WO2014046344A1 - Method for preparing calcium citrate using oyster shell chips - Google Patents

Method for preparing calcium citrate using oyster shell chips Download PDF

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WO2014046344A1
WO2014046344A1 PCT/KR2012/010981 KR2012010981W WO2014046344A1 WO 2014046344 A1 WO2014046344 A1 WO 2014046344A1 KR 2012010981 W KR2012010981 W KR 2012010981W WO 2014046344 A1 WO2014046344 A1 WO 2014046344A1
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calcium citrate
oyster shell
reaction
citric acid
oyster
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PCT/KR2012/010981
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French (fr)
Korean (ko)
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김학주
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주식회사 서진바이오텍
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/04—Calcium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
    • B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
    • B07B13/00—Grading or sorting solid materials by dry methods, not otherwise provided for; Sorting articles otherwise than by indirectly controlled devices
    • B07B13/10—Grading or sorting solid materials by dry methods, not otherwise provided for; Sorting articles otherwise than by indirectly controlled devices using momentum effects
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium

Definitions

  • the present invention relates to a method for producing calcium citrate using the oyster shell ( ⁇ ), more specifically, the oyster shell generated in the process of producing oyster dried through the removal and cleaning process to make the powder and then reacted by putting citric anhydride
  • the present invention relates to an invention having excellent effects, such as not only saving energy costs but also producing a high purity product by a simple method.
  • the main component of the oyster shell is calcium carbonate (CaCO 3 ), which contains about 95%, and contains a small amount of magnesium carbonate (MgCO 3 ) and calcium sulfate (CaSO 4 ).
  • CaCO 3 calcium carbonate
  • MgCO 3 magnesium carbonate
  • CaSO 4 calcium sulfate
  • Oyster shells are used as raw materials for various fillers, paper coatings, pigments, cosmetics and pharmaceuticals, and are also used for the production of calcium carbonate (CaCO 3 ).
  • Japan research is underway to use oyster shells as soft ground and sand pile materials.
  • In Korea efforts have been made to increase the amount of oyster shells recycled at calcium and fertilizer plants. It is not present.
  • Korean Laid-Open Patent Publication No. 2001-0098992 discloses the production of calcium hydrogen citrate or calcium citrate by reacting calcium carbonate powdered with shellfish or limestone, such as oyster shell, cockle or clam, with citric acid. And a method of producing calcium hydrogen citrate or calcium citrate by reacting calcined shells or quicklimes calcined with shellfish and limestone at 800 to 1300 ° C. with citric acid, but this method requires calcining shellfish at high temperature. Energy costs are high, and the purity of the product was low, there was an uneconomic problem.
  • the present inventors have realized that, unlike the prior art, the shell of the oyster can be reacted with anhydrous citric acid at a relatively low temperature, thereby significantly reducing energy costs and producing calcium citrate with high purity by a simple method. Was done.
  • An object of the present invention is to provide a method capable of producing a high purity calcium citrate by a simple method, as well as significantly reducing the energy cost by reacting the oyster shell by adding citric anhydride at a relatively low temperature.
  • the present invention provides a method for producing calcium citrate using oyster shells, comprising: 1) preliminary step of pulverizing oyster shells by removing foreign matters attached to oyster shells, washing with water and then drying; 2) a reaction step of obtaining a reaction product by adding citric anhydride to the oyster shell powder obtained in the preliminary step to react; 3) a precipitation step of obtaining a pellet-like precipitate by centrifuging the reaction product obtained in the reaction step; 4) a drying step of drying the pellet-like precipitate obtained in the precipitation step by hot air; 5) It provides a method for producing calcium citrate using the oyster shell comprising the completion step of pulverizing the calcium citrate obtained in the drying step by using an air mill.
  • the present invention is a method for producing calcium citrate using oyster shell characterized in that for 1 to 24 hours at 4 ⁇ 100 °C by adding citric anhydride 1: 0.1921 ⁇ 1.9212 parts by weight to the oyster shell powder in the reaction step. to provide.
  • the present invention provides calcium citrate, which is characterized in that the production method.
  • the energy cost can be greatly reduced by adding citric anhydride to the oyster shell at a relatively low temperature.
  • 1 is a schematic process diagram of a method for producing calcium citrate using the oyster shell of the present invention.
  • Figure 2 is a graph of the HLPC analysis of calcium citrate prepared in Example 1 of the present invention.
  • Method for producing calcium citrate using the oyster shell in the present invention is a preliminary step of powdering the oyster shell by removing foreign matter attached to the oyster shell washed with water and then dried; 2) a reaction step of obtaining a reaction product by adding citric anhydride to the oyster shell powder obtained in the preliminary step to react; 3) a precipitation step of obtaining a pellet-like precipitate by centrifuging the reaction product obtained in the reaction step; 4) a drying step of drying the pellet-like precipitate obtained in the precipitation step by hot air; 5) Comprising a calcium citrate obtained in the drying step is completed using a air mill to form a complete step.
  • the reaction step of obtaining a reaction product by adding citric anhydride to the oyster shell powder obtained in the preliminary step is the most important step in the production of calcium citrate using the oyster shell of the present invention.
  • Citric anhydride as a reactant for preparing the calcium citrate of the present invention has a molecular formula C 6 H 8 O 7 or HOC (CO 2 H) (CH 2 CO 2 H) 2 .
  • HOC CO 2 H
  • the chemical formula related to this is as follows (1) to (3).
  • the combination of calcium and citric acid is a form of sharing calcium, and citric acid is surrounded by calcium atoms, and large molecules are formed and precipitation occurs. Therefore, two citric acid molecules and three calcium carbonates react.
  • the citric acid molecular weight is 192.12 and the calcium carbonate molecular weight is 100.09.
  • Anhydrous citric acid is added to the oyster shell powder obtained in the preliminary step in a ratio of 1: 0.1921 to 1.9212 parts by weight, and the reaction is preferably performed at a relatively low temperature of 4 to 100 ° C. for 1 to 24 hours.
  • Anhydrous citric acid is dissolved in water and used as an aqueous citric acid solution. 10 l of 0.1 to 1.0 M citric acid solution (0.1921 to 1.9212 kg) is added to 1 kg of oyster shell powder, followed by stirring.
  • the reaction product produced by the reaction of the oyster shell powder with citric acid is mixed with calcium citrate, water, carbon dioxide, and the like. Centrifugation of the remaining mixture is carried out to separate the precipitate of the calcium phosphate.
  • centrifugation is performed at room temperature for 8,000 rpm for 20 minutes to separate the supernatant and pellet precipitate.
  • the drying step of drying the pellet-like precipitate obtained in the precipitation step with hot air is an operation for drying moisture adhered to the surface of the pellet-like calcium citrate using a hot air dryer to dry the moisture attached to the surface of the pellet-like calcium citrate. .
  • the final step of pulverizing the calcium citrate obtained in the drying step is the final step of the production method of calcium citrate using the oyster shell of the present invention, the dried pelleted calcium citrate to the size of 100 ⁇ 300mesh using an air mill To get the finished product.
  • Oyster shells generated from oyster farms were collected, foreign matters attached to the surface were removed, washed with water, dried naturally, and then pulverized dry to 50-300mesh using an air mill.
  • Dissolve 0.9606 kg of anhydrous citric acid in water to make 10 L of 0.5M citric acid solution add it to 1 kg of oyster shell powder, mix well, and then centrifuge the reaction product at 4 °C for 20 minutes at 8,000 rpm for 20 minutes. The supernatant and the pellet precipitate were separated by separation.
  • the separated pellets were dried with hot air at 45 ° C. for 48 hours, and then pulverized to obtain 1.719 kg of calcium citrate of 100 to 300mesh using an air mill. The yield was 87.67%.
  • Example 1 0.1729 kg was dissolved in water instead of 0.9606 kg of anhydrous citric acid to obtain 0.930 kg of calcium citrate, which was obtained in the same manner as in 10 L of 0.09M citric acid aqueous solution, yielding 79.29%.
  • Example 1 2.0173 kg was dissolved in water, instead of 0.9606 kg of anhydrous citric acid, to obtain 2.131 kg of calcium citrate.
  • Example 2 is an analysis result of the calcium citrate obtained in Example 1
  • B is an analysis result for the citric acid standard.
  • the position of the citric acid standard is RT 4.821, and in Graph A, no citric acid is found at the same position as the citric acid standard, and no citric acid remains after the reaction.
  • Example 1 and Comparative Examples 1 and 2 were subjected to purity verification using an atomic absorption spectrophotometer.
  • each sample was completely dried in a 110 ° C. dryer for 5 hours, and 5 ppm of sample was dissolved in 5% nitric acid for each sample, and calcium, citrate, magnesium and sodium contents were analyzed.
  • the absorbance values analyzed at the same concentration were compared with the prepared standard curve and the analyzed absorbance values [Table 1], and the purity of the product was converted into percent (%).
  • the absorbance value of the same concentration may be expressed by the following equation.
  • Example 1 and Comparative Examples 1 and 2 the purity of calcium citrate obtained in Example 1 and Comparative Examples 1 and 2 was found to be 98.29%, 94.80% and 94.70%, respectively, and other small amounts of magnesium, sodium and other minerals were found. Is shown in [Table 2].
  • the standards and standards of the food additives of the Korea Food and Drug Administration and the US USP specify that the purity of calcium citrate is 97.5 to 100.5%.
  • the calcium citrate obtained in Example 1 has a purity of 98.29 Although it can be said that it is an excellent product because it is judged to be suitable by exceeding the standard in%, both of Comparative Examples 1 and 2, which are low-cost Chinese products, were found to be less than the standard.

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Abstract

The present invention relates to a method for preparing calcium citrate using oyster shell chips, and more specifically, to a method for preparing calcium citrate by removing impurities and washing oyster shells, which are produced during a process of producing oysters, drying same, forming a powder from the oyster shells, and adding anhydrous citric acid to same for a reaction, and then separating the product using a centrifuge. By adding the anhydrous citric acid to the oyster shell chips for the reaction at a relatively low temperature, the present invention provides superior advantages, such as significantly reducing energy costs and producing a product with high purity with a simple method.

Description

굴 패각을 이용한 구연산칼슘의 제조방법Method for preparing calcium citrate using oyster shell
본 발명은 굴 패각(貝殼)을 이용한 구연산칼슘의 제조방법에 관한 것으로, 더욱 상세하게는 굴 생산과정에서 발생되는 굴 껍질을 이물질 제거 및 세척과정을 거쳐 건조하여 분말로 한 다음 무수구연산을 넣어 반응시킨 후에 원심분리시켜 구연산칼슘을 제조하는 방법으로서, 비교적 저온에서 반응시키므로 에너지 비용을 절감할 수 있을 뿐만 아니라 고순도의 제품을 간단한 방법으로 제조할 수 있는 등 우수한 효과를 갖는 발명에 관한 것이다.The present invention relates to a method for producing calcium citrate using the oyster shell (더욱), more specifically, the oyster shell generated in the process of producing oyster dried through the removal and cleaning process to make the powder and then reacted by putting citric anhydride As a method for producing calcium citrate by centrifugation and then reacting at a relatively low temperature, the present invention relates to an invention having excellent effects, such as not only saving energy costs but also producing a high purity product by a simple method.
우리나라의 굴 패각은 한 해에 약 90만 톤이 발생되고 그 중 70만 톤은 폐기되는 것으로 추산되고 있으며, 폐기되는 굴 패각은 심각한 공해문제와 경제성 재평가 대상으로 대두되고 있는 실정이다. 굴 패각의 주성분은 탄산칼슘(CaCO3)으로 약 95%를 함유하고 있으며, 탄산마그네슘(MgCO3), 황산칼슘(CaSO4)가 소량 포함되어 있다. 굴 패각의 용도는 각종 충전제, 종이 코팅제, 안료, 화장품 및 의약품 등의 원료로 사용되고 있으며, 탄산칼슘(CaCO3)의 제조에도 사용되고 있다. 일본에서는 굴 패각을 연약 지반 개량재, 샌드 파일재로서 활용하고자 하는 연구가 진행 중에 있고, 국내에서는 칼슘공장 및 비료공장 등에서 굴 패각의 재활용량을 증가시키려는 노력이 시도되고 있으나, 아직까지 적절한 처리 방안이 제시되지 못하고 있는 실정이다.It is estimated that about 900,000 tons of oyster shells are generated per year and 700,000 tons of them are discarded, and the discarded oyster shells are emerging as a serious pollution problem and economic reassessment. The main component of the oyster shell is calcium carbonate (CaCO 3 ), which contains about 95%, and contains a small amount of magnesium carbonate (MgCO 3 ) and calcium sulfate (CaSO 4 ). Oyster shells are used as raw materials for various fillers, paper coatings, pigments, cosmetics and pharmaceuticals, and are also used for the production of calcium carbonate (CaCO 3 ). In Japan, research is underway to use oyster shells as soft ground and sand pile materials. In Korea, efforts have been made to increase the amount of oyster shells recycled at calcium and fertilizer plants. It is not present.
이와 관련한 종래기술로서, 공개특허공보 특2001-0098992호에는 굴 껍질, 꼬막, 바지락 등과 같은 패각류 또는 석회석을 50∼325mesh로 분말화시킨 탄산칼슘을 구연산과 반응시켜 수소구연산칼슘 또는 구연산칼슘을 제조하는 방법 및 패각류, 석회석을 800∼1300℃로 소성한 소성 패각 또는 생석회를 구연산과 반응시켜 수소구연산칼슘 또는 구연산칼슘을 제조하는 방법이 개시되어 있으나, 이 방법은 패각류를 고온에서 소성하여야 하므로 에너지비용이 많이 소요되고, 제품의 순도가 낮아 비경제적인 문제점이 있었다. As a related art in this regard, Korean Laid-Open Patent Publication No. 2001-0098992 discloses the production of calcium hydrogen citrate or calcium citrate by reacting calcium carbonate powdered with shellfish or limestone, such as oyster shell, cockle or clam, with citric acid. And a method of producing calcium hydrogen citrate or calcium citrate by reacting calcined shells or quicklimes calcined with shellfish and limestone at 800 to 1300 ° C. with citric acid, but this method requires calcining shellfish at high temperature. Energy costs are high, and the purity of the product was low, there was an uneconomic problem.
이에 본 발명자는 종래 기술과 달리 굴 패각을 비교적 저온에서 무수구연산을 가하여 반응시킴으로써 에너지비용을 대폭적으로 절감할 수 있을 뿐만 아니라 간단한 방법으로 고순도의 구연산칼슘을 제조할 수 있음을 알게 되어 본 발명을 완성하게 되었다.Accordingly, the present inventors have realized that, unlike the prior art, the shell of the oyster can be reacted with anhydrous citric acid at a relatively low temperature, thereby significantly reducing energy costs and producing calcium citrate with high purity by a simple method. Was done.
본 발명은 굴 패각을 비교적 저온에서 무수구연산을 첨가하여 반응시킴으로써 에너지비용을 대폭적으로 절감할 수 있을 뿐만 아니라 간단한 방법으로 고순도의 구연산칼슘을 제조할 수 있는 방법의 제공을 그 과제로 한다.An object of the present invention is to provide a method capable of producing a high purity calcium citrate by a simple method, as well as significantly reducing the energy cost by reacting the oyster shell by adding citric anhydride at a relatively low temperature.
본 발명은 굴 패각을 이용한 구연산칼슘의 제조방법에 있어서, 1) 굴 패각에 부착된 이물질을 제거하여 물로 세척한 다음 건조시켜 굴 패각을 분말화하는 예비단계; 2) 상기 예비단계에서 얻은 굴 패각 분말에 무수구연산을 가하여 반응시킴으로써 반응생성물을 얻는 반응단계; 3) 상기 반응단계에서 얻은 반응생성물을 원심분리시켜 펠렛상 침전물을 얻는 침전단계; 4) 상기 침전단계에서 얻은 펠렛상 침전물을 열풍으로 건조시키는 건조단계; 5) 상기 건조단계에서 얻은 구연산칼슘을 에어밀을 사용하여 분쇄시켜 제품화하는 완성단계를 포함하는 것을 특징으로 하는 굴 패각을 이용한 구연산칼슘의 제조방법을 제공한다.The present invention provides a method for producing calcium citrate using oyster shells, comprising: 1) preliminary step of pulverizing oyster shells by removing foreign matters attached to oyster shells, washing with water and then drying; 2) a reaction step of obtaining a reaction product by adding citric anhydride to the oyster shell powder obtained in the preliminary step to react; 3) a precipitation step of obtaining a pellet-like precipitate by centrifuging the reaction product obtained in the reaction step; 4) a drying step of drying the pellet-like precipitate obtained in the precipitation step by hot air; 5) It provides a method for producing calcium citrate using the oyster shell comprising the completion step of pulverizing the calcium citrate obtained in the drying step by using an air mill.
또한 본 발명은 상기 반응단계 중 굴 패각 분말에 무수구연산을 1 : 0.1921~1.9212 중량부의 비율로 가하여 4~100℃에서 1~24시간 반응시키는 것을 특징으로 하는 굴 패각을 이용한 구연산칼슘의 제조방법을 제공한다.In another aspect, the present invention is a method for producing calcium citrate using oyster shell characterized in that for 1 to 24 hours at 4 ~ 100 ℃ by adding citric anhydride 1: 0.1921 ~ 1.9212 parts by weight to the oyster shell powder in the reaction step. to provide.
마지막으로 본 발명은 상기 제조방법에 의하여 제조되는 것을 특징으로 하는 구연산칼슘을 제공한다. Finally, the present invention provides calcium citrate, which is characterized in that the production method.
본 발명에 따른 굴 패각을 이용한 구연산칼슘의 제조방법은Method for producing calcium citrate using the oyster shell according to the present invention
첫째, 비교적 저온에서 굴 패각에 무수구연산을 첨가하여 반응시킴으로써 에너지비용을 대폭적으로 절감할 수 있으며,First, the energy cost can be greatly reduced by adding citric anhydride to the oyster shell at a relatively low temperature.
둘째, 시판되는 제품보다 고순도의 구연산칼슘을 간단한 방법으로 제조할 수 있으므로 가격경쟁력이 탁월한 장점이 있다.Second, it is possible to manufacture a high purity calcium citrate by a simple method than the commercially available product has an excellent price competitiveness.
도 1은 본 발명의 굴 패각을 이용한 구연산칼슘의 제조방법에 대한 개략적인 공정도이다.1 is a schematic process diagram of a method for producing calcium citrate using the oyster shell of the present invention.
도 2는 본 발명의 실시예 1에서 제조된 구연산칼슘의 HLPC 분석결과 그래프이다. Figure 2 is a graph of the HLPC analysis of calcium citrate prepared in Example 1 of the present invention.
이하에서는 본 발명의 구체적 내용을 바람직한 실시예와 비교예를 포함하여 상세하게 설명하되, 이는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 상세하게 설명하기 위한 것이지, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.DETAILED DESCRIPTION Hereinafter, specific contents of the present invention will be described in detail including a preferred embodiment and a comparative example, which will be described in detail so that a person skilled in the art can easily carry out the invention. This does not mean that the technical spirit and scope of the present invention are limited.
본 발명에 굴 패각을 이용한 구연산칼슘의 제조방법은 1) 굴 패각에 부착된 이물질을 제거하여 물로 세척한 다음 건조시켜 굴 패각을 분말화하는 예비단계; 2) 상기 예비단계에서 얻은 굴 패각 분말에 무수구연산을 가하여 반응시킴으로써 반응생성물을 얻는 반응단계; 3) 상기 반응단계에서 얻은 반응생성물을 원심분리시켜 펠렛상 침전물을 얻는 침전단계; 4) 상기 침전단계에서 얻은 펠렛상 침전물을 열풍으로 건조시키는 건조단계; 5) 상기 건조단계에서 얻은 구연산칼슘을 에어밀을 사용하여 분쇄시켜 제품화하는 완성단계를 포함하여 이루어진다.Method for producing calcium citrate using the oyster shell in the present invention is a preliminary step of powdering the oyster shell by removing foreign matter attached to the oyster shell washed with water and then dried; 2) a reaction step of obtaining a reaction product by adding citric anhydride to the oyster shell powder obtained in the preliminary step to react; 3) a precipitation step of obtaining a pellet-like precipitate by centrifuging the reaction product obtained in the reaction step; 4) a drying step of drying the pellet-like precipitate obtained in the precipitation step by hot air; 5) Comprising a calcium citrate obtained in the drying step is completed using a air mill to form a complete step.
먼저, 굴 패각에 부착된 이물질을 제거하여 물로 세척한 다음 건조시켜 굴 패각을 분말화하는 예비단계는 굴 양식장 등에서 발생되는 굴 패각을 수거하면 그 표면에 각종 이물질이 부착되어 있으므로 이를 칼 등을 사용하여 제거한다. 이어서 굴 패각을 물로 깨끗이 세척하여 자연 건조시킨 후에 구연산과 반응을 용이하게 하기 위하여 에어밀을 사용하여 적당한 크기인 50~300mesh로 건식 분쇄한다.First, remove the foreign substances attached to the oyster shells, wash them with water, and then dry them to powder the oyster shells. When collecting the oyster shells generated in the oyster farm, various foreign substances are attached to the surface. To remove it. Subsequently, the oyster shells are washed thoroughly with water and naturally dried, followed by dry grinding to an appropriate size of 50 to 300 mesh using an air mill to facilitate reaction with citric acid.
상기 예비단계에서 얻은 굴 패각 분말에 무수구연산을 가하여 반응시킴으로써 반응생성물을 얻는 반응단계는 본 발명의 굴 패각을 이용한 구연산칼슘의 제조 단계 중 제일 중요한 단계이다. The reaction step of obtaining a reaction product by adding citric anhydride to the oyster shell powder obtained in the preliminary step is the most important step in the production of calcium citrate using the oyster shell of the present invention.
본 발명의 구연산칼슘을 제조하기 위한 반응물질로서 무수구연산은 분자식이 C6H8O7 또는 HOC(CO2H)(CH2CO2H)2이다. 이는 칼슘(Ca)과 만나면 수소이온(H+)을 잃고 칼슘과 반응하여 구연산칼슘이라는 화합물을 형성하는데, 그 과정에서 물(H2O)과 이산화탄소(CO2) 기체가 발생하며, 구연산 한 분자는 최대 3개의 칼슘 원자와 반응할 수 있다. 이와 관련된 화학식은 다음 (1) 내지 (3)과 같다.Citric anhydride as a reactant for preparing the calcium citrate of the present invention has a molecular formula C 6 H 8 O 7 or HOC (CO 2 H) (CH 2 CO 2 H) 2 . When it meets calcium (Ca), it loses hydrogen ions (H + ) and reacts with calcium to form a compound called calcium citrate, in which water (H 2 O) and carbon dioxide (CO 2 ) gases are generated, and one molecule of citric acid Can react with up to three calcium atoms. The chemical formula related to this is as follows (1) to (3).
HOC(CO2H)(CH2CO2H)2 + CaCO3 → HOC(CO2Ca)(CH2CO2H)2 + CO2↑ + H2O (1)HOC (CO 2 H) (CH 2 CO 2 H) 2 + CaCO 3 → HOC (CO 2 Ca) (CH 2 CO 2 H) 2 + CO 2 ↑ + H 2 O (1)
HOC(CO2Ca)(CH2CO2H)(CH2CO2H) + CaCO3 → HOC(CO2Ca)(CO2Ca)(CH2CO2H) + CO2 ↑+ H2O (2)HOC (CO 2 Ca) (CH 2 CO 2 H) (CH 2 CO 2 H) + CaCO 3 → HOC (CO 2 Ca) (CO 2 Ca) (CH 2 CO 2 H) + CO 2 ↑ + H 2 O (2)
HOC(CO2Ca)(CH2CO2Ca)(CH2CO2H) + CaCO3 → HOC(CO2Ca)(CO2Ca)2 + CO2 ↑+ H2O (3)HOC (CO 2 Ca) (CH 2 CO 2 Ca) (CH 2 CO 2 H) + CaCO 3 → HOC (CO 2 Ca) (CO 2 Ca) 2 + CO 2 ↑ + H 2 O (3)
만일, 구연산에 3개의 칼슘이 모두 결합한다고 하면 화학식은 다음 (4)와 같이 표현할 수 있다.If all three calcium are bound to citric acid, the chemical formula can be expressed as (4) below.
HOC(CO2H)(CH2CO2H)2 + 3CaCO3 → HOC(CO2Ca)(CH2CO2Ca)2 + 3CO2 ↑+ 3H2O (4)HOC (CO 2 H) (CH 2 CO 2 H) 2 + 3 CaCO 3 → HOC (CO 2 Ca) (CH 2 CO 2 Ca) 2 + 3CO 2 ↑ + 3H 2 O (4)
이 때 칼슘과 구연산의 결합은 칼슘을 공유하는 형태로 칼슘 원자 주위를 구연산기가 둘러싸면서 거대 분자가 형성되어 침전이 일어나게 되는 원리이다. 따라서 2개의 구연산 분자와 3개의 탄산칼슘이 반응을 하며, 구연산 분자량은 192.12, 탄산칼슘 분자량은 100.09이다.At this time, the combination of calcium and citric acid is a form of sharing calcium, and citric acid is surrounded by calcium atoms, and large molecules are formed and precipitation occurs. Therefore, two citric acid molecules and three calcium carbonates react. The citric acid molecular weight is 192.12 and the calcium carbonate molecular weight is 100.09.
상기 예비단계에서 얻어진 굴 패각 분말에 무수구연산을 1 : 0.1921~1.9212 중량부의 비율로 가하여 비교적 저온인 4~100℃에서 1~24시간 반응시키는 것이 바람직하다. 무수구연산은 물에 녹여 구연산수용액으로 하여 사용하는데, 0.1~1.0M 구연산수용액 10ℓ(구연산 0.1921~1.9212㎏)을 굴 패각 분말 1㎏에 가하여 교반한 후 반응시킨다. Anhydrous citric acid is added to the oyster shell powder obtained in the preliminary step in a ratio of 1: 0.1921 to 1.9212 parts by weight, and the reaction is preferably performed at a relatively low temperature of 4 to 100 ° C. for 1 to 24 hours. Anhydrous citric acid is dissolved in water and used as an aqueous citric acid solution. 10 l of 0.1 to 1.0 M citric acid solution (0.1921 to 1.9212 kg) is added to 1 kg of oyster shell powder, followed by stirring.
이 때 무수구연산의 첨가량이 0.1921 중량부 미만일 경우에는 굴 패각 분말과 충분한 반응이 일어나지 않으며, 1.9212 중량부를 초과할 경우에는 구연산의 잔류량이 발생되어 구연산칼슘의 순도가 낮아지고, 회수비용이 증가하는 문제점이 발생한다. 아울러 반응온도가 4℃, 반응시간이 1시간 미만일 경우에는 반응속도가 느려져 반응이 충분히 일어나지 않으며, 100℃, 24시간을 초과할 경우에는 반응속도는 더 이상 증가하지 않고 에너지비용이 더 많이 소요되는 문제가 발생한다. At this time, when the amount of citric anhydride added is less than 0.1921 parts by weight, sufficient reaction does not occur with the oyster shell powder, and when the amount is more than 1.9212 parts by weight, the residual amount of citric acid is generated to lower the purity of calcium citrate and increase the recovery cost. This happens. In addition, if the reaction temperature is 4 ℃, the reaction time is less than 1 hour, the reaction rate is slow, the reaction does not occur sufficiently. If the temperature exceeds 100 ℃, 24 hours, the reaction rate does not increase any more and energy costs are increased. A problem arises.
상기 반응단계에서 얻은 반응생성물을 원심분리시켜 펠렛상 침전물을 얻는 침전단계는 굴 패각 분말이 구연산과 반응됨으로써 생성된 반응생성물에는 구연산칼슘, 물, 이산화탄소 등이 혼합되어 있는데, 이산화탄소는 기체이므로 공중으로 날아가고 남은 혼합액을 원심분리시켜 침전물인 펠레상 구연산칼슘을 분리하는 것이다. In the precipitation step of obtaining a pellet-like precipitate by centrifuging the reaction product obtained in the reaction step, the reaction product produced by the reaction of the oyster shell powder with citric acid is mixed with calcium citrate, water, carbon dioxide, and the like. Centrifugation of the remaining mixture is carried out to separate the precipitate of the calcium phosphate.
이때 원심분리는 상온에서 20분간 8,000rpm으로 하여 상등액과 펠렛상 침전물을 분리한다. At this time, centrifugation is performed at room temperature for 8,000 rpm for 20 minutes to separate the supernatant and pellet precipitate.
상기 침전단계에서 얻은 펠렛상 침전물을 열풍으로 건조시키는 건조단계는 펠렛상 구연산칼슘의 표면에 부착된 수분을 건조시키기 위한 조작으로서 열풍건조기를 사용여 펠렛상 구연산칼슘의 표면에 부착된 수분을 건조시킨다.The drying step of drying the pellet-like precipitate obtained in the precipitation step with hot air is an operation for drying moisture adhered to the surface of the pellet-like calcium citrate using a hot air dryer to dry the moisture attached to the surface of the pellet-like calcium citrate. .
상기 건조단계에서 얻은 구연산칼슘을 분쇄시켜 제품화하는 완성단계는 본 발명인 굴 패각을 이용한 구연산칼슘의 제조방법 중 마지막 단계로서, 건조된 펠렛상 구연산칼슘을 에어밀을 사용하여 100~300mesh의 크기로 분쇄하여 완제품을 얻는 단계이다.The final step of pulverizing the calcium citrate obtained in the drying step is the final step of the production method of calcium citrate using the oyster shell of the present invention, the dried pelleted calcium citrate to the size of 100 ~ 300mesh using an air mill To get the finished product.
이하에서 실시예를 통하여 본 발명을 보다 구체적으로 설명하도록 한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
[실시예 1]Example 1
굴 양식장에서 발생되는 굴 패각을 수거하여 그 표면에 부착된 이물질을 제거하고 물로 깨끗이 세척하여 자연 건조시킨 후에 에어밀을 사용하여 50~300mesh로 건식 분쇄하였다. 무수구연산 0.9606㎏을 물에 녹여 0.5M 구연산 수용액 10ℓ로 만든 다음 굴 패각 분말 1㎏에 가하여 잘 혼합한 후에 혼합액을 30℃에서 5시간 동안 반응시켜 얻은 반응생성물을 4℃에서 20분간 8,000rpm으로 원심분리시켜 상등액과 펠렛상 침전물을 분리하였다. 분리된 펠렛상 침전물을 45℃에서 48시간 열풍으로 건조시킨 후에 분쇄하여 에어밀을 사용하여 100~300mesh의 구연산칼슘 1.719㎏을 얻어 수율 87.67%를 나타내었다.Oyster shells generated from oyster farms were collected, foreign matters attached to the surface were removed, washed with water, dried naturally, and then pulverized dry to 50-300mesh using an air mill. Dissolve 0.9606 kg of anhydrous citric acid in water to make 10 L of 0.5M citric acid solution, add it to 1 kg of oyster shell powder, mix well, and then centrifuge the reaction product at 4 ℃ for 20 minutes at 8,000 rpm for 20 minutes. The supernatant and the pellet precipitate were separated by separation. The separated pellets were dried with hot air at 45 ° C. for 48 hours, and then pulverized to obtain 1.719 kg of calcium citrate of 100 to 300mesh using an air mill. The yield was 87.67%.
[실시예 2]Example 2
실시예 1에서 무수구연산 0.9606㎏ 대신에 0.1729㎏을 물에 녹여 0.09M 구연산 수용액 10ℓ으로 만드는 것을 제외하고는 동일한 방법으로 실시하여 구연산칼슘 0.930kg 을 얻어 수율 79.29%을 나타내었다.In Example 1, 0.1729 kg was dissolved in water instead of 0.9606 kg of anhydrous citric acid to obtain 0.930 kg of calcium citrate, which was obtained in the same manner as in 10 L of 0.09M citric acid aqueous solution, yielding 79.29%.
[실시예 3]Example 3
실시예 1에서 무수구연산 0.9606㎏ 대신에 2.0173㎏을 물에 녹여 1.05M 구연산 수용액 10ℓ으로 만드는 것을 제외하고는 동일한 방법으로 실시하여 구연산칼슘 2.131㎏을 얻어 수율 70.63%를 나타내었다.In Example 1, 2.0173 kg was dissolved in water, instead of 0.9606 kg of anhydrous citric acid, to obtain 2.131 kg of calcium citrate.
<비교예 1>Comparative Example 1
2012년 중국 상하이에서 열린 의약품원료 박람회에 참가한 중국 Heng Sheng Fine Chemical Co., Ltd.의 구연산칼슘 제품을 구입하였다.He bought calcium citrate products from Heng Sheng Fine Chemical Co., Ltd., China, who attended the 2012 Pharmaceutical Raw Materials Fair in Shanghai, China.
<비교예 2>Comparative Example 2
2012년 중국 상하이에서 열린 의약품원료 박람회에 참가한 중국 Tai He Fine Chemical Co., Ltd.의 구연산칼슘 제품을 구입하였다.He bought calcium citrate products from Tai He Fine Chemical Co., Ltd., China, who attended the 2012 Pharmaceutical Raw Materials Fair in Shanghai, China.
이하에서는 상기 실시예 1 및 비교예 1, 2에서 얻은 구연산칼슘의 순도 검증에 대한 여러 가지 실험을 실시하였다.Hereinafter, various experiments were conducted for the purity verification of the calcium citrate obtained in Example 1 and Comparative Examples 1 and 2.
<실험예 1> 잔류 구연산 확인시험Experimental Example 1 Residual Citric Acid Identification Test
상기 실시예 1에서 얻은 구연산칼슘에 대하여 반응 후에 잔류하는 구연산을 분석하기 위해 HPLC를 사용하여 회수된 구연산칼슘 분말 10g에 물 100㎖를 넣고 1시간 동안 상온에서 마그네틱바를 사용하여 교반 추출하였다. 계속하여 원심분리기를 사용하여 3,000rpm에서 10분 동안 원심분리시켜 0.2㎛ 실린지 필터로 여과한 후에 정량 분석하였다. 사용된 column은 CAP CELL PAK C18(5㎛, I.d. 4.6㎜ x 250㎜ Shisheido, Co., Japan)을 사용하였고, 용매는 물과 아세토니트릴을 사용하였으며, 아세토니트릴의 농도 0 → 35%까지 20분간 254㎚에서 분석한 결과를 [도 2]에 나타내었다. [도 2]에 보이는 A는 실시예 1에서 얻은 구연산칼슘의 분석결과이며, B는 구연산 표준물질에 대한 분석결과이다. 구연산 표준물질의 위치는 RT 4.821이며, 그래프 A에는 구연산 표준물질과 동일한 위치에 구연산이 없는 것으로 확인되어, 반응 후에 잔류하는 구연산은 없는 것으로 확인되었다. In order to analyze the citric acid remaining after the reaction with respect to the calcium citrate obtained in Example 1, 100ml of water was added to 10g of calcium citrate powder recovered using HPLC and stirred for 1 hour using a magnetic bar at room temperature. Subsequently, the resultant was centrifuged at 3,000 rpm for 10 minutes using a centrifuge, filtered through a 0.2 μm syringe filter, and quantitated. The column used was CAP CELL PAK C18 (5㎛, Id 4.6mm x 250mm Shisheido, Co., Japan), the solvent was water and acetonitrile, the concentration of acetonitrile from 0 to 35% for 20 minutes The results analyzed at 254 nm are shown in FIG. 2. 2 is an analysis result of the calcium citrate obtained in Example 1, B is an analysis result for the citric acid standard. The position of the citric acid standard is RT 4.821, and in Graph A, no citric acid is found at the same position as the citric acid standard, and no citric acid remains after the reaction.
<실험예 2> 구연산칼슘의 순도 분석Experimental Example 2 Purity Analysis of Calcium Citrate
실시예 1 및 비교예 1, 2에서 얻은 구연산칼슘에 대하여 원자흡광분광강도계를 사용하여 순도검증을 실시하였다. 시료 전처리는 각각의 시료를 110℃ 건조기에서 5시간 완전 건조한 시료를 사용하였으며, 각 시료별로 5% 질산에 5ppm의 시료를 넣고 용해시킨 후에 구연산칼슘을 비롯하여, 마그네슘, 나트륨 함량 분석을 실시하였다. 시료분석은 동일한 농도에서 분석한 흡광도 값을 미리 작성해둔 표준곡선과 분석한 흡광도값[표 1]을 비교하여 제품의 순도를 환산하여 퍼센트(%)로 표기하였다. Calcium citrate obtained in Example 1 and Comparative Examples 1 and 2 was subjected to purity verification using an atomic absorption spectrophotometer. For sample pretreatment, each sample was completely dried in a 110 ° C. dryer for 5 hours, and 5 ppm of sample was dissolved in 5% nitric acid for each sample, and calcium, citrate, magnesium and sodium contents were analyzed. In the sample analysis, the absorbance values analyzed at the same concentration were compared with the prepared standard curve and the analyzed absorbance values [Table 1], and the purity of the product was converted into percent (%).
표 1 제품별 흡광도값
구연산칼슘 마그네슘 나트륨
실시예 1 0.0906 0.0058 0.0031
비교예 1 0.0875 0.0116 0.0029
비교예 2 0.0874 0.0051 0.0021
Table 1 Absorbance value by product
Calcium citrate magnesium salt
Example 1 0.0906 0.0058 0.0031
Comparative Example 1 0.0875 0.0116 0.0029
Comparative Example 2 0.0874 0.0051 0.0021
* 시료분석 농도 : 구연산칼슘 5 ppm, 마그네슘 및 나트륨 각 0.5 ppm* Sample concentration: 5 ppm calcium citrate, 0.5 ppm magnesium and sodium
상기에서 퍼센트(%) 농도로 순도를 환산하는 방식은 동일 농도의 흡광도값을 기준으로 다음 식으로 표시할 수 있다. In the above method of converting purity to a percentage (%) concentration, the absorbance value of the same concentration may be expressed by the following equation.
(측정시료 흡광도값/ 표준시료의 흡광도값) x 100 = 순도(%)(Absorbance value of measured sample / absorbance value of standard sample) x 100 = purity (%)
그 결과 실시예 1 및 비교예 1, 2에서 얻은 구연산칼슘의 순도는 각각 98.29%, 94.80%, 94.70%로 확인되었으며, 그 밖에 마그네슘, 나트륨, 기타 미네랄이 소량 존재하는 것으로 확인되었는바, 그 결과를 [표 2]에 나타내었다. As a result, the purity of calcium citrate obtained in Example 1 and Comparative Examples 1 and 2 was found to be 98.29%, 94.80% and 94.70%, respectively, and other small amounts of magnesium, sodium and other minerals were found. Is shown in [Table 2].
표 2 구연산칼슘의 순도 (%)
구연산칼슘 마그네슘 나트륨 기타 계
실시예 1 98.29 0.86 0.84 0.01 100
비교예 1 94.80 2.03 0.77 2.40 100
비교예 2 94.70 0.72 0.58 4.00 100
TABLE 2 Purity of Calcium Citrate (%)
Calcium citrate magnesium salt Other system
Example 1 98.29 0.86 0.84 0.01 100
Comparative Example 1 94.80 2.03 0.77 2.40 100
Comparative Example 2 94.70 0.72 0.58 4.00 100
한편, 식품첨가물 및 의약품용 칼슘제의 경우 우리나라 식품의약품안전청의 식품첨가물의 기준 및 규격, 미국 USP에 의하면 구연산칼슘의 순도는 97.5~100.5% 사이로 규정되어 있는데, 실시예 1에서 얻은 구연산칼슘은 순도 98.29%로 기준을 초과하여 적합한 것으로 판단되어 우수한 제품이라고 할 수 있으나, 저가의 중국 제품인 비교예 1, 2는 모두 기준치보다 순도가 미달된 것으로 확인되었다. Meanwhile, in the case of food additives and calcium for pharmaceuticals, the standards and standards of the food additives of the Korea Food and Drug Administration and the US USP specify that the purity of calcium citrate is 97.5 to 100.5%. The calcium citrate obtained in Example 1 has a purity of 98.29 Although it can be said that it is an excellent product because it is judged to be suitable by exceeding the standard in%, both of Comparative Examples 1 and 2, which are low-cost Chinese products, were found to be less than the standard.

Claims (3)

  1. 굴 패각을 이용한 구연산칼슘의 제조방법에 있어서,In the manufacturing method of calcium citrate using the oyster shell,
    1) 굴 패각에 부착된 이물질을 제거하여 물로 세척한 다음 건조시켜 굴 패각을 분말화하는 예비단계;1) a preliminary step of powdering the oyster shell by removing foreign matters attached to the oyster shell, washing with water and then drying;
    2) 상기 예비단계에서 얻은 굴 패각 분말에 무수구연산을 가하여 반응시킴으로써 반응생성물을 얻는 반응단계;2) a reaction step of obtaining a reaction product by adding citric anhydride to the oyster shell powder obtained in the preliminary step to react;
    3) 상기 반응단계에서 얻은 반응생성물을 원심분리시켜 펠렛상 침전물을 얻는 침전단계;3) a precipitation step of obtaining a pellet-like precipitate by centrifuging the reaction product obtained in the reaction step;
    4) 상기 침전단계에서 얻은 펠렛상 침전물을 열풍으로 건조시키는 건조단계;4) a drying step of drying the pellet-like precipitate obtained in the precipitation step by hot air;
    5) 상기 건조단계에서 얻은 구연산칼슘을 에어밀로 분쇄시켜 제품화하는 완성단계를 포함하는 것을 특징으로 하는 굴 패각을 이용한 구연산칼슘의 제조방법.5) A method for producing calcium citrate using an oyster shell, characterized in that it comprises a completion step of grinding the calcium citrate obtained in the drying step with an air mill to commercialize.
  2. 청구항 1에 있어서, The method according to claim 1,
    상기 반응단계 중 굴 패각 분말에 무수구연산을 1 : 0.1921~1.9212 중량부의 비율로 가하여 4~100℃에서 1~24시간 반응시키는 것을 특징으로 하는 굴 패각을 이용한 구연산칼슘의 제조방법.The method for producing calcium citrate using oyster shell characterized in that for 1 to 24 hours at 4 ~ 100 ℃ by adding citric anhydride 1: 0.1921 ~ 1.9212 parts by weight to the oyster shell powder in the reaction step.
  3. 청구항 1 또는 청구항 2의 제조방법에 의하여 제조되는 것을 특징으로 하는 구연산칼슘. Calcium citrate, characterized in that produced by the manufacturing method of claim 1 or 2.
PCT/KR2012/010981 2012-09-18 2012-12-17 Method for preparing calcium citrate using oyster shell chips WO2014046344A1 (en)

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EP4180414A4 (en) * 2020-07-13 2024-08-14 Korea Res Inst Chemical Tech Method for manufacturing mono calcium citrate by using shell and application thereof

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KR102383847B1 (en) * 2020-03-04 2022-04-06 한국화학연구원 Preparation method of desulfurizing agent for flue gas desulfurization using disposal oyster shell and desulfurization method of flue gas using the same
KR102582387B1 (en) 2022-02-24 2023-10-19 주식회사 마이크로젠 Manufacturing Method for Soluble Ionized Organic Calcium Using Shell and Reaction Tank Thereof
WO2023163369A1 (en) * 2022-02-24 2023-08-31 (주)피엠아이바이오텍 Method for preparing nano calcium citrate
KR102457957B1 (en) 2022-02-28 2022-10-24 주식회사 블루랩스 Manufacturing method of calcium chloride using oyster shells
KR102613250B1 (en) 2022-09-08 2023-12-13 주식회사 블루랩스 Manufacturing method of activated carbon substitutes using oyster shells and starfish
KR102696130B1 (en) * 2023-09-18 2024-08-16 주식회사 케이바이오닉스 Calcium active organic acid prepared through mechano-chemical treatment and calcium organic acid prepared therefrom.

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EP4180414A4 (en) * 2020-07-13 2024-08-14 Korea Res Inst Chemical Tech Method for manufacturing mono calcium citrate by using shell and application thereof

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