KR20010098992A - The preparation method of calcium hydrogen citrate and calcium citrate used as lime stone or shells - Google Patents
The preparation method of calcium hydrogen citrate and calcium citrate used as lime stone or shells Download PDFInfo
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- KR20010098992A KR20010098992A KR1020010046098A KR20010046098A KR20010098992A KR 20010098992 A KR20010098992 A KR 20010098992A KR 1020010046098 A KR1020010046098 A KR 1020010046098A KR 20010046098 A KR20010046098 A KR 20010046098A KR 20010098992 A KR20010098992 A KR 20010098992A
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- calcium
- citrate
- calcium citrate
- citric acid
- shells
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- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 title claims abstract description 49
- 239000001354 calcium citrate Substances 0.000 title claims abstract description 49
- 235000013337 tricalcium citrate Nutrition 0.000 title claims abstract description 48
- 235000019738 Limestone Nutrition 0.000 title claims abstract description 9
- 239000006028 limestone Substances 0.000 title claims abstract description 9
- PFKGDYCESFRMAP-UHFFFAOYSA-L dicalcium citrate Chemical compound [Ca+2].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O PFKGDYCESFRMAP-UHFFFAOYSA-L 0.000 title abstract description 12
- 238000002360 preparation method Methods 0.000 title 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 81
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 9
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 7
- 210000004087 cornea Anatomy 0.000 claims abstract 2
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 15
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 11
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 11
- 239000000920 calcium hydroxide Substances 0.000 claims description 11
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 10
- 239000000292 calcium oxide Substances 0.000 claims description 6
- 235000010216 calcium carbonate Nutrition 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 abstract description 24
- 235000015170 shellfish Nutrition 0.000 abstract description 10
- 241000237502 Ostreidae Species 0.000 abstract description 4
- 235000020636 oyster Nutrition 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 2
- 241000237519 Bivalvia Species 0.000 abstract 1
- 235000020639 clam Nutrition 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 229960005069 calcium Drugs 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 235000013361 beverage Nutrition 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-L 2-(carboxymethyl)-2-hydroxysuccinate Chemical compound [O-]C(=O)CC(O)(C(=O)O)CC([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-L 0.000 description 4
- 159000000007 calcium salts Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229940043430 calcium compound Drugs 0.000 description 3
- 150000001674 calcium compounds Chemical class 0.000 description 3
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 3
- 239000001527 calcium lactate Substances 0.000 description 3
- 235000011086 calcium lactate Nutrition 0.000 description 3
- 229960002401 calcium lactate Drugs 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000020510 functional beverage Nutrition 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 206010006956 Calcium deficiency Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011001 calcium citrates Nutrition 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- -1 organic acid calcium salt Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019614 sour taste Nutrition 0.000 description 1
- 235000019640 taste Nutrition 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Classifications
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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
- C07F3/04—Calcium compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L17/00—Food-from-the-sea products; Fish products; Fish meal; Fish-egg substitutes; Preparation or treatment thereof
- A23L17/40—Shell-fish
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
본 발명은 석회석 또는 패각류와 구연산을 이용하여 구연산칼슘을 제조하는 방법에 관한 것으로 상세하게는 굴껍질, 꼬막, 바지락 등과 같은 패각류 또는 석회석를 50∼325mesh로 분말화 시킨 탄산칼슘을 구연산과 반응시켜 수소구연산칼슘 또는 구연산칼슘을 제조하는 방법에 관한 것이다. 그리고 패각류, 석회석을 800∼1300℃로 소성한 소성 패각 또는 생석회를 구연산과 반응시켜 수소구연산칼슘 또는 구연산칼슘을 제조하는 방법에 관한 것이다.The present invention relates to a method for producing calcium citrate using limestone or shellfish and citric acid. Specifically, by reacting calcium carbonate powdered with 50 to 325 mesh of shellfish or limestone such as oyster shells, corneas, and clams with citric acid. It relates to a method of producing calcium hydrogen citrate or calcium citrate. The present invention relates to a method for 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.
Description
본 발명은 석회석 또는 패각류등의 칼슘염을 유기산과 반응시켜 유기산칼슘을 제조하는 방법에 관한 것으로, 더욱 상세하게는 석회석, 탄산칼슘, 생석회, 소석회, 패각류, 소성패각 등을 구연산과 반응시켜 수소구연산칼슘(calcium hydrogen citrate)과 구연산칼슘(calcium citrate)을 제조하는 것이다. 특히 생명체가 만든 칼슘화합물인 패각류를 사용한 경우에는 제품 생산단가와 물성이 뛰어나고, 식품용으로 적합하다. 종래의 수용성 유기산칼슘에 대한 제조 방법으로는 대한민국 특허 특1996-0001421에서는 패각 분말을 실온의 35∼45% 초산수용액에 반응시키고, 건조하여 이온화칼슘을 제조하였다. 여기에 40% 수산화나트륨을 실온에서 다시 반응시켜 건조하여 수산화칼슘을 제조하였다. 대한민국 특허 특0173556에서는 구연산을 1∼3%함유한 식초에 패각을 용해함으로써 유용한 미네랄 성분을 1.5%이상 함유한 패각 용해액에 제조하였다. 대한민국 특허 10-0238838에서는 굴패각 분말을 분쇄, 소성 처리하여 소성분말을 얻고 이를 초산용액에서 산처리하여 pH를 조절하여 활성화된 용액을 제조하고, 건조시켜 분말형 담체를 얻고, 여기에 다시 초산 및 물을 첨가 활성화 용액을 만들고, 항균성 금속이온을 포함한 금속이온을 첨가하여 이온교환 후 무기 항균제를 제조하였다. 또한, 특허 공개번호 특2001-0044280에서는 패각류를 소성시켜 젖산과 반응시켜 젖산칼슘을 만드는 젖산칼슘의 제조 방법에 관한 것이 특허출원 되어 있다.The present invention relates to a method for producing an organic calcium by reacting calcium salts such as limestone or shellfish with an organic acid, and more particularly, by reacting limestone, calcium carbonate, quicklime, calcareous, shellfish, calcined shells with citric acid, and the like. Calcium hydrogen citrate and calcium citrate will be prepared. In particular, shellfish, which are calcium compounds made by living organisms, are excellent in production cost and physical properties and are suitable for food use. As a manufacturing method for a conventional water-soluble organic acid calcium salt in the Republic of Korea Patent No. 1996-0001421 was prepared by reacting the shell powder in a 35-45% acetic acid aqueous solution at room temperature, dried to produce an ionized calcium. 40% sodium hydroxide was reacted again at room temperature and dried to prepare calcium hydroxide. In Korean Patent No. 0173556, a shell was dissolved in vinegar containing 1 to 3% citric acid to prepare a shell solution containing 1.5% or more of useful minerals. In Korean Patent 10-0238838, the oyster shell powder is pulverized and calcined to obtain a small powder, which is acid-treated in acetic acid solution to adjust the pH to prepare an activated solution, and dried to obtain a powder carrier, and again acetic acid and water The addition of the activation solution was made, and an inorganic antimicrobial agent was prepared after ion exchange by adding metal ions including antimicrobial metal ions. In addition, Japanese Patent Application Laid-Open No. 2001-0044280 discloses a patent application relating to a method for producing calcium lactate in which shells are calcined to react with lactic acid to produce calcium lactate.
이와 같이 산과 패각류를 이용한 종래의 기술에서는 초산과 젖산을 주로 사용하여 유기산칼슘을 제조하였다. 즉, 젖산칼슘과 초산칼슘의 경우 신맛이 강하여 음료수와 같은 식품에는 적합하지 않다. 본 발명에서는 식품용에 적합한 수소구연산칼슘 또는 구연산칼슘을 제조하고자 한다.As described above, in the conventional technology using acid and shellfish, organic acid calcium was prepared mainly using acetic acid and lactic acid. That is, calcium lactate and calcium acetate are not so suitable for foods such as drinks because of their strong sour taste. In the present invention, it is intended to prepare calcium citrate or calcium citrate suitable for food use.
본 발명은 국내에 폐기물로 야적되어 있는 패각류 또는 탄산칼슘 등을 구연산과 반응시켜 고가의 수소구연산칼슘과 구연산칼슘을 제조하였다. 국내의 기능성 음료에는 구연산이 많이 첨가되어 있으나, 고가의 수소구연산칼슘과 구연산칼슘을 첨가한 음료는 드문 것으로 되어 있다.The present invention produced expensive hydrogen citrate and calcium citrate by reacting shellfish or calcium carbonate, which is piled as waste in Korea, with citric acid. In domestic functional beverages, citric acid is added a lot, but beverages in which expensive calcium citrate and calcium citrate are added are rare.
따라서 본 발명은 수소구연산칼슘과 구연산칼슘을 대량으로 생산할 수 있는 제조 방법으로 투명한 음료성 식품에 적합한 무색, 무미, 무취의 구연산칼슘을 제공할 수 있어 국민 건강에 이바지 하고자 한다.Therefore, the present invention can provide a colorless, tasteless, and odorless calcium citrate suitable for transparent beverage food as a production method capable of producing a large amount of calcium citrate and calcium citrate to contribute to national health.
도 1는 본 발명에 따른 수소구연산칼슘 제조 공정도.1 is a manufacturing process of calcium hydrogen citrate according to the present invention.
도 2는 본 발명에 따른 구연산칼슘 제조 공정도.Figure 2 is a process for producing calcium citrate according to the present invention.
본 발명은 해안가에 버려진 채 쌓여가는 굴 껍질과 같은 패각류를 수거하여 어민들의 양식사업에 이익을 증대시키고, 현대인에게 발생하는 칼슘결핍 현상을 해결하고, 음료시장에 저렴한 가격으로 대량의 칼슘을 공급하기 위하여 다년간의 연구 끝에 수소구연산칼슘과 구연산칼슘을 제조하였다.The present invention collects shellfish such as oyster shells piled up on the shore and increases the profits for fishermen's aquaculture business, solves the calcium deficiency that occurs in modern people, and supplies large amounts of calcium at low prices to the beverage market. In order to do this, calcium hydrogen citrate and calcium citrate were prepared after many years of research.
본 발명을 더욱 더 상세하게 설명하면 다음과 같다. 우선, 해안가에 야적되어 있는 패각을 회수하고 이것을 세척하고, 표면의 불순물을 제거하여 자연건조 한 후 분쇄기를 사용하여 50-325mesh의 패각분말을 제조한다. 제조된 패각분말은 구연산과 반응하여 수소구연산칼슘과 구연산칼슘으로 제조되며 반응식으로 나타내면 다음과 같다.The present invention will be described in more detail as follows. First, the shells collected on the shore are collected and washed, and the surface impurities are removed and dried naturally to prepare 50-325 mesh shell powder using a grinder. The prepared shell powder is made of calcium hydrogen citrate and calcium citrate by reacting with citric acid.
즉, 불순물이 포함된 패각분말을 구연산수용액에 투입시켜 반응식 (2)와 같이 제조한다. 이때 패각이 투입되면 구연산과 반응하여 투명한 수소구연산칼슘수용액으로 전이되며 불순물(SiO2, 유기물 등)은 용해되지 않고 존재한다. 또한 패각분말은 용해된 구연산의 당량비 보다 적은 양을 투입하여 과포화도가 발생하지 않을 정도로 투입하여 수소구연산칼슘수용액을 제조한다. 이러한 수용액은 반응식 (3)에서 불순물을 제거 시켜 투명한 수소구연산칼슘과 구연산이 포함된 수용액으로 제조한다. 이 수용액을 반응식 (4-1)에서는 소량의 탄산칼슘, 산화칼슘, 수산화칼슘, 순수패각, 소성패각 등의 칼슘명을 사용하여 수소구연산칼슘으로 전환시킨다. 그러면 액 중에 수소구연산칼슘의 증가로 과포화현상이 발생하여 수소구연산칼슘은 결정형태로 침전된다. 결정화된 수소구연산칼슘은 여과 분리하여 순수 수소구연산칼슘을 제조한다. 본 발명의 수소구연산칼슘 제조 공정을 도 1에 나타내었다. 또한 반응식 (3)에서 제조된 수소구연산칼슘수용액을 반응식 (4-2)에서는 다량의 칼슘염을 사용하여 구연산칼슘을 제조한다. 본 발명의 구연산칼슘의 제조 공정을 도 2에 나타내었다.That is, the shell powder containing the impurity is added to the citric acid aqueous solution to prepare a reaction formula (2). In this case, the shell is reacted with citric acid to transfer to a transparent aqueous solution of calcium citrate, and impurities (SiO 2 , organic matter, etc.) are present without being dissolved. In addition, the shell powder is added in an amount less than the equivalent ratio of dissolved citric acid to the extent that the degree of supersaturation does not occur to prepare an aqueous solution of calcium citrate. This aqueous solution is prepared as an aqueous solution containing transparent calcium citrate and citric acid by removing impurities in the reaction (3). This aqueous solution is converted into calcium hydrogen citrate using a small amount of calcium carbonate, calcium oxide, calcium hydroxide, pure shell, calcined shell, and the like in the reaction formula (4-1). Then, supersaturation occurs due to the increase of calcium citrate in the liquid, and the calcium citrate precipitates in crystalline form. Crystallized calcium citrate is filtered off to produce pure calcium citrate. Calcium hydrogen citrate manufacturing process of the present invention is shown in FIG. In addition, the aqueous calcium citrate solution prepared in Scheme (3) is prepared by using a large amount of calcium salt in Scheme (4-2). The manufacturing process of the calcium citrate of this invention is shown in FIG.
이하 실시예를 통하여 본 발명을 더욱 상세히 한다.The present invention through the following examples in more detail.
[실시예 1] 해안가의 굴패각을 수거하여 물로 세척하고, 자연 건조 후 굴패각의 표면에 남아 있는 불순물을 최대한 제거한다. 불순물이 제거된 패각을 50∼325mesh로 건식 분쇄한다.[Example 1] The oyster shells of the shore are collected and washed with water, and after the natural drying, impurities remaining on the surface of the oyster shells are removed as much as possible. The shell from which impurities are removed is dry milled to 50 to 325 mesh.
[실시예 2] 실시예 1의 분쇄 패각을 대차식로 또는 회전식로 등을 사용하여 800-1300℃로 소성하여 소성패각(생석회)을 제조하고, 수화하여 소석회를 제조한다.[Example 2] The pulverized shell of Example 1 was calcined at 800-1300 ° C. using a bogie furnace or a rotary furnace to prepare a calcined shell (quick lime), followed by hydration to prepare calcined lime.
[실시예 3] 수용액에서 구연산의 농도에 따른 수소구연산칼슘의 과포화도를 측정하기 위하여 물 1000㎖에 구연산 20g을 용해시켜 구연산수용액을 제조한 후 탄산칼슘을 1g씩 증가시켜 투입시켜면 11g까지는 반응식 (1)에 의해 27g의 수소구연산칼슘으로 전환하여 투명한 수소구연산칼슘 수용액이 된다. 그러나 총 투입된 탄산칼슘의 양이 12g이 되면 수소구연산칼슘이 수용액에 과포화되어 핵 생성과 성장을 통하여 수소구연산칼슘이 결정으로 석출된다. 따라서 과포화가 일어나기 시작할 때까지 투입된 탄산칼슘의 양을 측정하여 표 1에 나타내있다.Example 3 In order to measure the degree of supersaturation of calcium citrate in accordance with the concentration of citric acid in an aqueous solution, 20 g of citric acid was dissolved in 1000 ml of water to prepare an aqueous citric acid solution. It converts into 27 g of calcium citrates by 1), and turns into transparent aqueous calcium citrate. However, when the total amount of calcium carbonate added is 12 g, calcium citrate is supersaturated in aqueous solution, and calcium citrate precipitates as crystals through nucleation and growth. Therefore, it is shown in Table 1 by measuring the amount of calcium carbonate added until supersaturation starts to occur.
[실시예 4∼7] 실시예 3에서 구연산의 농도를 40, 100, 200, 400g으로 변화시켜 각각의 수소구연산칼슘이 과포화현상이 발생할 때까지 투입된 탄산칼슘의 양을 측정하였다, 그 결과를 표 1에 나타내었다.[Examples 4 to 7] In Example 3, the concentration of citric acid was changed to 40, 100, 200, and 400 g, and the amount of calcium carbonate added until each hydrogen citrate was supersaturated was measured. 1 is shown.
[실시예 8] 용량 1500㎖의 회분식 반응기에 물 1000㎖을 채운다. 여기에 구연산 20g을 투입, 교반하여 구연산수용액을 제조한다. 실시예 1의 패각 분말을 11g을 취하여 구연산수용액에 투입하여 교반시킨다. 이때 액 중에 용해되지 않은 불순물은 여과필터를 사용하여 제거함으로 맑은 수소구연산칼슘 수용액으로 제조되며 pH는 4.0정도이다. 이 제조된 수소구연산칼슘 수용액에 실시예 2의 소석회(수산화칼슘) 1g을 첨가하면 용액에 수소구연산칼슘이 과포화되어 핵생성과 핵성장으로 수소구연산칼슘 28g이 침전된다.Example 8 A batch reactor with a capacity of 1500 ml was charged with 1000 ml of water. 20 g of citric acid was added thereto and stirred to prepare an aqueous citric acid solution. 11 g of the shell powder of Example 1 was taken and added to the citric acid aqueous solution and stirred. In this case, impurities not dissolved in the liquid are removed by using a filtration filter to prepare a clear aqueous solution of calcium citrate, pH is about 4.0. When 1 g of hydrated lime (calcium hydroxide) of Example 2 is added to the prepared aqueous hydrogen citrate solution, calcium hydrogen citrate is supersaturated in the solution, and 28 g of calcium hydrogen citrate precipitates due to nucleation and nuclear growth.
[실시예 9∼12] 실시예 8에서 구연산의 농도를 40, 100, 200, 400g으로 하여 각각 패각 23, 60, 88, 141g을 취하여 반응시켜 수소구연산칼슘수용액을 제조하여 불순물을 제거한다. 그리고 수소구연산칼슘수용액에 각각 소석회 1g씩을 더 투입하면 과포화현상에 의해 수소구연산칼슘이 결정으로 침전이 되고, 그 양은 55, 140, 205, 326g이었으며 결과를 표 1에 나타내었다.[Examples 9 to 12] In Example 8, the concentrations of citric acid were 40, 100, 200, and 400 g, and shells 23, 60, 88, and 141 g were respectively reacted to prepare an aqueous solution of calcium citrate to remove impurities. When 1 g of each of the calcined lime was further added to the aqueous hydrogen citrate solution, calcium citrate precipitated as a crystal due to supersaturation, and the amounts thereof were 55, 140, 205, and 326 g, and the results are shown in Table 1.
[실시예 13∼17] 실시예 8∼12에서 결절형 수소구연산칼슘을 제조 후 용액속에 남아있는 구연산의 함량을 분석한 결과 각각 5, 9, 22, 86, 218g이었다. 이러한 현상은 반응이 진행되면 초기구연산의 농도가 클수록 수용액 내에 공통이온화 효과가 커져 미반응 구연산이 증가되는 것을 알 수 있고, 표 1에 결과를 나타내었다.Examples 13 to 17 As a result of analyzing the content of citric acid remaining in the solution after preparing the nodular calcium citrate in Examples 8 to 12, the amounts were 5, 9, 22, 86, and 218 g, respectively. This phenomenon can be seen that as the reaction proceeds, the greater the concentration of initial citric acid, the greater the common ionization effect in the aqueous solution, and thus the unreacted citric acid is increased.
[실시예 18] 실시예 8에서 제조된 수소구연산칼슘 수용액에 실시예 2의 소석회(수산화칼슘) 4g을 투입하여 10분간 반응시켜 구연산칼슘 30g을 제조한다. 이때 수용액의 pH는 4.8이었다Example 18 4 g of hydrated lime (calcium hydroxide) of Example 2 was added to an aqueous solution of calcium citrate prepared in Example 8 and reacted for 10 minutes to prepare 30 g of calcium citrate. At this time, the pH of the aqueous solution was 4.8
[실시예 19∼22] 실시예 9∼12에서 구연산의 농도를 40, 100, 200, 400g으로 하여 각각 패각 23, 60, 88, 141g을 취하여 반응시켜 불순물을 제거하여 밝은 수소구연산칼슘수용액을 제조한다. 그리고 각각의 용액에 실시예 2에서 제조된 소석회(수산화칼슘) 9, 23, 33, 52g을 각각 투입하여 10분간 교반하여 구연산칼슘 60, 152, 222, 353g을 제조하였다. 표 1에 그 결과를 나타내었다.[Examples 19 to 22] In Examples 9 to 12, citric acid concentrations were 40, 100, 200 and 400 g, and shells 23, 60, 88 and 141 g were taken and reacted to remove impurities to prepare a bright aqueous solution of calcium citrate. do. Then, 9, 23, 33, 52 g of hydrated lime (calcium hydroxide) prepared in Example 2 were added to each solution, and stirred for 10 minutes to prepare calcium citrate 60, 152, 222, and 353 g. Table 1 shows the results.
상기한 결과에서 알 수 있듯이 구연산과 칼슘화합물을 맑고 투명한 수소구연산칼슘수용액을 제조할 수 있다. 그리고 수소구연산칼슘수용액의 과포화도 현상을 이용하여 수소구연산칼슘과 구연산칼슘을 제조할 수 있다.As can be seen from the above results, a clear and transparent calcium citrate aqueous solution of citric acid and calcium compound can be prepared. And calcium citrate and calcium citrate can be prepared using the supersaturation phenomenon of the aqueous solution of calcium citrate.
본 발명은 폐기물로 분류되는 패각류 또는 칼슘염을 구연산과 반응시켜 고품위 수소구연산칼슘과 구연산칼슘을 제조함으로 기능성 음료 제품에 큰 변화를 가져올 수 있으며, 국민건강에 이익을 줄 수 있다. 그 동안 투명성 음료수에 칼슘제를 첨가할 경우 맛에 큰 영향을 주거나 용해성이 없어서 문제가 되었으나, 본 발명에서는 식품용 칼슘화합물 또는 생명체가 만든 칼슘염 등을 사용하여 수소구연산칼슘과 구연산칼슘을 제조하였다. 따라서 본 발명의 제조 방법으로 만들어진 유기산칼슘은 음료사업자에게 큰 효과가 있다.The present invention can produce a high-quality calcium citrate and calcium citrate by reacting the shellfish or calcium salt classified as waste with citric acid can bring a big change in the functional beverage products, and can benefit the national health. In the meantime, when the calcium agent is added to the transparent beverage, there is a problem in that it has a great influence on the taste or there is no solubility, but in the present invention, calcium hydrogen citrate and calcium citrate were prepared using a calcium compound for food or a calcium salt made by an organism. Therefore, the organic acid calcium produced by the manufacturing method of the present invention has a great effect on beverage companies.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100491554B1 (en) * | 2001-12-24 | 2005-05-31 | 문병우 | Liquid calcium composition extracted from oyster shell and its using method |
| CN102816059A (en) * | 2012-08-28 | 2012-12-12 | 中粮生物化学（安徽）股份有限公司 | Production method and application of calcium hydrogen citrate |
| WO2014046344A1 (en) * | 2012-09-18 | 2014-03-27 | 주식회사 서진바이오텍 | Method for preparing calcium citrate using oyster shell chips |
| CN105418411A (en) * | 2015-12-21 | 2016-03-23 | 日照金禾博源生化有限公司 | Preparation method for easily soluble calcium hydrogen citrate |
| KR101683150B1 (en) | 2016-07-21 | 2016-12-06 | 주식회사 나예코스메틱 | Method of manufacturing calcium citrate with high degree of electrolytic dissociation |
| KR20210112068A (en) * | 2020-03-04 | 2021-09-14 | 한국화학연구원 | Preparation method of desulfurizing agent for flue gas desulfurization using disposal oyster shell and desulfurization method of flue gas using the same |
| KR20230126906A (en) | 2022-02-24 | 2023-08-31 | 주식회사 마이크로젠 | Manufacturing Method for Soluble Ionized Organic Calcium Using Shell and Reaction Tank Thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100491554B1 (en) * | 2001-12-24 | 2005-05-31 | 문병우 | Liquid calcium composition extracted from oyster shell and its using method |
| CN102816059A (en) * | 2012-08-28 | 2012-12-12 | 中粮生物化学（安徽）股份有限公司 | Production method and application of calcium hydrogen citrate |
| WO2014046344A1 (en) * | 2012-09-18 | 2014-03-27 | 주식회사 서진바이오텍 | Method for preparing calcium citrate using oyster shell chips |
| KR101499292B1 (en) * | 2012-09-18 | 2015-03-09 | 주식회사 서진바이오텍 | Process for Preparing of Calcium Citrate Using Oyster Shells |
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| KR101683150B1 (en) | 2016-07-21 | 2016-12-06 | 주식회사 나예코스메틱 | Method of manufacturing calcium citrate with high degree of electrolytic dissociation |
| KR20210112068A (en) * | 2020-03-04 | 2021-09-14 | 한국화학연구원 | Preparation method of desulfurizing agent for flue gas desulfurization using disposal oyster shell and desulfurization method of flue gas using the same |
| KR20230126906A (en) | 2022-02-24 | 2023-08-31 | 주식회사 마이크로젠 | Manufacturing Method for Soluble Ionized Organic Calcium Using Shell and Reaction Tank Thereof |
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