WO2013039360A2 - Ionized calcium aqueous solution and a production method therefor - Google Patents

Ionized calcium aqueous solution and a production method therefor Download PDF

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Publication number
WO2013039360A2
WO2013039360A2 PCT/KR2012/007406 KR2012007406W WO2013039360A2 WO 2013039360 A2 WO2013039360 A2 WO 2013039360A2 KR 2012007406 W KR2012007406 W KR 2012007406W WO 2013039360 A2 WO2013039360 A2 WO 2013039360A2
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calcium
solution
calcium oxide
aqueous solution
container
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PCT/KR2012/007406
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French (fr)
Korean (ko)
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WO2013039360A3 (en
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김미영
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주식회사 시로미
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Publication of WO2013039360A2 publication Critical patent/WO2013039360A2/en
Publication of WO2013039360A3 publication Critical patent/WO2013039360A3/en

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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K50/00Feeding-stuffs specially adapted for particular animals
    • A23K50/80Feeding-stuffs specially adapted for particular animals for aquatic animals, e.g. fish, crustaceans or molluscs
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K20/00Accessory food factors for animal feeding-stuffs
    • A23K20/20Inorganic substances, e.g. oligoelements
    • A23K20/24Compounds of alkaline earth metals, e.g. magnesium
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K50/00Feeding-stuffs specially adapted for particular animals
    • A23K50/10Feeding-stuffs specially adapted for particular animals for ruminants

Definitions

  • the present invention relates to an aqueous calcium ion solution and a method for manufacturing the same, and more particularly, to an aqueous calcium ion solution and a method for producing the same, which maximize the absorption of calcium into the body of animals and promote metabolism and biological function of the animals. It is about.
  • Calcium ions (Ca 2+) derived from calcium carbonate contained in limestone, etc., require a long time to naturally exist in the groundwater, and limestone itself is hard rock and does not easily dissolve in water.
  • An object of the present invention is to provide a method for preparing an aqueous calcium ion solution to stabilize the content and specification of calcium ion and to thereby maintain an appropriate level of trace elements, and to maintain an appropriate pH.
  • Another object of the present invention is to increase the shelf life by inhibiting the alteration and bacterial generation of livestock feed, thereby minimizing the loss of nutrients, ionization that can be used as a livestock feed that can increase the body absorption rate of calcium It is to provide an aqueous solution of calcium.
  • the present invention provides the following specific problem solving means.
  • Method for producing an aqueous calcium ion solution washing step of removing foreign matter and impurities through the washing of shells;
  • a high temperature firing step of heating and calcining the dried shellfish to produce calcium oxide by removing organic substances and residual toxicity contained in the dried shellfish;
  • Grinding the calcium oxide to produce a calcium oxide powder A stirring step of preparing a calcium oxide solution by mixing and stirring the calcium oxide powder and water; Supplying saturated steam to the container containing the calcium oxide solution, inducing an ionic reaction by generating static electricity in the container to produce an ionized calcium solution;
  • a hydrogen ion concentration adjusting step of adding the soft water treated water or pure water to the ionized calcium aqueous solution to maintain the hydrogen ion concentration at pH 12-13.
  • the high temperature firing step it is preferable to heat and fire shellfish dried for 1 to 3 hours at a temperature of 1100 ⁇ 2000 °C. This is the temperature and time necessary to allow the dried shellfish to be completely fired, and thus the temperature and time can be adjusted according to the application.
  • the firing temperature is gradually increased gradually over 2 to 3 hours from the initial temperature of 1100 ° C to the final temperature of 1600 ° C. This is because when the calcium ionized aqueous solution is used as an additive for livestock animals for constant temperature animals, the effect can be seen even if the particles are somewhat large or the ionization degree is lower, and the sensitivity to the components is less than that of the fish.
  • the particle size of the calcium oxide powder pulverized in the crushing step is preferably 20 ⁇ m or less, the particle size can be adjusted depending on whether the aqueous solution of calcium ionization is used.
  • the particle size of the calcium oxide powder when added to aquaculture feed, it is desirable to limit the particle size of the calcium oxide powder to 10 ⁇ m or less in consideration of the sensitivity of the fish, which is a transgenic animal, but for feed additives of livestock such as mammals or birds, which are relatively less sensitive. This is because even if the particle size of the calcium oxide powder is set to 20 ⁇ m, it is not too much.
  • the stirring step it is preferable to mix and stir the calcium oxide powder at a ratio of 0.1 to 2 parts by weight with respect to 100 parts by weight of water, because the calcium oxide powder is best ionized in water when mixing and stirring at this weight ratio.
  • the stirring time in the stirring step is preferably stirred for 2 to 5 hours after mixing, when used as an additive for livestock feed for constant temperature animals such as mammals and birds, it is preferable to stir for 2 to 4 hours, and relatively When the particle size is small, it is preferable to stir for 3 to 5 hours because the degree of ionization should be increased by dispersing it evenly in water.
  • the pressure of the saturated steam supplied in the ion reaction step is preferably 1.4 ⁇ 5MPa.
  • the method for producing an aqueous calcium ion solution according to the present invention, the ion reaction step of each step constituting the calcium oxide solution injection step of injecting the calcium oxide solution into the container;
  • the aqueous solution of calcium ion which is another aspect of the present invention is characterized in that it is produced by the above production method.
  • the method for preparing an aqueous calcium ion solution reaches a high concentration such that the content of pure calcium reaches 94 to 97%, and provides a high purity stable alkaline ionized calcium aqueous solution having a hydrogen ion concentration of pH 12 to 13, thereby adding food additives and calcium.
  • the absorption rate in the body is high when used, thereby maximizing the effect of calcium.
  • the ionized calcium aqueous solution according to the present invention increases the shelf life by inhibiting the alteration and bacterial generation of animal feed when used in animal feed, minimizes the loss of nutrients, and increases the body absorption rate of calcium by absorbing calcium It is effective in reducing intestinal gas generated by deficiency, ascites caused by calcium metabolic disorder, lowering immunity due to calcium deficiency, and lowering skin mucus.
  • FIG. 1 is a process chart showing a manufacturing process of an aqueous calcium ion solution according to an embodiment of the present invention.
  • Figure 2 shows a graph showing the results for the growth experiments of the flounder fed with the feed added as an additive to the halibut calcium aqueous solution prepared in accordance with an embodiment of the flounder and the flounder fed with the general feed.
  • Figure 3 is the blood of the halibut fed the feed with the addition of the aqueous solution of ionized calcium prepared according to an embodiment of the present invention as a feed additive and the blood of the halibut fed the normal feed to measure the aspartic acid amino-transferase (AST)
  • AST aspartic acid amino-transferase
  • Figure 4 is a graph showing the results of measuring the glucose (Glucose) by collecting the blood of the olive flounder fed the feed and the general feed fed with the calcium ionized aqueous solution prepared according to an embodiment of the present invention as a feed additive .
  • Figure 5 shows the results of measuring the lysozyme activity by collecting the slime and the slime of the halibut fed the feed with the feed added to the ionized calcium aqueous solution prepared according to an embodiment of the present invention as a feed additive It is a graph.
  • FIG. 1 is a process chart showing a manufacturing process of an aqueous calcium ion solution according to an embodiment of the present invention.
  • Shell refers to the inorganic secretion formation to protect the molluscs in mollusks, where shells may be used such as oyster shells, shell shells.
  • the dried shellfish is heated and calcined in the high temperature baking step to remove organic matter and residual toxicity contained in the dried shellfish, thereby preparing calcium oxide.
  • calcium oxide may be prepared by heating and firing the dried shellfish at 1100 ° C. to 2000 ° C. for 1 to 3 hours.
  • calcium oxide may be prepared by heating and firing the dried shellfish at an initial temperature of 1100 ° C. and gradually raising the temperature to a final temperature of 2000 ° C.
  • CaCO 3 calcium carbonate (CaCO 3 ), which is a constituent of shellfish, is calcined and converted to calcium oxide (CaO) in solid state.
  • Calcium oxide powder is prepared by grinding the calcium oxide prepared in the high temperature firing step. At this time, it is preferable to grind using a wet ball mill.
  • the particle diameter of the pulverized calcium oxide powder may be 20 ⁇ m or less. If the particle size of the calcium oxide powder exceeds 20 ⁇ m is because there is a problem that is not well mixed when preparing a calcium oxide solution by mixing with water. On the other hand, in order to obtain an ionized calcium solution used as a fish feed additive, it is preferable to grind to have a particle diameter of 10 ⁇ m or less, because the calcium oxide powder of 10 ⁇ m or less size is better mixed with water.
  • the calcium oxide powder and water are mixed and stirred to prepare a calcium oxide solution.
  • the calcium oxide solution prepared here is strongly alkaline.
  • the mixed weight ratio of water and calcium oxide powder is preferably 0.1 to 2 parts by weight of calcium oxide powder based on 100 parts by weight of water. Because if the weight ratio of calcium oxide powder to 100 parts by weight of water exceeds 2 parts by weight may not be sufficiently mixed in water, if less than 0.1 parts by weight prepared aqueous solution of calcium ion may not supply enough calcium in the body Because. Therefore, when the weight ratio is maintained, the calcium oxide powder is well mixed with water, and when used as a feed additive as an aqueous solution of calcium ion, it exhibits the effect of supplying sufficient calcium in the body.
  • the calcium oxide solution may be prepared by mixing the calcium oxide powder and water, followed by stirring for 2 to 5 hours. At this time, the calcium oxide powder is evenly mixed with water by stirring for 2 to 5 hours.
  • the calcium oxide solution when preparing an aqueous calcium ion solution used as additives for fish feed it is good to stir for about 3 to 5 hours to finely disperse the fine calcium oxide powder mixed in water well.
  • Saturated steam is supplied to a vessel containing the calcium oxide solution prepared in the stirring step (S400) to generate an electrostatic reaction in the vessel to prepare an ionized calcium aqueous solution.
  • saturated steam generated in a boiler generates some condensation due to the temperature drop in the vessel, which results in the formation of droplets.
  • the generated droplets collide or rub against each other, thereby generating static electricity.
  • the supplied air is expelled by the supplied saturated steam, and saturated steam also penetrates into the calcium oxide solution.
  • the static electricity accumulated in the droplets reaches the container either directly or through calcium oxide solution.
  • the portion where the static electricity flows in the calcium oxide solution is locally heated to rise in temperature and ion structure, but the current is not continuously flowing and the amount of power is small, so the temperature rise is small.
  • the average temperature in the container does not rise above the temperature of the saturated steam supplied, harmful components hardly occur.
  • the vessel and the stirring means are made of a chargeable material, ionization may be promoted according to the following mechanism.
  • the vessel and the stirring means When the vessel and the stirring means are charged and provided in an insulated state with respect to the base, the calcium oxide solution, the vessel and the stirring means have positive or negative charges (electrostatic) due to friction with the calcium oxide solution. Accumulates.
  • the saturated steam heated and pressurized is supplied in the container, and since this saturated vapor penetrates into the inside of the calcium oxide solution, the electrical resistance inside the calcium oxide solution decreases, so that electricity easily flows.
  • the charging property means that the electrical resistance is large and that the added calcium oxide solution can be positively or negatively charged.
  • the charging may be performed either positively or negatively.
  • the charge flows through the inside of the calcium oxide solution and into the vessel and the stirring means. Since the calcium oxide solution is agitated, the amount of charge collection varies with each part, and the path and time through which the charge flows also differ. In addition, since saturated steam is filled in the container, the electrical resistance is not too high or the static electricity is not collected too much. Therefore, the static electricity is discharged little by little, and instantaneously generates heat in the discharge path during discharge, while the calcium oxide solution is converted into a stable aqueous solution of calcium ionization. However, since discharge is not carried out continuously, it does not become a high temperature, the entire temperature in the container does not increase significantly at the set temperature by heating steam, and water suppresses the generation of harmful components.
  • the pressure of the saturated steam supplied to the container including the calcium oxide aqueous solution may be 1.4 to 5 MPa.
  • the ion reaction step (S500) is a calcium oxide solution injection step (S510) specifically injecting the calcium oxide solution into the container;
  • Hydrogen ion concentration is maintained at pH 12-13 by adding soft water or pure water to the calcium ionized solution.
  • soft water treated water refers to water whose hardness is adjusted to less than 0 to 60 mg / L
  • pure water treated water refers to water from which impurities including hardness components are removed.
  • the aqueous solution of calcium ion prepared according to the embodiment of the present invention can be used as additives of fish feed, additives of livestock feed, calcium ionized drinks and calcium fortification of plants, but is not limited thereto.
  • the dried shellfish was gradually heated up to 1300 to 2000 ° C. so that the total heating and calcining time was 2 to 3 hours.
  • the calcium oxide produced in the high temperature firing step was pulverized with a wet ball mill to have a particle size of 8 ⁇ m, and then mixed with water and stirred. At this time, the water and calcium oxide powder was mixed in a ratio of 1 weight ratio of calcium oxide powder to 100 parts by weight of water and then stirred for 5 hours to prepare a calcium oxide solution.
  • Saturated steam with a pressure of 4 MPa was supplied to the vessel containing the prepared calcium oxide solution to induce an ionic reaction to prepare a calcium ionized aqueous solution.
  • the prepared was added to the feed for the flounder and then fed to the flounder. In case of fry, 10 times diluted with water is used, but it is preferable to use it without diluting as it becomes adult.
  • the calcium ionized aqueous solution was used as an additive to the olive flounder for the entire period, it was used by adding 1 g of calcium ionized aqueous solution to 1 kg of olive flounder.
  • Table 1 below shows the hydrogen ion concentration according to the content ratio of the calcium oxide powder of the aqueous solution of calcium ionized according to Example 1 of the present invention.
  • the pH value gradually increases from 12.340 to 12.412.
  • the calcium oxide powder becomes more alkaline as it is dissolved in water.
  • Table 2 shows the results of disinfection, pH change and dissolution rate of the calcium ionized aqueous solution prepared according to Example 1 of the present invention.
  • Figure 2 is a graph showing the results for the growth experiments of the flounder (experimental group) and the flounder (control group) fed the feed supplemented with the additives to the flounder feed prepared by the aqueous solution of ionized calcium prepared according to Example 1 of the present invention It is shown.
  • the experimental group had an average body weight of 154 g and a control group of 144 g on May 14, the early stage of the experiment.
  • the final mean weight of the experimental group on July 13 was 283g and the control group was 254g.
  • Table 3 below shows the mean weight, survival rate and weight gain rate of the experimental and control groups.
  • the survival rate of the experimental group was 87.3%, higher than the 86.6% of the control group, the weight gain rate was 83.8% in the experimental group, 76.4% in the control group and the ion calcium aqueous solution prepared according to the embodiment of the present invention was used as a feed additive. It can be seen that the efficacy of.
  • FIG. 3 shows the blood of the flounder (experimental group) fed with the feed added with the aqueous calcium ionized solution prepared according to Example 1 as a feed additive and the blood of the flounder (control group) fed with the general feed, and aspartate amino group transfer.
  • the graph shows the result of measuring enzyme (AST).
  • the AST value was about 9U / L, whereas in the control group, the amount of aspartic acid aminotransferase was high in the experimental group.
  • the amount of glucose was high in the experimental group.
  • Figure 5 is a lysozyme (Lysozyme) by collecting the slime of the flounder (experimental group) and the halibut (control group) fed the feed with the feed added the calcium ionized aqueous solution prepared according to Example 1 of the present invention as a feed additive
  • This graph shows the result of measuring activity.
  • the experimental group was about 0.009 unit / mL, whereas the control group was measured at about 0.008 unit / mL, so the lysozyme activity was high in the experimental group.
  • the aqueous calcium ion solution prepared according to Example 1 of the present invention is easily absorbed into the cell body without the aid of an absorption promoter such as vitamin D3, thereby maximizing the efficacy of the calcium ion when absorbed into the cell body.
  • the present invention reaches a high concentration of pure calcium content of 94-97%, and provides a high purity stable alkaline ionized calcium aqueous solution in which hydrogen ion concentration is pH 12-13, food additives, calcium ion drink, animal feed, aquaculture It can be applied to fish feed, agricultural calcium ion, etc.

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Abstract

The present invention relates to an ionized calcium aqueous solution and to a production method therefor. More specifically, the invention relates to: an ionized calcium aqueous solution which has the effects of maximising the absorption of calcium into the bodies of livestock and promoting metabolism and vital functions in livestock; and to a production method therefor. The production method for the ionized calcium aqueous solution constituting the present invention provides a high-purity stable alkaline ionized calcium aqueous solution which achieves a high concentration with a pure calcium content of between 94 and 97% and in which the hydrogen ion concentration is from pH 12 to 13, thereby having the effect of increasing absorption and consequently maximising calcium efficacy when used in food additives, calcium ion drinks, animal feed, farmed fish feed, agricultural ionized calcium and the like. In addition, when the ionized calcium aqueous solution constituting another facet of the present invention is fed to livestock as an additive in feed, it has the effect of increasing the storage period by suppressing denaturing and microbial growth in the livestock feed, and minimising consequent loss of nutrients, and increasing the bodily absorption of calcium.

Description

이온화칼슘 수용액 및 그 제조방법Calcium ionized solution and preparation method thereof
본 발명은 이온화칼슘 수용액 및 그 제조방법에 관한 것으로, 더욱 자세하게는 가축의 체내로의 칼슘의 흡수를 극대화시키고, 가축의 신진대사 및 생체기능을 촉진시키는 효과가 있는 이온화칼슘 수용액 및 그 제조방법에 관한 것이다.The present invention relates to an aqueous calcium ion solution and a method for manufacturing the same, and more particularly, to an aqueous calcium ion solution and a method for producing the same, which maximize the absorption of calcium into the body of animals and promote metabolism and biological function of the animals. It is about.
칼슘의 세포 내 흡수율을 높이려면 칼슘이 수용성으로 이온화되어 있어야 한다. 석회암 등에 포함된 탄산칼슘으로부터 유래하는 칼슘이온(Ca2+)이 지하수 속에 자연적으로 풍부하게 존재하기 위해서는 오랜 세월을 요구할 뿐만 아니라, 석회암 그 자체가 단단한 암석질로 되어있어 물속에 쉽게 용출되지 않는다. In order to increase the intracellular absorption of calcium, calcium must be ionized to be water soluble. Calcium ions (Ca 2+) derived from calcium carbonate contained in limestone, etc., require a long time to naturally exist in the groundwater, and limestone itself is hard rock and does not easily dissolve in water.
이러한 점을 극복하기 위해 칼슘이온 용출을 위한 맥반석, 일라이트 및 석회석 등을 이용한 점토광물의 인공적인 다공성 세라믹 소결체의 제조기술이 있으나 제품화하는 과정에서 신뢰도가 떨어진다는 문제점이 있다. In order to overcome this point, there is a manufacturing technology of artificial porous ceramic sintered body of clay mineral using elvan, illite and limestone for elution of calcium ions, but there is a problem in that reliability is lowered during commercialization.
또한, 패각류의 단순 소성으로 회분류를 다량 포함하는 석회칼슘이 토양 개량제로 활용되어 집적될 경우 토양 내 석회화를 가속화하기도 하며, 이러한 석회칼슘은 사료보조제로 활용되고 있으나 불용성의 한계가 있다. In addition, when lime calcium containing a large amount of ash is accumulated as a soil improver by the simple firing of shellfish, the calcium calcification in the soil may be accelerated, and the lime calcium is used as a feed supplement, but there is a limit of insolubility.
이러한 점을 극복하기 위한 초고온 소성의 방법으로서 탄소 및 코크스를 패각류와 함께 고온 소성하여 불순물을 제거한 후, 인체나 동물에 적용할 수 있는 수소이온농도(pH)를 갖는 이온화칼슘의 제조기술이 있다. 이때 기술적으로 합리적인 소성의 조건을 갖춘다 하더라도 주어진 재료의 여건에 따라 제조물의 수소이온농도(pH) 및 칼슘 함량의 편차를 극복하기가 어렵다. 따라서 제품화하는 과정에서 성분의 함량 및 규격에 신뢰도가 떨어진다는 문제점이 있었다.As a method of ultra high temperature calcination to overcome this point, there is a manufacturing technique of calcium ion having a hydrogen ion concentration (pH) that can be applied to humans or animals after removing impurities by high temperature calcination of carbon and coke together with shells. . At this time, even if technically reasonable conditions of firing, it is difficult to overcome the variation in the pH and calcium content of the product according to the conditions of the given material. Therefore, there was a problem in that the reliability of the content and specification of the ingredients in the process of commercialization.
본 발명은 상술한 것과 같은 문제점 및 한계점을 극복하기 위하여 안출된 것으로서, The present invention has been made to overcome the problems and limitations as described above,
본 발명의 목적은 이온화칼슘의 함유량 및 규격을 안정화하고 그에 따른 미량요소의 적정 수준이 유지될 수 있고, 적절한 pH를 유지하는 이온화칼슘 수용액의 제조방법을 제공하는 데 있다. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for preparing an aqueous calcium ion solution to stabilize the content and specification of calcium ion and to thereby maintain an appropriate level of trace elements, and to maintain an appropriate pH.
또한, 본 발명의 다른 목적은 가축사료의 변질 및 세균 발생을 억제하여 보존기간을 증가시키고, 그에 따른 영양분의 손실을 최소화하며, 칼슘의 체내흡수율을 높여줄 수 있는 가축사료로 활용될 수 있는 이온화칼슘 수용액을 제공하는 데 있다.In addition, another object of the present invention is to increase the shelf life by inhibiting the alteration and bacterial generation of livestock feed, thereby minimizing the loss of nutrients, ionization that can be used as a livestock feed that can increase the body absorption rate of calcium It is to provide an aqueous solution of calcium.
상기 목적을 달성하기 위하여 본 발명은 다음과 같은 구체적인 과제해결수단을 제시한다.In order to achieve the above object, the present invention provides the following specific problem solving means.
본 발명에 의한 이온화칼슘 수용액의 제조방법은, 패각류의 세척을 통해 이물질 및 불순물을 제거한 후 건조시키는 세척단계; 상기 건조된 패각류를 가열 및 소성시켜 건조된 패각류에 포함된 유기물 및 잔류 독성을 제거하여 산화칼슘을 제조하는 고온소성단계; 상기 산화칼슘을 분쇄하여 산화칼슘분말을 제조하는 분쇄단계; 상기 산화칼슘분말과 물을 혼합 및 교반하여 산화칼슘용액을 제조하는 교반단계; 상기 산화칼슘용액을 포함하는 용기에 포화증기를 공급하여, 상기 용기 내에 정전기를 발생시킴으로써 이온반응을 유도하여 이온화칼슘 수용액을 제조하는 이온반응단계; 및 상기 이온화칼슘 수용액에 연수처리된 물 또는 순수처리된 물을 첨가하여 수소이온농도가 pH 12~13을 유지하도록 하는 수소이온농도조절단계;를 포함하는 것을 특징으로 한다.Method for producing an aqueous calcium ion solution according to the present invention, washing step of removing foreign matter and impurities through the washing of shells; A high temperature firing step of heating and calcining the dried shellfish to produce calcium oxide by removing organic substances and residual toxicity contained in the dried shellfish; Grinding the calcium oxide to produce a calcium oxide powder; A stirring step of preparing a calcium oxide solution by mixing and stirring the calcium oxide powder and water; Supplying saturated steam to the container containing the calcium oxide solution, inducing an ionic reaction by generating static electricity in the container to produce an ionized calcium solution; And a hydrogen ion concentration adjusting step of adding the soft water treated water or pure water to the ionized calcium aqueous solution to maintain the hydrogen ion concentration at pH 12-13.
이때, 상기 고온소성단계에서는, 1100~2000℃의 온도에서, 1~3시간 동안 건조된 패각류를 가열 및 소성시키는 것이 좋다. 이는 건조된 패각류가 완전히 소성되도록 하기 위하여 필요한 온도 및 시간으로서 용도에 따라 온도 및 시간을 조절할 수 있다. 이때, 패각류의 완전 소성 및 칼슘화를 촉진시키기 위하여 초기온도 1100℃에서 최종온도 2000℃까지 1~3시간에 걸쳐 점진적으로 온도를 상승시켜 건조된 패각류를 가열 및 소성시키는 것이 바람직하다.At this time, in the high temperature firing step, it is preferable to heat and fire shellfish dried for 1 to 3 hours at a temperature of 1100 ~ 2000 ℃. This is the temperature and time necessary to allow the dried shellfish to be completely fired, and thus the temperature and time can be adjusted according to the application. At this time, in order to promote complete calcining and calciumation of the shellfish, it is preferable to gradually raise the temperature from 1100 ° C to the final temperature of 2000 ° C over 1 to 3 hours to heat and calcine the dried shellfish.
나아가, 포유류나 조류와 같은 항온동물에 대한 가축사료 첨가제로서 사용하고자 하는 경우에는 건조된 패각류를 1100~1600℃의 범위에서 2~3시간 동안 가열 및 소성시키는 것이 좋다. 물론 이 경우에도 처음온도 1100℃에서부터 최종온도 1600℃에 이르기까지 소성온도를 2~3시간에 걸쳐 조금씩 순차적으로 높이는 것이 바람직하다. 이는 상대적으로 항온동물에 대한 가축사료 첨가제로 이온화칼슘 수용액을 사용하는 경우에 입자가 다소 크거나 이온화도가 떨어진다 하더라도 그 효과를 잘 볼 수 있기 때문이며 성분에 대한 민감성이 어류에 비해 떨어지기 때문이다.Furthermore, when it is intended to be used as a livestock feed additive for constant temperature animals such as mammals or birds, it is preferable to heat and calcined dried shellfish for 2 to 3 hours in the range of 1100 to 1600 ° C. Of course, even in this case, it is preferable that the firing temperature is gradually increased gradually over 2 to 3 hours from the initial temperature of 1100 ° C to the final temperature of 1600 ° C. This is because when the calcium ionized aqueous solution is used as an additive for livestock animals for constant temperature animals, the effect can be seen even if the particles are somewhat large or the ionization degree is lower, and the sensitivity to the components is less than that of the fish.
한편, 상기 분쇄단계에서 분쇄된 산화칼슘분말의 입자크기는 20㎛이하인 것이 좋은데, 이온화칼슘 수용액이 어떤 용도로 사용되는지 여부에 따라 입자 크기를 조절할 수 있다. 예를 들어 어류양식용 사료에 첨가할 경우에는 변온동물인 어류의 민감성을 감안하여 산화칼슘분말의 입자 크기를 10㎛이하로 제한하는 것이 바람직하나 상대적으로 덜 민감한 포유류나 조류와 같은 가축의 사료용 첨가제로 사용할 경우에는 산화칼슘분말의 입자 크기를 20㎛로 하여도 별 무리가 없기 때문이다.On the other hand, the particle size of the calcium oxide powder pulverized in the crushing step is preferably 20㎛ or less, the particle size can be adjusted depending on whether the aqueous solution of calcium ionization is used. For example, when added to aquaculture feed, it is desirable to limit the particle size of the calcium oxide powder to 10 μm or less in consideration of the sensitivity of the fish, which is a transgenic animal, but for feed additives of livestock such as mammals or birds, which are relatively less sensitive. This is because even if the particle size of the calcium oxide powder is set to 20㎛, it is not too much.
상기 교반단계에서는 물 100중량부에 대해 산화칼슘분말을 0.1~ 2중량부의 비율로 혼합 및 교반하는 것이 좋은데, 이러한 중량비로 혼합 및 교반할 때 산화칼슘분말이 가장 잘 물에 이온화되기 때문이다. 아울러 교반단계에서의 교반시간은 혼합 후 2~5시간 동안 교반하는 것이 좋은데, 포유류나 조류와 같은 항온동물에 대한 가축사료의 첨가제로 사용할 때에는 2~4시간 정도 교반하는 것이 좋으며, 상대적으로 분말의 입자크기가 적은 경우에는 물에 고르게 분산시키도록 하여 이온화도를 높여야 하기 때문에 3~5시간 정도 교반을 시키는 것이 바람직하다.In the stirring step, it is preferable to mix and stir the calcium oxide powder at a ratio of 0.1 to 2 parts by weight with respect to 100 parts by weight of water, because the calcium oxide powder is best ionized in water when mixing and stirring at this weight ratio. In addition, the stirring time in the stirring step is preferably stirred for 2 to 5 hours after mixing, when used as an additive for livestock feed for constant temperature animals such as mammals and birds, it is preferable to stir for 2 to 4 hours, and relatively When the particle size is small, it is preferable to stir for 3 to 5 hours because the degree of ionization should be increased by dispersing it evenly in water.
또한, 상기 이온반응단계에서 공급되는 포화증기의 압력은 1.4~5MPa인 것이 좋다. In addition, the pressure of the saturated steam supplied in the ion reaction step is preferably 1.4 ~ 5MPa.
아울러, 본 발명에 의한 이온화칼슘 수용액의 제조방법은 이를 구성하는 각 단계 중 이온반응단계가, 상기 용기에 상기 산화칼슘용액을 주입하는 산화칼슘용액주입단계; 상기 용기에 300℃ 이하의 온도 및 1.4~5㎫의 압력을 가지는 포화증기를 공급하면서 생성되는 물방울에 의해 정전기가 발생하는 정전기발생단계; 상기 용기 내부의 압력을 일정하게 유지하면서 상기 용기 내부를 교반함으로써 이온반응을 유도하는 이온반응유도단계; 상기 용기 내부의 포화증기를 제1감압탱크로 배출하여 상기 용기 내부와 상기 제1감압탱크 내부가 압력평형을 이루는 제1포화증기배출단계; 상기 제1 감압탱크를 폐쇄한 후, 상기 용기 내부의 포화증기를 상기 제1 감압탱크보다 큰 체적을 갖는 제2감압탱크로 배출하는 제2포화증기배출단계; 및 상기 제1감압탱크 및 상기 제2감압탱크에서 상기 이온화칼슘 수용액을 획득하는 이온화칼슘수용액획득단계;를 포함하여 구성되는 것이 다른 특징이다. In addition, the method for producing an aqueous calcium ion solution according to the present invention, the ion reaction step of each step constituting the calcium oxide solution injection step of injecting the calcium oxide solution into the container; An electrostatic generating step of generating static electricity by water droplets generated while supplying saturated steam having a temperature of about 300 ° C. or less and a pressure of 1.4 to 5 MPa to the vessel; An ion reaction inducing step of inducing an ionic reaction by stirring the inside of the container while maintaining a constant pressure inside the container; A first saturated steam discharge step of discharging saturated steam in the container to a first pressure reducing tank to balance pressure between the inside of the container and the inside of the first pressure reducing tank; A second saturated steam discharging step of discharging saturated steam in the container to a second pressure reducing tank having a volume larger than that of the first pressure reducing tank after closing the first pressure reducing tank; And an ionizing calcium aqueous solution obtaining step of obtaining the aqueous calcium ionization solution in the first and second decompression tanks.
한편, 본 발명의 다른 관점인 이온화칼슘 수용액은 상기 제조방법에 의해 제조된 것을 특징으로 한다.On the other hand, the aqueous solution of calcium ion which is another aspect of the present invention is characterized in that it is produced by the above production method.
본 발명인 이온화칼슘 수용액의 제조방법에 따르면 순수한 칼슘의 함유량이 94~97%에 이를 정도로 고농도에 달하고, 수소이온농도가 pH 12~13에 속하는 고순도의 안정된 알칼리성 이온화칼슘 수용액을 제공함으로써 식품첨가물, 칼슘이온음료, 동물사료, 양식어류사료, 농업용 이온화칼슘 등에 적용하여 사용시에 체내 흡수율이 높고 그에 따라 칼슘의 효능이 극대화되는 효과가 있다.According to the present invention, the method for preparing an aqueous calcium ion solution reaches a high concentration such that the content of pure calcium reaches 94 to 97%, and provides a high purity stable alkaline ionized calcium aqueous solution having a hydrogen ion concentration of pH 12 to 13, thereby adding food additives and calcium. When applied to ionic beverages, animal feeds, farmed fish feeds, agricultural ionized calcium, etc., the absorption rate in the body is high when used, thereby maximizing the effect of calcium.
또한 본 발명에 의한 이온화칼슘 수용액은 가축사료에 첨가되어 사용될 경우 가축사료의 변질 및 세균 발생을 억제하여 보존 기간을 증가시키고, 그에 따른 영양분의 손실을 최소화하며, 칼슘의 체내흡수율을 높여주어 칼슘흡수 부족으로 인해 발생하는 장내가스발생, 칼슘대사장애에 의한 복수발생, 칼슘부족으로 인한 면역력 저하, 피부점액질 저하 등을 줄여주는 효과가 있다.In addition, the ionized calcium aqueous solution according to the present invention increases the shelf life by inhibiting the alteration and bacterial generation of animal feed when used in animal feed, minimizes the loss of nutrients, and increases the body absorption rate of calcium by absorbing calcium It is effective in reducing intestinal gas generated by deficiency, ascites caused by calcium metabolic disorder, lowering immunity due to calcium deficiency, and lowering skin mucus.
도 1은 본 발명의 일실시예에 따른 이온화칼슘 수용액의 제조공정을 도시한 공정도이다. 1 is a process chart showing a manufacturing process of an aqueous calcium ion solution according to an embodiment of the present invention.
도 2는 본 발명의 실시예에 따라 제조된 이온화칼슘 수용액을 넙치사료에 첨가제로 첨가한 사료를 먹인 넙치 및 일반사료를 먹인 넙치의 생육실험에 대한 결과를 보여주는 그래프를 나타낸 것이다.Figure 2 shows a graph showing the results for the growth experiments of the flounder fed with the feed added as an additive to the halibut calcium aqueous solution prepared in accordance with an embodiment of the flounder and the flounder fed with the general feed.
도 3은 본 발명의 실시예에 따라 제조된 이온화칼슘 수용액을 사료첨가제로써 첨가한 사료를 먹인 넙치의 혈액 및 일반사료를 먹인 넙치의 혈액을 각각 채취하여 아스파르트산아미노기전달효소(AST)를 측정한 결과를 보여주는 그래프를 나타낸 것이다. Figure 3 is the blood of the halibut fed the feed with the addition of the aqueous solution of ionized calcium prepared according to an embodiment of the present invention as a feed additive and the blood of the halibut fed the normal feed to measure the aspartic acid amino-transferase (AST) The graph shows the results.
도 4는 본 발명의 실시예에 따라 제조된 이온화칼슘 수용액을 사료첨가제로써 첨가한 사료를 먹인 넙치의 혈액 및 일반사료를 먹인 넙치의 혈액을 채취하여 글루코오스(Glucose)를 측정한 결과를 보여주는 그래프이다.Figure 4 is a graph showing the results of measuring the glucose (Glucose) by collecting the blood of the olive flounder fed the feed and the general feed fed with the calcium ionized aqueous solution prepared according to an embodiment of the present invention as a feed additive .
도 5는 본 발명의 실시예에 따라 제조된 이온화칼슘 수용액을 사료첨가제로써 첨가한 사료를 먹인 넙치의 점액 및 일반사료를 먹인 넙치의 점액을 각각 채취하여 라이소자임(Lysozyme) 활성도를 측정한 결과를 보여주는 그래프이다.Figure 5 shows the results of measuring the lysozyme activity by collecting the slime and the slime of the halibut fed the feed with the feed added to the ionized calcium aqueous solution prepared according to an embodiment of the present invention as a feed additive It is a graph.
이하 첨부된 도면을 통하여 본 발명의 일실시예를 상세하게 설명하기로 한다.Hereinafter, an embodiment of the present invention will be described in detail with reference to the accompanying drawings.
도 1은 본 발명의 일실시예에 따른 이온화칼슘 수용액의 제조공정을 도시한 공정도이다. 1 is a process chart showing a manufacturing process of an aqueous calcium ion solution according to an embodiment of the present invention.
1. 세척단계(S100)1. Cleaning step (S100)
세척단계에서는 패각류의 세척을 통해 이물질 및 불순물을 제거한 후 건조시킨다. 패각(Shell, 貝殼)은 연체동물에서 연체를 싸서 보호하는 무기질의 분비형성물을 말하며, 여기서 패각류는 굴패각, 조개패각 등이 사용될 수 있다.In the washing step, foreign substances and impurities are removed by washing shellfish and dried. Shell (Shell, 貝殼) refers to the inorganic secretion formation to protect the molluscs in mollusks, where shells may be used such as oyster shells, shell shells.
2. 고온소성단계(S200)2. High temperature firing step (S200)
이어서, 고온소성단계에서 건조된 패각류를 가열 및 소성시켜 건조된 패각류에 포함된 유기물 및 잔류 독성을 제거하여 산화칼슘을 제조한다.Subsequently, the dried shellfish is heated and calcined in the high temperature baking step to remove organic matter and residual toxicity contained in the dried shellfish, thereby preparing calcium oxide.
이때 건조된 패각류를 1100℃ 내지 2000℃에서, 1~3시간 동안 가열 및 소성시킴으로써 산화칼슘을 제조할 수 있다. 그리고, 이때 건조된 패각류를 초기온도 1100℃에서, 최종온도 2000℃까지 점진적으로 온도를 상승시켜 가열 및 소성시킴으로써 산화칼슘을 제조할 수 있다.In this case, calcium oxide may be prepared by heating and firing the dried shellfish at 1100 ° C. to 2000 ° C. for 1 to 3 hours. In this case, calcium oxide may be prepared by heating and firing the dried shellfish at an initial temperature of 1100 ° C. and gradually raising the temperature to a final temperature of 2000 ° C.
고온소성단계에서 패각류를 구성하는 성분인 탄산칼슘(CaCO3)은 소성되어 고체상태의 산화칼슘(CaO)으로 전환된다.In the high temperature firing step, calcium carbonate (CaCO 3 ), which is a constituent of shellfish, is calcined and converted to calcium oxide (CaO) in solid state.
3. 분쇄단계(S300)3. Grinding step (S300)
상기 고온소성단계에서 제조된 산화칼슘을 분쇄하여 산화칼슘분말을 제조한다. 이때 습식 볼밀을 이용하여 분쇄하는 것이 바람직하다.Calcium oxide powder is prepared by grinding the calcium oxide prepared in the high temperature firing step. At this time, it is preferable to grind using a wet ball mill.
이때, 분쇄된 산화칼슘분말의 입자직경은 20㎛이하일 수 있다. 여기서 산화칼슘분말의 입자직경이 20㎛를 초과하게 되면 물과 혼합하여 산화칼슘용액을 제조할 때 잘 섞이지 않게 되는 문제점이 있기 때문이다. 한편, 어류사료첨가제로서 사용되는 이온화칼슘 용액을 얻고자 할 때에는 10㎛이하의 입자직경을 갖도록 분쇄하는 것이 바람직한데 이는 10㎛ 이하 크기의 산화칼슘분말이 보다 물에 잘 섞이기 때문이다. At this time, the particle diameter of the pulverized calcium oxide powder may be 20㎛ or less. If the particle size of the calcium oxide powder exceeds 20㎛ is because there is a problem that is not well mixed when preparing a calcium oxide solution by mixing with water. On the other hand, in order to obtain an ionized calcium solution used as a fish feed additive, it is preferable to grind to have a particle diameter of 10㎛ or less, because the calcium oxide powder of 10㎛ or less size is better mixed with water.
4. 교반단계(S400)4. Stirring step (S400)
교반단계에서 산화칼슘분말과 물을 혼합 및 교반하여 산화칼슘용액을 제조한다. 여기서 제조된 산화칼슘용액은 강알칼리성이다.In the stirring step, the calcium oxide powder and water are mixed and stirred to prepare a calcium oxide solution. The calcium oxide solution prepared here is strongly alkaline.
이때 물과 산화칼슘분말의 혼합 중량비는 물 100중량부에 대하여 산화칼슘분말 0.1~2 중량부인 것이 바람직하다. 왜냐하면 물 100중량부에 대해 산화칼슘분말의 중량 비율이 2중량부를 초과하게 되면 물에 충분하게 섞이지 않을 수 있고, 0.1중량부 미만이라면 제조된 이온화칼슘 수용액은 체내에 충분한 칼슘을 공급하지 못할 수 있기 때문이다. 따라서 상기 중량비를 유지할 경우에는 산화칼슘분말은 물에 충분히 잘 섞이며, 이온화칼슘 수용액으로서 사료첨가제로 사용할 경우 체내에 충분한 칼슘을 공급하는 효과를 발휘하게 된다.At this time, the mixed weight ratio of water and calcium oxide powder is preferably 0.1 to 2 parts by weight of calcium oxide powder based on 100 parts by weight of water. Because if the weight ratio of calcium oxide powder to 100 parts by weight of water exceeds 2 parts by weight may not be sufficiently mixed in water, if less than 0.1 parts by weight prepared aqueous solution of calcium ion may not supply enough calcium in the body Because. Therefore, when the weight ratio is maintained, the calcium oxide powder is well mixed with water, and when used as a feed additive as an aqueous solution of calcium ion, it exhibits the effect of supplying sufficient calcium in the body.
한편, 산화칼슘분말과 물을 혼합한 후에 2~5시간 동안 교반함으로써 산화칼슘용액을 제조할 수 있다. 이때 2~5시간 동안 교반함으로써 산화칼슘분말이 물에 골고루 섞이게 한다. 한편, 어류사료용 첨가제로서 사용되는 이온화칼슘 수용액을 제조하는 경우에는 3~5시간 정도 교반을 시켜 미세한 산화칼슘분말이 물에 잘 섞여서 분산이 잘 되도록 하는 것이 좋다.Meanwhile, the calcium oxide solution may be prepared by mixing the calcium oxide powder and water, followed by stirring for 2 to 5 hours. At this time, the calcium oxide powder is evenly mixed with water by stirring for 2 to 5 hours. On the other hand, when preparing an aqueous calcium ion solution used as additives for fish feed it is good to stir for about 3 to 5 hours to finely disperse the fine calcium oxide powder mixed in water well.
5. 이온반응단계(S500)5. Ion reaction step (S500)
상기 교반단계(S400)에서 제조된 산화칼슘용액을 포함하는 용기에 포화증기를 공급하여, 용기 내에 정전기를 발생시킴으로써 이온반응을 유도하여 이온화칼슘 수용액을 제조한다.Saturated steam is supplied to a vessel containing the calcium oxide solution prepared in the stirring step (S400) to generate an electrostatic reaction in the vessel to prepare an ionized calcium aqueous solution.
우선 보일러에서 발생한 포화증기는 용기에 투입 시 용기 내에서의 온도 저하로 인해 약간의 응축 현상이 발생하며 그로 인해 작은 물방울이 생성된다. 생성된 작은 물방울은 서로 충돌하거나 마찰함으로써, 정전기를 발생시킨다. 또한 공급된 포화증기에 의해 내부의 공기가 축출되며, 산화칼슘용액 내에도 포화증기가 침투한다. 작은 물방울에 축적된 정전기는 산화칼슘용액을 통하거나 또는 직접 용기에 도달한다.First of all, saturated steam generated in a boiler generates some condensation due to the temperature drop in the vessel, which results in the formation of droplets. The generated droplets collide or rub against each other, thereby generating static electricity. In addition, the supplied air is expelled by the supplied saturated steam, and saturated steam also penetrates into the calcium oxide solution. The static electricity accumulated in the droplets reaches the container either directly or through calcium oxide solution.
산화칼슘용액 중 정전기가 흐른 부분은 국소적으로 발열하여 온도가 상승하고 이온구조화 되지만 전류는 연속하여 흐르는 것은 아니고 또한 전력량은 작기 때문에 온도의 상승량은 적다. 그리고 용기 내의 평균 온도는 공급되는 포화증기의 온도 이상으로는 상승하지 않기 때문에 유해성분이 발생하기 어렵다.The portion where the static electricity flows in the calcium oxide solution is locally heated to rise in temperature and ion structure, but the current is not continuously flowing and the amount of power is small, so the temperature rise is small. In addition, since the average temperature in the container does not rise above the temperature of the saturated steam supplied, harmful components hardly occur.
또한, 용기 내에는 포화증기가 충진되어 있기 때문에 정전기가 흐름으로써 불꽃이 발생하더라도 가연성 가스 등으로 인화하여 폭발하는 것이 방지된다.In addition, since saturated steam is filled in the container, even if sparks are generated by the flow of static electricity, it is prevented from being flammed by flammable gas or the like.
이와 같이 포화증기의 열, 압력 및 정전기를 이용함으로써 안정적인 수용성 이온화칼슘화 작용이 발생한다.Thus, by using the heat, pressure and static electricity of saturated steam, a stable water-soluble ionization calciumation action occurs.
한편 용기 및 교반 수단이 대전성 재질로 구성되어 있어 다음과 같은 메커니즘에 따라 이온화가 촉진될 수 있다. 용기 및 교반 수단이 대전성을 갖고, 기대(基台)에 대하여 절연상태로 설치되어 있게 되면 산화칼슘용액과의 마찰에 의해, 산화칼슘용액, 용기 및 교반 수단에는 플러스 또는 마이너스의 전하(정전기)가 축적된다. 한편, 용기 내에는 가열 및 가압된 포화증기가 공급되고, 이 포화증기가 산화칼슘용액의 내부에 침투하기 때문에 산화칼슘용액 내부의 전기 저항이 내려가 전기가 흐르기 쉬워져 있다.Meanwhile, since the vessel and the stirring means are made of a chargeable material, ionization may be promoted according to the following mechanism. When the vessel and the stirring means are charged and provided in an insulated state with respect to the base, the calcium oxide solution, the vessel and the stirring means have positive or negative charges (electrostatic) due to friction with the calcium oxide solution. Accumulates. On the other hand, the saturated steam heated and pressurized is supplied in the container, and since this saturated vapor penetrates into the inside of the calcium oxide solution, the electrical resistance inside the calcium oxide solution decreases, so that electricity easily flows.
여기에서 대전성을 갖는다는 것은 전기 저항이 크고, 투입되는 산화칼슘용액에 대해서 플러스 또는 마이너스로 대전가능한 것을 말하며 플러스 또는 마이너스 어느 쪽으로 대전해도 상관없다.Here, the charging property means that the electrical resistance is large and that the added calcium oxide solution can be positively or negatively charged. The charging may be performed either positively or negatively.
예를 들어 용기 및 교반 수단에 플러스 전하가 축적되어 있을 때 산화칼슘용액 내에 일정량의 마이너스 전하가 모이면 이 전하는 산화칼슘용액의 내부를 지나, 용기 및 교반 수단으로 흐른다. 산화칼슘용액은 교반되기 때문에, 전하가 모이는 양은 각 부분에 따라 다르고 또한 전하가 흐르는 경로나 시간도 다르다. 또한, 용기 내에는 포화증기가 충진되어 있기 때문에, 전기 저항이 너무 커지거나, 정전기가 너무 모이는 일도 없다. 따라서, 정전기는 조금씩 방전되고 방전시의 방전 경로에 순간적으로 열량을 발생시키면서 산화칼슘용액은 안정적인 이온화칼슘 수용액으로 변환한다. 그러나 방전은 연속적으로는 행해지지 않기 때문에 고온으로 되지 않고, 용기 내 전체 온도는 가열 증기에 의한 설정온도에서 크게 상승하지 않으며, 물은 유해성분의 발생을 억제하게 된다.For example, when a certain amount of negative charge is accumulated in the calcium oxide solution when positive charge is accumulated in the vessel and the stirring means, the charge flows through the inside of the calcium oxide solution and into the vessel and the stirring means. Since the calcium oxide solution is agitated, the amount of charge collection varies with each part, and the path and time through which the charge flows also differ. In addition, since saturated steam is filled in the container, the electrical resistance is not too high or the static electricity is not collected too much. Therefore, the static electricity is discharged little by little, and instantaneously generates heat in the discharge path during discharge, while the calcium oxide solution is converted into a stable aqueous solution of calcium ionization. However, since discharge is not carried out continuously, it does not become a high temperature, the entire temperature in the container does not increase significantly at the set temperature by heating steam, and water suppresses the generation of harmful components.
이때 산화칼슘수용액을 포함하는 용기에 공급되는 포화증기의 압력은 1.4~5㎫일 수 있다.In this case, the pressure of the saturated steam supplied to the container including the calcium oxide aqueous solution may be 1.4 to 5 MPa.
한편, 이온반응단계(S500)은 구체적으로는 상기 용기에 상기 산화칼슘용액을 주입하는 산화칼슘용액주입단계(S510); 상기 용기에 300℃ 이하의 온도 및 1.4~5㎫의 압력을 가지는 포화증기를 공급하면서 생성되는 물방울에 의해 정전기가 발생하는 정전기발생단계(S520); 상기 용기 내부의 압력을 일정하게 유지하면서 상기 용기 내부를 교반함으로 써 이온반응을 유도하는 이온반응유도단계(S530); 상기 용기 내부의 포화증기를 제1감압탱크로 배출하여 상기 용기 내부와 상기 제1감압탱크 내부가 압력평형을 이루는 제1포화증기배출단계(S540); 상기 제1 감압탱크를 폐쇄한 후, 상기 용기 내부의 포화증기를 상기 제1 감압탱크보다 큰 체적을 갖는 제2감압탱크로 배출하는 제2포화증기배출단계(S550); 및 상기 제1감압탱크 및 상기 제2감압탱크에서 상기 이온화칼슘 수용액을 획득하는 이온화칼슘수용액획득단계(S560)으로 구성된다. On the other hand, the ion reaction step (S500) is a calcium oxide solution injection step (S510) specifically injecting the calcium oxide solution into the container; An electrostatic generating step (S520) in which static electricity is generated by water droplets generated while supplying saturated steam having a temperature of about 300 ° C. or less and a pressure of 1.4 to 5 MPa to the vessel; An ion reaction inducing step (S530) of inducing an ionic reaction by stirring the inside of the container while maintaining a constant pressure in the container; A first saturated steam discharge step (S540) of discharging saturated steam in the container to a first pressure reducing tank to achieve a pressure balance between the inside of the container and the first pressure reducing tank; A second saturated steam discharge step (S550) of discharging saturated steam in the container to a second pressure reducing tank having a volume larger than that of the first pressure reducing tank after closing the first pressure reducing tank; And an aqueous calcium ion solution acquisition step (S560) of obtaining the aqueous calcium ionization solution from the first pressure reducing tank and the second pressure reducing tank.
6. 수소이온농도 조절단계(S600)6. Hydrogen ion concentration adjusting step (S600)
이온화칼슘 수용액에 연수처리된 물 또는 순수처리된 물을 첨가함으로써 수소이온농도가 pH12~13을 유지하도록 한다.Hydrogen ion concentration is maintained at pH 12-13 by adding soft water or pure water to the calcium ionized solution.
여기서 연수처리된 물이란 경도를 0~60mg/L 미만으로 조정한 물을 말하고, 순수처리된 물이란 경도분(硬度分)을 포함하는 불순물을 제거한 물을 말한다.Herein, soft water treated water refers to water whose hardness is adjusted to less than 0 to 60 mg / L, and pure water treated water refers to water from which impurities including hardness components are removed.
한편, 본 발명의 실시예에 따라 제조된 이온화칼슘 수용액은 어류사료의 첨가제, 가축사료의 첨가제, 이온화칼슘 음료 및 식물의 칼슘강화제 등으로 사용될 수 있지만, 이에만 한정되는 것은 아니다.On the other hand, the aqueous solution of calcium ion prepared according to the embodiment of the present invention can be used as additives of fish feed, additives of livestock feed, calcium ionized drinks and calcium fortification of plants, but is not limited thereto.
<실시예 1><Example 1>
넙치와 같은 변온동물인 어류에 사료첨가제로서 사용하고자 하는 경우에는 건조된 패각류를 1300~2000℃에 이르기까지 점진적으로 온도를 올려 총 가열 및 소성시키는 시간이 2~3시간이 되도록 하였다. 아울러, 고온소성단계에서 생성된 산화칼슘을 입자크기가 8㎛이 되도록 습식 볼밀로 분쇄한 후 이를 물과 혼합 및 교반을 하였다. 이때 물과 산화칼슘분말은 물 100중량부에 대해 산화칼슘분말 1중량비의 비율로 혼합한 후에 이를 5시간 동안 교반하여 산화칼슘용액을 제조하였다. 제조된 산화칼슘용액을 포함하는 용기에 4MPa의 압력을 가진 포화증기를 공급하여 이온반응을 유도하여 이온화칼슘 수용액을 제조한 후 여기에 연수처리된 물을 첨가하여 수소이온농도가 pH 13이 된 것을 제조한 것을 넙치용 사료에 첨가한 후 이를 넙치에 공급하였다. 치어기의 경우 물로 10배 희석한 것을 사용하되 성어가 되어 갈수록 희석을 하지 않고 사용하는 것이 바람직하다.In the case of using as a feed additive for fish, such as a flatfish, such as flounder, the dried shellfish was gradually heated up to 1300 to 2000 ° C. so that the total heating and calcining time was 2 to 3 hours. In addition, the calcium oxide produced in the high temperature firing step was pulverized with a wet ball mill to have a particle size of 8㎛, and then mixed with water and stirred. At this time, the water and calcium oxide powder was mixed in a ratio of 1 weight ratio of calcium oxide powder to 100 parts by weight of water and then stirred for 5 hours to prepare a calcium oxide solution. Saturated steam with a pressure of 4 MPa was supplied to the vessel containing the prepared calcium oxide solution to induce an ionic reaction to prepare a calcium ionized aqueous solution. The prepared was added to the feed for the flounder and then fed to the flounder. In case of fry, 10 times diluted with water is used, but it is preferable to use it without diluting as it becomes adult.
한편 전체 기간동안 넙치사료에 첨가제로 이온화칼슘 수용액을 사용할 때에는 넙치사료 1kg에 대해 이온화칼슘 수용액 1g의 비율로 첨가하여 사용하였다.On the other hand, when the calcium ionized aqueous solution was used as an additive to the olive flounder for the entire period, it was used by adding 1 g of calcium ionized aqueous solution to 1 kg of olive flounder.
아래의 표 1은 본 발명의 실시예 1에 따라 제조된 이온화칼슘 수용액의 산화칼슘분말의 함량비에 따른 수소이온농도를 나타낸다.Table 1 below shows the hydrogen ion concentration according to the content ratio of the calcium oxide powder of the aqueous solution of calcium ionized according to Example 1 of the present invention.
표 1
이온화칼슘 수용액(g/10㎖) pH측정값
0.01 12.340
0.02 12.387
0.03 12.394
0.04 12.411
0.05 12.412
Table 1
Calcium ionized solution (g / 10mL) pH measurement
0.01 12.340
0.02 12.387
0.03 12.394
0.04 12.411
0.05 12.412
물 10ml에 용해되는 산화칼슘분말이 0.01g에서 0.05g으로 증가할수록 pH값은 12.340에서 12.412로 점차적으로 증가하는 것을 볼 수 있는데, 산화칼슘분말은 물에 녹을수록 알칼리성이 강해짐을 나타낸다.As the calcium oxide powder dissolved in 10 ml of water increases from 0.01 g to 0.05 g, the pH value gradually increases from 12.340 to 12.412. The calcium oxide powder becomes more alkaline as it is dissolved in water.
아래의 표 2는 본 발명의 실시예 1에 따라 제조된 이온화칼슘 수용액의 살균성, pH변화 및 용해율 측정결과를 나타낸다.Table 2 below shows the results of disinfection, pH change and dissolution rate of the calcium ionized aqueous solution prepared according to Example 1 of the present invention.
표 2
증류수양 측정시간 O.D.값(600) pH 침전물 유무
40㎖ 초기 0.005 12.785
1hr 이후 0.010 12.592
50㎖ 초기 0.005 12.662
1hr 이후 0.010 12.512
TABLE 2
Distilled water Measuring time OD value (600) pH Presence of sediment
40 ml Early 0.005 12.785 U
After 1hr 0.010 12.592 radish
50 ml Early 0.005 12.662 U
After 1hr 0.010 12.512 radish
증류수의 양이 40 또는 50ml일 때 O.D. 값이 0.005에서 1시간 후 0.010으로 증가하고, 침전물은 1시간 후 사라진다.O.D. when the amount of distilled water is 40 or 50 ml. The value increases from 0.005 to 0.010 after 1 hour and the precipitate disappears after 1 hour.
도 2는 본 발명의 실시예 1에 따라 제조된 이온화칼슘 수용액을 넙치사료에 첨가제로 첨가한 사료를 먹인 넙치(실험군) 및 일반사료를 먹인 넙치(대조군)의 생육실험에 대한 결과를 보여주는 그래프를 나타낸 것이다.Figure 2 is a graph showing the results for the growth experiments of the flounder (experimental group) and the flounder (control group) fed the feed supplemented with the additives to the flounder feed prepared by the aqueous solution of ionized calcium prepared according to Example 1 of the present invention It is shown.
실험군은 실험초기인 5월 14일에 평균체중이 154g이고, 대조군은 144g이었다. 2개월간의 비교실험 결과 7월 13일 실험군의 최종평균체중은 283g이고, 대조군은 254g이다. 초기에는 10g정도의 차이가 있었지만 2개월간 다른 사료를 먹인 결과 약 30g의 체중차이가 생겼다.The experimental group had an average body weight of 154 g and a control group of 144 g on May 14, the early stage of the experiment. As a result of the two-month comparison experiment, the final mean weight of the experimental group on July 13 was 283g and the control group was 254g. Initially, there was a difference of about 10g, but after two months of feeding different feeds, there was a weight difference of about 30g.
아래의 표 3은 실험군 및 대조군의 평균체중, 생존율 및 체중증가율을 나타낸다.Table 3 below shows the mean weight, survival rate and weight gain rate of the experimental and control groups.
표 3
구분 실험군 대조군
초기사육미수 6,209 6,232
최종사육미수 5,419 5,420
초기평균체중(g) 154 144
최종평균체중(g) 283 254
생존율(%) 87.3 86.6
체중증가율(%) 83.8 76.4
TABLE 3
division Experimental group Control
Early breeding failure 6,209 6,232
Final breeding failure 5,419 5,420
Initial average weight (g) 154 144
Final average weight (g) 283 254
Survival rate (%) 87.3 86.6
% Weight gain 83.8 76.4
기간 : 2011.5.14~7.14Period: 2011.5.14 ~ 7.14
실험군의 생존율은 87.3%로 대조군의 86.6%보다 높고, 체중증가율은 실험군이 83.8%, 대조군이 76.4%로 높게 나와 본 발명의 실시예에 따라 제조된 이온화칼슘 수용액이 사료첨가제로 사용된 어류용 사료의 효능이 뛰어남을 알 수 있다.The survival rate of the experimental group was 87.3%, higher than the 86.6% of the control group, the weight gain rate was 83.8% in the experimental group, 76.4% in the control group and the ion calcium aqueous solution prepared according to the embodiment of the present invention was used as a feed additive. It can be seen that the efficacy of.
도 3은 본 발명의 실시예 1에 따라 제조된 이온화칼슘 수용액을 사료첨가제로써 첨가한 사료를 먹인 넙치(실험군)의 혈액 및 일반사료를 먹인 넙치(대조군)의 혈액을 각각 채취하여 아스파르트산아미노기전달효소(AST)를 측정한 결과를 보여주는 그래프를 나타낸 것이다. FIG. 3 shows the blood of the flounder (experimental group) fed with the feed added with the aqueous calcium ionized solution prepared according to Example 1 as a feed additive and the blood of the flounder (control group) fed with the general feed, and aspartate amino group transfer. The graph shows the result of measuring enzyme (AST).
실험군의 경우에는 AST값이 9U/L 정도인 반면, 대조군의 경우 8U/L 정도로 측정되어 아스파르트산아미노기전달효소의 양은 실험군이 높게 측정되었다.In the experimental group, the AST value was about 9U / L, whereas in the control group, the amount of aspartic acid aminotransferase was high in the experimental group.
도 4는 본 발명의 실시예 1에 따라 제조된 이온화칼슘 수용액을 사료첨가제로써 첨가한 사료를 먹인 넙치(실험군)의 혈액 및 일반사료를 먹인 넙치(대조군)의 혈액을 채취하여 글루코오스(Glucose)를 측정한 결과를 보여주는 그래프이다.4 is a blood glucose of the olive flounder (experimental group) fed with the feed added to the ionized calcium aqueous solution prepared according to Example 1 as a feed additive and the blood of the flounder (control) fed the normal feed glucose (Glucose) This graph shows the result of the measurement.
실험군의 경우에는 60mg/dL 정도인 반면, 대조군의 경우 50mg/dL 미만인 것으로 측정되어 글루코오스량은 실험군이 높게 측정되었다.In the experimental group was about 60mg / dL, while the control group was measured to be less than 50mg / dL, the amount of glucose was high in the experimental group.
도 5는 본 발명의 실시예 1에 따라 제조된 이온화칼슘 수용액을 사료첨가제로써 첨가한 사료를 먹인 넙치(실험군)의 점액 및 일반사료를 먹인 넙치(대조군)의 점액을 각각 채취하여 라이소자임(Lysozyme) 활성도를 측정한 결과를 보여주는 그래프이다. Figure 5 is a lysozyme (Lysozyme) by collecting the slime of the flounder (experimental group) and the halibut (control group) fed the feed with the feed added the calcium ionized aqueous solution prepared according to Example 1 of the present invention as a feed additive This graph shows the result of measuring activity.
실험군의 경우에는 0.009unit/mL 정도인 반면, 대조군의 경우 0.008unit/mL정도로 측정되어 라이소자임 활성도는 실험군이 높게 측정되었다.The experimental group was about 0.009 unit / mL, whereas the control group was measured at about 0.008 unit / mL, so the lysozyme activity was high in the experimental group.
본 발명의 실시예 1에 따라 제조된 이온화칼슘 수용액은 비타민 D3와 같은 흡수 촉진제의 도움 없이도 세포 체내에 쉽게 흡수됨으로써 세포 체내 흡수 시 이온화칼슘의 효능을 극대화시킨다. The aqueous calcium ion solution prepared according to Example 1 of the present invention is easily absorbed into the cell body without the aid of an absorption promoter such as vitamin D3, thereby maximizing the efficacy of the calcium ion when absorbed into the cell body.
즉, 직접 섭취 및 흡수가 가능하도록 함과 동시에 이를 주재료 또는 보조재료로 하여 어류 및 가축사료에 소정량 첨가하여서 사료 내에 함유된 수용성 이온화칼슘이 사료의 변질이나 세균 발생을 억제하여 보존기간을 증가시킨다. 그에 따라 영양분의 손실을 최소화하며 수용성 이온화칼슘을 첨가한 사료는 이온화칼슘 섭취가 더욱 용이하도록 함은 물론 칼슘의 체내흡수율을 높여주어 사료의 부족한 칼슘이 충분히 보충되도록 하여 양식어류나 동식물의 신진대사 또는 생체기능을 촉진시킨다.In other words, it is possible to directly ingest and absorb, and to add a predetermined amount to fish and livestock feed as a main ingredient or auxiliary material, so that the water-soluble ionized calcium contained in the feed inhibits the deterioration of the feed and the generation of bacteria to increase the shelf life. . This minimizes the loss of nutrients and adds water-soluble ionized calcium to make calcium ionization easier to eat, and increases the body's absorption of calcium to make up for the lack of calcium in the feed, thereby increasing the metabolism of fish and plants and animals. Promotes biological function
특히 변온동물인 어류의 칼슘흡수 부족으로 인해 발생하는 장내가스발생, 칼슘대사장애에 의한 어류 복수발생, 산란기 칼슘부족으로 인한 면역력저하, 칼슘부족에 의한 피부 점액질 저하 등을 예방함으로써 면역력은 물론 생육과 생존율을 올려 수산양식업의 수익성 증대 및 경쟁력을 증진시킬 수 있다.In particular, it prevents immunity as well as growth by preventing intestinal gas generation caused by lack of calcium absorption of fish, which is caused by deficiency of calcium metabolism, multiple occurrences of fish due to calcium metabolism disorders, immunity deterioration due to calcium deficiency, and deterioration of skin mucus due to lack of calcium. Increasing the survival rate can increase the profitability and competitiveness of the aquaculture industry.
한편, 본 명세서와 도면에 개시된 본 발명의 실시예들은 이해를 돕기 위해 특정 예를 제시한 것에 지나지 않으며, 본 발명의 범위를 한정하고자 하는 것은 아니다. 여기에 개시된 실시예들 이외에도 본 발명의 기술적 사상에 바탕을 둔 다른 변형예들이 실시 가능하다는 것은 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 자명한 것이다.On the other hand, the embodiments of the present invention disclosed in the specification and drawings are merely presented specific examples to aid understanding, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that other modifications based on the technical idea of the present invention can be carried out in addition to the embodiments disclosed herein.
본 발명은 순수한 칼슘의 함유량이 94~97%에 이를 정도로 고농도에 달하고, 수소이온농도가 pH 12~13에 속하는 고순도의 안정된 알칼리성 이온화칼슘 수용액을 제공함으로써 식품첨가물, 칼슘이온음료, 동물사료, 양식어류사료, 농업용 이온화칼슘 등에 적용할 수 있다.The present invention reaches a high concentration of pure calcium content of 94-97%, and provides a high purity stable alkaline ionized calcium aqueous solution in which hydrogen ion concentration is pH 12-13, food additives, calcium ion drink, animal feed, aquaculture It can be applied to fish feed, agricultural calcium ion, etc.

Claims (10)

  1. 패각류의 세척을 통해 이물질 및 불순물을 제거한 후 건조시키는 세척단계;A washing step of removing foreign matters and impurities by washing shellfish and then drying them;
    상기 건조된 패각류를 가열 및 소성시켜 건조된 패각류에 포함된 유기물 및 잔류 독성을 제거하여 산화칼슘을 제조하는 고온소성단계;A high temperature firing step of heating and calcining the dried shellfish to produce calcium oxide by removing organic substances and residual toxicity contained in the dried shellfish;
    상기 산화칼슘을 분쇄하여 산화칼슘분말을 제조하는 분쇄단계;Grinding the calcium oxide to produce a calcium oxide powder;
    상기 산화칼슘분말과 물을 혼합 및 교반하여 산화칼슘용액을 제조하는 교반단계;A stirring step of preparing a calcium oxide solution by mixing and stirring the calcium oxide powder and water;
    상기 산화칼슘용액을 포함하는 용기에 포화증기를 공급하여, 상기 용기 내에 정전기를 발생시킴으로써 이온반응을 유도하여 이온화칼슘 수용액을 제조하는 이온반응단계; 및Supplying saturated steam to the container containing the calcium oxide solution, inducing an ionic reaction by generating static electricity in the container to produce an ionized calcium solution; And
    상기 이온화칼슘 수용액에 연수처리된 물 또는 순수처리된 물을 첨가하여 수소이온농도가 pH 12~13을 유지하도록 하는 수소이온농도조절단계;를 포함하는 것을 특징으로 하는 이온화칼슘 수용액의 제조방법.And a hydrogen ion concentration adjusting step of adding a softened water or purely treated water to the aqueous solution of calcium ion to maintain a hydrogen ion concentration of pH 12 to 13; and a method for producing an aqueous calcium ion solution.
  2. 제1항에 있어서, The method of claim 1,
    상기 고온소성단계에서는, In the high temperature baking step,
    1100~2000℃의 온도에서, 1~3시간 동안 건조된 패각류를 가열 및 소성시키는 것을 특징으로 하는 이온화칼슘 수용액의 제조방법.Method for producing an aqueous calcium ion solution, characterized in that for heating at 1100 ~ 2000 ℃, dried shellfish for 1 to 3 hours and calcining.
  3. 제2항에 있어서, The method of claim 2,
    상기 고온소성단계에서는,In the high temperature baking step,
    초기온도 1100℃에서 최종온도 2000℃까지 점진적으로 온도를 상승시켜 건조된 패각류를 가열 및 소성시키는 것을 특징으로 하는 이온화칼슘 수용액의 제조 방법.A method for producing an aqueous calcium ion solution, comprising heating and calcining dried shellfish by gradually raising the temperature from an initial temperature of 1100 ° C to a final temperature of 2000 ° C.
  4. 제1항에 있어서, The method of claim 1,
    상기 분쇄단계에서 분쇄된 산화칼슘분말의 입자크기는 20㎛이하인 것을 특징으로 하는 이온화칼슘 수용액의 제조방법.The particle size of the calcium oxide powder pulverized in the grinding step is a method for producing an aqueous calcium ion solution, characterized in that 20㎛ or less.
  5. 제1항에 있어서, The method of claim 1,
    상기 교반단계에서는 물 100중량부에 대해 산화칼슘분말을 0.1~ 2중량부의 비율로 혼합 및 교반하는 것을 특징으로 하는 이온화칼슘 수용액의 제조방법.In the stirring step, the calcium oxide powder is mixed and stirred at a ratio of 0.1 to 2 parts by weight with respect to 100 parts by weight of water.
  6. 제5항에 있어서,The method of claim 5,
    상기 교반단계에서 물과 산화칼슘분말을 혼합한 후 2~5시간 동안 교반하는 것을 특징으로 하는 이온화칼슘 수용액의 제조방법.Method for producing an aqueous calcium ion solution, characterized in that for stirring for 2 to 5 hours after mixing water and calcium oxide powder in the stirring step.
  7. 제1항에 있어서,The method of claim 1,
    상기 이온반응단계에서 공급되는 포화증기의 압력은 1.4~5MPa인 것을 특징으로 하는 이온화칼슘 수용액의 제조방법.Pressure of saturated steam supplied in the ion reaction step is a method for producing an aqueous calcium ion solution, characterized in that 1.4 ~ 5MPa.
  8. 제1항 내지 제7항 중 어느 한 항에 있어서, The method according to any one of claims 1 to 7,
    상기 이온반응단계는,The ion reaction step,
    상기 용기에 상기 산화칼슘용액을 주입하는 산화칼슘용액주입단계;Calcium oxide solution injection step of injecting the calcium oxide solution into the container;
    상기 용기에 300℃ 이하의 온도 및 1.4~5㎫의 압력을 가지는 포화증기를 공급하면서 생성되는 물방울에 의해 정전기가 발생하는 정전기발생단계;An electrostatic generating step of generating static electricity by water droplets generated while supplying saturated steam having a temperature of about 300 ° C. or less and a pressure of 1.4 to 5 MPa to the vessel;
    상기 용기 내부의 압력을 일정하게 유지하면서 상기 용기 내부를 교반함으로 써 이온반응을 유도하는 이온반응유도단계;An ion reaction inducing step of inducing an ionic reaction by stirring the inside of the container while maintaining a constant pressure in the container;
    상기 용기 내부의 포화증기를 제1감압탱크로 배출하여 상기 용기 내부와 상기 제1감압탱크 내부가 압력평형을 이루는 제1포화증기배출단계;A first saturated steam discharge step of discharging the saturated steam in the container to a first pressure reducing tank to achieve a pressure balance between the inside of the container and the first pressure reducing tank;
    상기 제1 감압탱크를 폐쇄한 후, 상기 용기 내부의 포화증기를 상기 제1 감압탱크보다 큰 체적을 갖는 제2감압탱크로 배출하는 제2포화증기배출단계; 및A second saturated steam discharging step of discharging saturated steam in the container to a second pressure reducing tank having a volume larger than that of the first pressure reducing tank after closing the first pressure reducing tank; And
    상기 제1감압탱크 및 상기 제2감압탱크에서 상기 이온화칼슘 수용액을 획득하는 이온화칼슘수용액획득단계;를 포함하여 구성되는 것을 특징으로 하는 이온화칼슘 수용액의 제조방법.And a calcium ionized aqueous solution obtaining step of obtaining the aqueous calcium ionized solution in the first reduced pressure tank and the second reduced pressure tank.
  9. 제1항 내지 제7항 중 어느 한 항의 방법에 의해 제조된 것을 특징으로 하는 이온화칼슘 수용액.An aqueous calcium ion solution prepared by the method of any one of claims 1 to 7.
  10. 제8항의 방법에 의해 제조된 것을 특징으로 하는 이온화칼슘 수용액.Aqueous calcium ion solution prepared by the method of claim 8.
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