, iron, lead, zinc, chromium, molybdenum, and mercury were detected.

Example 2

In the first step prepared by the above method, the skin part of the sea urchin was taken, washed with water and dehydrated, and then freeze-dried (-10 to -25 ° C) for easy grinding.

Allow enough drying time (more than 24 hours) to remove moisture and odor present in the dermis.

 In the second step, the dried dermis in the first process was pulverized (less than 60 to 200 mesh) to remove suspended matters remaining in the dermis of the sea urchin.

In the third step, the pulverized particles are hot-air dried (25 ~ 60 ℃ for 24 hours) to remove residual water, and then sieved (less than 60 mesh) to distribute the particle size of the pulverized powder evenly.

In the fourth step, in order to increase the solubilization rate, heat was applied to the electric furnace at 700 to 900 ° C., followed by calcining, and regrind to equalize particle sizes.

When the first calcium is ground before treatment, it contains some organic matter. Therefore, it can be seen that the calcium content increased when the remaining organics were removed by washing with chloroform. Toxicity test and solubility test were prepared by adding deionized water to saturate the sample, shaking for 3 hours at room temperature, and then filtering. The filtrate was wet decomposed with nitric acid and calcium was analyzed by ICP (Inductivel coupled plasma spectrophotometer, Atomscan 25, TJA) to obtain the concentration.

In the content measurement test, minerals were measured by ICP (Inductivel coupled plasma spectrophotometer, Atomscan 25, TJA) after wet decomposition of the organic material of the sample by the method of Tsutagawa et al, (1984).

Example 2 ANALYSIS-1  AB Ca Mg Na Sr 92.74 4.67 1.88 0.71

ANALYSIS-1: CONCENTRATION (Unit: wt%)

AB: after organic acid treatment

PH measurement was measured with a PH meter (Metrohm 691, swiss).

The pH of 6-7 was measured. Therefore, it has a neutral value after organic acid treatment.

As shown in Examples 1 and 2, it can be seen that the difference between the pH values after the firing and the organic acid treatment is large.

The reason why the pH after firing is high is that the organic acid present before firing is decomposed or evaporated after firing, so that the PH appears as a strong base.

In the heavy metal test, minerals were measured by ICP (Inductivel coupled plasma spectrophotometer, Atomscan 25, TJA) after wet decomposition of the organic material of the sample by the method of Tsutagawa et al, (1984).

As a result, no harmful components such as cadmium, copper, iron, lead, zinc, chromium, molybdenum, and mercury were detected, proving safety.

Example 3

In the first step prepared by the above method, the sea urchin spine and the skin part were taken, washed with water, dehydrated and freeze-dried (-10--25 ° C.) for easy grinding.

A sufficient drying time was given (more than 24 hours) to remove moisture and odors present in the spiny and skin parts of the sea urchin.

 In the second step, the thorns and the skin part dried in the first step were pulverized (less than 60 to 200 mesh) to remove suspended substances, etc. remaining in the sea urchin with an organic compound.

In the third step, the pulverized particles are hot-air dried (25 ~ 60 ℃ for 24 hours) to remove residual water, and then sieved (less than 60 mesh) to distribute the particle size of the pulverized powder evenly.

In the fourth step, in order to increase the solubilization rate, heat was applied to the electric furnace at 700 to 900 ° C., followed by calcining, and regrind to equalize particle sizes.

When the first calcium is ground before treatment, it contains some organic matter. Therefore, it can be seen that the calcium content increased when the remaining organics were removed by washing with chloroform. Toxicity test and solubility test were prepared by adding deionized water to saturate the sample, shaking for 3 hours at room temperature, and then filtering. The filtrate was wet decomposed with nitric acid and calcium was analyzed by ICP (Inductivel coupled plasma spectrophotometer, Atomscan 25, TJA) to obtain the concentration.

In the content measurement test, minerals were measured by ICP (Inductivel coupled plasma spectrophotometer, Atomscan 25, TJA) after wet decomposition of the organic material of the sample by the method of Tsutagawa et al, (1984).

Example 3 ANALYSIS-1  AC Ca Mg Na Sr B K Other 91.33 5.90 1.57 0.73 0.21 0.24 0.02

ANALYSIS-1: CONCENTRATION (Unit: wt%)

AC: after organic acid treatment

PH measurement was measured with a PH meter (Metrohm 691, swiss).

The pH of 6-7 was measured. Therefore, it has a neutral value after organic acid treatment.

As shown in Examples 1, 2, and 3, it can be seen that the difference between the pH values after the firing and the organic acid treatment is large.

The reason why the pH after firing is high is that the organic acid present before firing is decomposed or evaporated after firing, so that the PH appears as a strong base.

It can be seen that the component is not significantly different from Example 2.

Therefore, the calcium content of single and mixed materials of the above materials does not change significantly.

That is, as a result of component analysis based on food additives, the result is 40.4 wt% based on Ca (OH) 2 method.

That is, the wt% of the total inorganic and organic components is measured as 40.4 wt%.

The method used the method of food additive revolution.

Measure about 2g precisely, dissolve in 30ml of diluted hydrochloric acid, and add water to make 250ml. 15 ml of potassium hydroxide solution (1-10), 3 ml of potassium cyanide solution (1-20) and 100 ml of water are added to 10 ml of the solution, which is then left to stand for about 1 minute. 2-oxy-1- (2'-oxy-4'-sulfo- 0.1 g of 1'-naphthyl azo) -3-naphthoic acid reagent was added and immediately 0.05M nidy. tea. a. Titrate with solution. The end point is when the red color has completely disappeared and turned blue.

In the heavy metal test, minerals were measured by ICP (Inductivel coupled plasma spectrophotometer, Atomscan 25, TJA) after wet decomposition of the organic material of the sample by the method of Tsutagawa et al, (1984).

As a result, no harmful components such as cadmium, copper, iron, lead, zinc, molybdenum, and mercury were detected.

According to the invention, instead of producing calcium by chemical method, it is reliable by extracting calcium from pure natural marine life, high percentage of calcium, easy to process, fine particles, and pure white with good appearance. In addition, heavy metals, which are a social problem, are not detected, and in particular, it is possible to provide a calcium-containing composition suitable for the production of foods, and to produce excellent health foods in which the calcium-containing compositions are added and mixed with other food materials.

Claims (1)

In the method of producing calcium by firing sea urchin skin containing a lot of calcium components, the process of washing calcium raw material with sea water and the process of calcining the calcium raw material washed in the sea water in an electric furnace (temperature 700-900 when firing) Process for producing calcium by putting 0.1N ~ 0.5N of acetic acid after grinding for 2 hours at high temperature

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