KR20070109201A - Method for producing high purity calcium compound using shell - Google Patents
Method for producing high purity calcium compound using shell Download PDFInfo
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- KR20070109201A KR20070109201A KR1020060041828A KR20060041828A KR20070109201A KR 20070109201 A KR20070109201 A KR 20070109201A KR 1020060041828 A KR1020060041828 A KR 1020060041828A KR 20060041828 A KR20060041828 A KR 20060041828A KR 20070109201 A KR20070109201 A KR 20070109201A
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- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
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- C01P2006/80—Compositional purity
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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- 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
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Abstract
본 발명은 굴, 고막, 바지락, 동죽, 백합 등의 패각에 존재하는 나트륨, 스트론튬 이온을 제거하여, 세라믹콘덴서나 레조네이터 등의 전자세라믹스용 및 필름충전제의 재료 등으로 사용되는 고순도 칼슘계 화합물을 제조하기 위한 패각을 원료로 하는 고순도칼슘계 화합물 제조방법에 관한 것이다.The present invention removes sodium and strontium ions present in shells such as oysters, tympanic membranes, clams, donjuk, lilies, and the like to produce high purity calcium-based compounds used for electronic ceramics such as ceramic capacitors and resonators, and as materials for film fillers. It relates to a high-purity calcium compound production method using the shell as a raw material.
본 발명은, 세정된 패각을 염산 또는 질산 수용액에 투입하여 용해시켜 그 속에 포함된 불순물을 제거하고 암모니아수를 투입하여 pH 5 ~ 9가 되도록 조절한 후 침전물과 상등액을 분리시켜 염화칼슘 또는 질산칼슘 수용액을 제조하는 공정과; 상기 공정에서 제조된 염화칼슘 또는 질산칼슘 수용액 내에 포함된 염화나트륨, 염화스트론튬 또는 질산나트륨, 질산스트론튬을 수산화칼륨과 암모니아수를 첨가하여 pH 8 ~ 13으로 조절하여 수산화나트륨, 수산화스트론튬으로 변환시키는 공정과; 상기 수산화나트륨, 수산화스트론튬을 제거하기 위해 수산화칼슘 중에 존재하는 칼슘이온량의 0.1 ~ 0.5%중량의 계면활성제를 수산화칼슘의 슬러지에 투입하여 교반기를 이용하여 1 ~ 5시간 정도 교반하여 수산화칼슘과 수산화나트륨, 수산화스트론튬의 표면을 활성화시킨 후 원심여과기나 필터프레스를 이용하여 여과시키는 여과공정과; 상기 수산화칼슘을 탄산화하여 탄산칼슘으로 제조하는 탄산칼슘제조공정을 포함하여 이루어지는 것을 특징으로 한다. In the present invention, the washed shell is added to an aqueous solution of hydrochloric acid or nitric acid, dissolved to remove impurities contained therein, and adjusted to pH 5-9 by adding ammonia water, and then the precipitate and the supernatant are separated to obtain an aqueous solution of calcium chloride or calcium nitrate. Manufacturing process; Converting sodium chloride, strontium chloride or sodium nitrate and strontium nitrate contained in the aqueous calcium chloride or calcium nitrate solution prepared in the above step into potassium hydroxide and aqueous ammonia to adjust the pH to 8-13 to convert sodium hydroxide and strontium hydroxide; In order to remove the sodium hydroxide and strontium hydroxide, 0.1 to 0.5% by weight of the amount of calcium ions present in the calcium hydroxide is added to the sludge of calcium hydroxide and stirred for about 1 to 5 hours using a stirrer to make calcium hydroxide, sodium hydroxide and strontium hydroxide. Filtration step of activating the surface of the filter and filtration using a centrifugal filter or filter press; And calcium carbonate production step of carbonating the calcium hydroxide to produce calcium carbonate.
Description
도 1은 본 발명에 의한 합성된 탄산칼슘의 SEM 사진이다.1 is an SEM image of calcium carbonate synthesized according to the present invention.
본 발명은 패각을 원료로 하는 고순도칼슘계 화합물 제조방법에 관한 것으로서, 더욱 상세하게는 굴, 고막, 바지락, 동죽, 백합 등의 패각에 존재하는 나트륨, 스트론튬 이온을 제거하여, 세라믹콘덴서나 레조네이터 등의 전자세라믹스용 및 필름충전제의 재료 등으로 사용되는 고순도 칼슘계 화합물을 제조하기 위한 패각을 원료로 하는 고순도칼슘계 화합물 제조방법에 관한 것이다.The present invention relates to a method for producing a high purity calcium-based compound using shells, and more specifically, to remove sodium and strontium ions present in shells such as oysters, tympanic membranes, clams, donjuk, lilies, and the like, such as ceramic capacitors and resonators. The present invention relates to a method for producing a high purity calcium compound using a shell for producing a high purity calcium compound for use in electronic ceramics and as a material for a film filler.
일반적으로 패각은 폐자원으로써, 바닷가 등에서 흔히 볼 수 있는 것으로 그 원료의 구입이 용이하여 주로 물리적 분쇄만을 하여 패화석 비료로 사용되거나 저순도 석회분말 등의 제조를 위한 재료로 사용되기도 한다. 그러나, 이러한 패각은 사용용도가 많지 않아 상당부분은 매립할 수밖에 없었으며, 이로 인해 매립할 수 있는 한계를 벗어나 심각한 환경오염을 발생하고 있는 실정이다.In general, the shell is a waste resource, which is commonly found on the beach, etc., and the raw material is easy to purchase, and is mainly used as a fossil fertilizer only by physical grinding or as a material for manufacturing low-purity lime powder. However, these shells are not much use, but a large portion of them were to be landfilled, which causes serious environmental pollution beyond the landfill limits.
그리고 최근 들어 패각을 이용하여 경질 탄산칼슘을 제조하는 기술이 있으 나, 패각 내 다량으로 존재하는 나트륨, 스트론튬을 제거 또는 조절할 수 있는 기술이 없기 때문에 전자세라믹스용으로 사용되는 고순도의 탄산칼슘의 제조에 어려움을 겪고 있는 실정이다.In recent years, there has been a technology for producing hard calcium carbonate using shells, but there is no technology for removing or controlling sodium and strontium in large amounts in the shells, and thus for the manufacture of high purity calcium carbonate used for electronic ceramics. The situation is suffering.
본 발명은 상기의 문제점을 해결하기 위한 것으로, 본 발명은 폐자원을 효과적으로 활용하고 자연에서 쉽게 구입할 수 있는 패각을 주원료로 하여 고순도 칼슘계 화합물을 제조하는 것을 목적으로 한다. 또한, 본 발명은 패각의 주요 불순물로 함유되어 있는 나트륨, 스트론튬이온을 효과적으로 제거함으로서 초고순도 칼슘계 화합물을 제조하는 것을 목적으로 한다.The present invention is to solve the above problems, an object of the present invention is to produce a high-purity calcium-based compound using a shell that can be effectively used in the waste resources and easily purchased in nature as a main raw material. In addition, an object of the present invention is to prepare an ultra-high purity calcium-based compound by effectively removing sodium and strontium ions contained as major impurities of the shell.
본 발명은, 세정된 패각을 염산 또는 질산 수용액에 투입하여 용해시켜 그 속에 포함된 불순물을 제거하고 암모니아수를 투입하여 pH 5 ~ 9가 되도록 조절한 후 침전물과 상등액을 분리시켜 염화칼슘 또는 질산칼슘 수용액을 제조하는 공정과; 상기 공정에서 제조된 염화칼슘 또는 질산칼슘 수용액 내에 포함된 염화나트륨, 염화스트론튬 또는 질산나트륨, 질산스트론튬을 수산화칼륨과 암모니아수를 첨가하여 pH 8 ~ 13으로 조절하여 수산화나트륨, 수산화스트론튬으로 변환시키는 공정과; 상기 수산화나트륨, 수산화스트론튬을 제거하기 위해 수산화칼슘 중에 존재하는 칼슘이온량의 0.1 ~ 0.5%중량의 계면활성제를 수산화칼슘의 슬러지에 투입하여 교반기를 이용하여 1 ~ 5시간 정도 교반하여 수산화칼슘과 수산화나트륨, 수산화스트론튬의 표면을 활성화시킨 후 원심여과기나 필터프레스를 이용하여 여과시키는 여과공정과; 상기 수산화칼슘을 탄산화하여 탄산칼슘으로 제조하는 탄산칼슘제 조공정을 포함하여 이루어지는 것을 특징으로 한다.In the present invention, the washed shell is added to an aqueous solution of hydrochloric acid or nitric acid, dissolved to remove impurities contained therein, and adjusted to pH 5-9 by adding ammonia water, and then the precipitate and the supernatant are separated to obtain an aqueous solution of calcium chloride or calcium nitrate. Manufacturing process; Converting sodium chloride, strontium chloride or sodium nitrate and strontium nitrate contained in the aqueous calcium chloride or calcium nitrate solution prepared in the above step into potassium hydroxide and aqueous ammonia to adjust the pH to 8-13 to convert sodium hydroxide and strontium hydroxide; In order to remove the sodium hydroxide and strontium hydroxide, 0.1 to 0.5% by weight of the amount of calcium ions present in the calcium hydroxide is added to the sludge of calcium hydroxide and stirred for about 1 to 5 hours using a stirrer to make calcium hydroxide, sodium hydroxide and strontium hydroxide. Filtration step of activating the surface of the filter and filtration using a centrifugal filter or filter press; And a calcium carbonate preparation step of carbonating the calcium hydroxide to produce calcium carbonate.
이때, 상기 탄산칼슘제조공정은, 상기 수산화칼슘 내의 스트론튬이온을 제거한 후 CO2가스를 직접 주입하여 탄산칼슘을 제조하는 공정이거나, 탄산암모늄을 사용하여 공침시켜 탄산칼슘을 제조하는 공정일 수 있다.In this case, the manufacturing process of calcium carbonate may be a process of preparing calcium carbonate by directly injecting CO 2 gas after removing strontium ions in the calcium hydroxide, or a process of preparing calcium carbonate by coprecipitation using ammonium carbonate.
또한 본 발명에 의한 패각을 원료로 하는 고순도칼슘계 화합물 제조방법에서 상기 여과공정의 계면활성제는, 솔비탄에스테르 또는 슈거에스테르인 것이 바람직하다.Moreover, it is preferable that surfactant in the said filtration process is sorbitan ester or sugar ester in the manufacturing method of the high purity calcium-type compound which uses the shell by this invention as a raw material.
이하, 본 발명에 의한 패각을 원료로 하는 고순도칼슘계 화합물 제조방법을 상세히 설명한다.Hereinafter, a method for producing a high purity calcium compound using the shell of the present invention as a raw material will be described in detail.
패각은 탄산칼슘이 93%이상이고, 유기물이 약 2% 정도이며, 그 중 나트륨이온은 약 0.4%, 스트론튬이온은 약 0.1% 정도가 불순물로 함유되어 있다. 그런데 패각 내 나트륨, 스트론튬이온이 존재하게 되는 원인으로는 바닷물 중에는 칼슘이온이 400ppm, 스트론튬이온이 8ppm 그리고 다량의 나트륨이온이 용존되어 있으며 패류를 형성하는 박테리아가 바닷물에서 양분을 흡수하여 유기물 알맹이와 각질층을 형성하는 과정 중에서 각질층의 형성은 바닷물의 칼슘성분과 탄산수소가 반응하여 각피층과 각질층을 형성하게 되며, 그 과정을 반복하여 성장하게 된다. 이때 바닷물에 존재하는 칼슘이온과 나트륨, 스트론튬이온은 동일한 거동을 하는 것으로 판단된다.The shell has more than 93% of calcium carbonate, about 2% of organic matter, of which about 0.4% of sodium ions and about 0.1% of strontium ions are contained as impurities. However, the cause of the presence of sodium and strontium ions in shell is 400ppm of calcium ions, 8ppm of strontium ions, and a large amount of sodium ions. Formation of the stratum corneum in the process of forming a calcium component of the water and hydrogen carbonate reacts to form a stratum corneum and stratum corneum, it is grown by repeating the process. At this time, calcium ions, sodium, and strontium ions present in seawater are considered to be the same.
이로 인하여 패각의 각질층에 존재하는 나트륨, 스트론튬이온은 농축되어 다음 표 1과 같이 나트륨 4000ppm, 스트론튬 1000ppm이 존재하게 된다. 그러나 이러한 나트륨, 스트론튬이온은 탄산화되어 있을 경우 용해도가 매우 낮기 때문에 수세과정을 거치더라도 제거가 되지 않기 때문에 고순도 탄산칼슘의 제조는 매우 어렵게 된다.As a result, sodium and strontium ions present in the stratum corneum of the shell are concentrated, and as shown in Table 1 below, sodium 4000ppm and strontium 1000ppm are present. However, since sodium and strontium ions are very low in solubility, they cannot be removed even after washing with water, making high purity calcium carbonate very difficult.
본 발명은 먼저, 국내 특허 제0014886호에서 제시한 바와 같이, 패각을 염산이나 질산과 같은 무기산으로 용해하여 염화칼슘 또는 질산칼슘을 제조한다.First, the present invention, as shown in Korean Patent No. 0014886, the shell is dissolved with an inorganic acid such as hydrochloric acid or nitric acid to produce calcium chloride or calcium nitrate.
그 후, 수산화칼륨과 암모니아수를 첨가하여 pH 6 ~ 13 범위에서 중화반응시켜 수산화칼슘을 제조한다.Thereafter, potassium hydroxide and ammonia water are added to neutralize the mixture in a pH range of 6 to 13 to prepare calcium hydroxide.
상기와 같은 방식으로 수산화칼슘을 제조하면 염화칼슘 또는 질산칼슘 수용액 속에 용존되어 있는 나트륨, 스트론튬이온은 용해도가 높은 수산화나트륨, 수산화스트론튬으로 변화하게 된다. 그리고 솔비탄에스테르, 슈거에스테르 등과 같은 에스테르계 계면활성제를 투입하여 5 ~ 15시간 동안 강력 교반하여 수산화칼슘 표면을 활성화시킨 후 이를 여과하여 다시 물에 교반하여 여과한다. 이러한 방법으로 3 ~ 8회를 반복하여 수세, 여과하면 나트륨, 스트론튬이온은 다음 표 2와 같이, 각각 43ppm, 31ppm 정도가 남게 되어 나트륨, 스트론튬이온이 1차적으로 제거가 가능하다. 또한 이러한 과정 후 수산화나트륨, 수산화스트론튬을 수열법을 이용하여 130 ~ 170℃, 20 ~ 100MPa의 고온, 고압하에서 10 ~ 24시간 동안 수열처리 할 경우 잔류하는 나트륨, 스트론튬이온은 각각 22ppm, 17ppm 미만으로 감소하게 된다.When calcium hydroxide is prepared in the above manner, sodium and strontium ions dissolved in calcium chloride or calcium nitrate aqueous solution are changed to high solubility sodium hydroxide and strontium hydroxide. In addition, an ester-based surfactant such as sorbitan ester and sugar ester is added thereto, followed by strong stirring for 5 to 15 hours to activate the calcium hydroxide surface, which is then filtered and stirred again in water. In this way, repeated washing and filtration 3 to 8 times, sodium and strontium ions are left as 43ppm, 31ppm, respectively, as shown in Table 2, so that sodium, strontium ions can be removed first. In addition, the sodium and strontium ions remaining after the hydrothermal treatment for 10 to 24 hours at 130 to 170 ° C., 20 to 100 MPa at a high temperature, and a high pressure by using the hydrothermal method are used after the above process. Will decrease.
이렇게 수열처리된 수산화칼슘에 탄산가스를 주입하여 탄산칼슘으로 제조하거나, 염산이나 질산 등으로 재용한 후 암모니아수 등으로 pH 5 ~ 10으로 중화하여 탄산암모늄과 반응하여 탄산칼슘을 제조하면 나트륨, 스트론튬함량이 표 3과 같이 20 ~ 30ppm미만의 고순도 탄산칼슘을 제조하게 된다.When carbonic acid gas is injected into the hydrothermally treated calcium hydroxide to produce calcium carbonate, or recycled with hydrochloric acid or nitric acid, and then neutralized to pH 5-10 with aqueous ammonia to react with ammonium carbonate to produce calcium carbonate. As shown in Table 3, less than 20 to 30 ppm of high purity calcium carbonate is prepared.
이하, 본 발명의 바람직한 실시 예를 설명하면 다음과 같다.Hereinafter, the preferred embodiment of the present invention will be described.
(실시예)(Example)
[제1공정][Step 1]
패각 내에 존재하는 나트륨, 스트론튬의 양은 상기 표 1과 같이, 4000ppm, 1000ppm 정도이며 그 외에 다수의 불순물이 함유되어 있는데, 먼저 세정된 패각 100g을 염산 또는 질산 2몰의 수용액에 투입한다. 이때 거품이 발생하면서 CO2가스가 분리된다.The amount of sodium and strontium present in the shell is about 4000 ppm and 1000 ppm, as shown in Table 1 above, and contains a plurality of impurities. First, 100 g of the washed shell is added to an aqueous solution of 2 mol of hydrochloric acid or nitric acid. At this point, bubbles are generated and the CO 2 gas is separated.
용해 후 잔류하는 물질은 패각의 표면에 부착되어 있던 유기물과 패류가 서식하던 뻘 속에 존재하는 알루미나 또는 실리카 성분으로서 이와 같은 불순물은 마이크로 필터를 사용하여 제거하면, 연한 회색의 투명 용액이 된다.Substances remaining after dissolution are the alumina or silica components in the shell where the shells were inhabited with the organic matter attached to the shell surface. When such impurities are removed using a micro filter, they become a light gray transparent solution.
이 용액에 암모니아수를 투입하여 pH 5 ~ 9가 되도록 조절하면 용액은 연한 갈색으로 침전물이 발생하며, 이를 10 ~ 24시간 방치 상등액을 분리하여 염화칼슘 또는 질산칼슘 수용액을 제조한다.When the solution is adjusted to pH 5-9 by adding ammonia water to the solution, the solution is light brown, and precipitates are generated. The supernatant is separated from the solution for 10 to 24 hours to prepare an aqueous calcium chloride or calcium nitrate solution.
[제2공정][Step 2]
상기 제1공정에서 제조된 염화칼슘 또는 질산칼슘 수용액 내에는 칼슘과 동일한 거동을 하는 나트륨, 스트론튬이 불순물로서 함께 존재하며, 그 상태는 염화나트륨, 염화스트론튬 또는 질산나트륨, 질산스트론튬으로 존재하게 된다. 이러한 염화칼슘 또는 질산칼슘 수용액에 수산화칼륨과 암모니아수를 첨가하여 pH 8 ~ 13으로 조절하면 수산화 칼슘이 형성되며, 이때 나트륨, 스트론튬이온은 수산화나트륨, 수산화스트론튬으로 동시에 변화하게 된다.In the aqueous calcium chloride or calcium nitrate solution prepared in the first step, sodium and strontium having the same behavior as calcium are present as impurities, and the state is present as sodium chloride, strontium chloride or sodium nitrate, and strontium nitrate. When potassium hydroxide and ammonia water are added to the aqueous calcium chloride or calcium nitrate solution to adjust the pH to 8 to 13, calcium hydroxide is formed, wherein sodium and strontium ions are simultaneously changed to sodium hydroxide and strontium hydroxide.
[제3공정][Step 3]
본 공정은 수산화칼슘 내에 존재하는 수산화나트륨, 수산화스트론튬을 계면활성제를 사용하여 제거하기 위한 공정으로서, 수산화칼슘 슬러지 내에 존재하는 수산화나트륨, 수산화스트론튬을 효과적으로 제거하기 위해 수산화칼슘 중에 존재하는 칼슘이온량의 0.1 ~ 0.5%중량의 계면활성제(예를 들면 솔비탄에스테르 또는 슈거에스테르)를 사용한다.This process is to remove sodium hydroxide and strontium hydroxide in calcium hydroxide by using a surfactant, and 0.1 to 0.5% of the amount of calcium ion in calcium hydroxide to effectively remove sodium hydroxide and strontium hydroxide in calcium hydroxide sludge. Heavy surfactants (eg sorbitan esters or sugar esters) are used.
상기 계면활성제를 수산화칼슘 슬러지에 투입 교반기를 이용하여 1 ~ 5시간 정도 교반하여 수산화칼슘과 수산화나트륨, 수산화스트론튬의 표면을 활성화시킨 후 원심여과기나 필터프레스 등을 이용하여 여과시키며, 이러한 과정을 수회(2 ~ 5회)정도 반복하여 실시한다.The surfactant was added to calcium hydroxide sludge and stirred for about 1 to 5 hours using a stirrer to activate the surface of calcium hydroxide, sodium hydroxide and strontium hydroxide, and then filtered using a centrifugal filter or filter press. Repeat 5 times).
여과 후 120 ~ 150℃ 온도에서 3 ~ 10시간 동안 건조 후 정량분석하여 보면 수산화칼슘내 존재하는 나트륨, 스트론륨이온의 량은 상기 표 2에서 나타낸 것과 같이 각각 28ppm, 20ppm이 존재함을 확인하였다.After filtration and drying for 3 to 10 hours at 120 ~ 150 ℃ temperature, the amount of sodium and strontium ions present in the calcium hydroxide is as shown in Table 2, respectively It was confirmed that 28ppm, 20ppm was present.
[제4공정][Step 4]
본 공정은 수산화칼슘 내에 잔류하는 수산화나트륨, 수산화스트론튬을 수열법을 이용하여 제거하기 위한 공정이다.This step is a step for removing sodium hydroxide and strontium hydroxide remaining in calcium hydroxide by the hydrothermal method.
전 공정에서 제조된 수산화칼슘을 500ml 스테인레스 용기를 이용하여 수열처리하며, 이 과정에서 수산화칼슘 분말을 50g 투입 후 200ml의 물 또는 0.02몰 농도의 염화암모늄 수용액을 수열 용매로 사용하여 130 ~ 170℃의 온도에서 20 ~ 100MPa의 압력하에서 10 ~ 24시간 수열처리를 실시한 후, 수세 여과하여 수산화칼슘 내의 나트륨, 스트론튬이온의 함량을 분석하였다. 그 결과 나트륨과 스트론튬이온의 함량은 표 2에 나타낸 것과 같이 각각 22ppm, 17ppm이었다.Calcium hydroxide prepared in the previous process was hydrothermally treated using a 500 ml stainless steel container. In this process, 50 g of calcium hydroxide powder was added, followed by 200 ml of water or 0.02 molar ammonium chloride solution as a hydrothermal solvent at a temperature of 130 to 170 ° C. After performing hydrothermal treatment for 10 to 24 hours at a pressure of 20 ~ 100MPa, water filtration was performed to analyze the content of sodium and strontium ions in calcium hydroxide. As a result, the contents of sodium and strontium ions were 22 ppm and 17 ppm, respectively, as shown in Table 2.
[제5공정][Step 5]
본 공정은 수산화칼슘을 탄산화하여 탄산칼슘으로 제조하는 공정으로서 수산화칼슘내의 나트륨, 스트론튬이온을 제거한 후 탄산화공정은 CO2가스를 직접 주입하는 CO2 가스주입법과, 탄산암모늄을 사용하여 공침시키는 방법에서 선택하여 탄산칼슘을 제조하는 공정이다.In this process, calcium hydroxide is carbonated to make calcium carbonate. After removing sodium and strontium ions in calcium hydroxide, the carbonation process is selected from CO 2 gas injection method which directly injects CO 2 gas, and coprecipitation using ammonium carbonate. It is a process of manufacturing calcium carbonate.
먼저, CO2가스를 직접 주입하는 CO2 가스주입법으로, 수산화칼슘 10g에 물 300ml를 삼각 플라스크에 투입하여 CO2가스를 2 ~ 5 l/min 정도를 10 ~ 60분간 투입하여 pH 6 ~ 9의 범위에서 반응을 종료하고, 탄산칼슘 슬러지를 여과한 후 건조하여 나트륨과 스트론튬 이온의 함량을 분석하였다. 그 결과 나트륨, 스트론튬이온의 량은 표 3에 나타낸 것과 같이 각각 30ppm, 22ppm이었다.First, a CO 2 gas injection method for directly injecting CO 2 gas, in which 300 ml of water is added to 10 g of calcium hydroxide in an Erlenmeyer flask, and 2 to 5 l / min of CO 2 gas is added for 10 to 60 minutes to a pH range of 6 to 9. After completion of the reaction, the calcium carbonate sludge was filtered and dried to analyze the content of sodium and strontium ions. As a result, the amounts of sodium and strontium ions were 30 ppm and 22 ppm, respectively, as shown in Table 3.
또한, 탄산암모늄을 사용하여 공침시키는 방법으로, 수산화칼슘을 다시 염산이나 질산으로 용해 후 1몰의 염화칼슘이나 질산칼슘으로 제조한 후 여과하여 암모니아수를 이용하여 pH 6 ~ 9정도로 조절하여 다시 마이크로 필터를 사용하여 여과한다. 여과된 용액에 탄산암모늄을 1몰 농도의 수용액 상태에서 투입하여 탄산칼슘을 제조하였다. 그 결과 나트륨, 스트론튬이온의 함량은 표 3에 나타낸 것과 같이 각각 32ppm, 23ppm이었다.In addition, by co-precipitation using ammonium carbonate, calcium hydroxide is dissolved again with hydrochloric acid or nitric acid, and then prepared with 1 mole of calcium chloride or calcium nitrate, filtered and adjusted to pH 6-9 using ammonia water again using a micro filter. And filter. Calcium carbonate was prepared by adding ammonium carbonate to the filtered solution in an aqueous solution of 1 mol concentration. As a result, the contents of sodium and strontium ions were 32 ppm and 23 ppm, respectively, as shown in Table 3.
상술한 바와 같이 본 발명에 따르면, 폐자원을 효과적으로 활용하고 자연에서 쉽게 구입할 수 있는 패각을 주원료로 하여 패각내 불순물로 존재하는 나트륨, 스트론튬 등을 선택적으로 제거하여 유전체, 압전체 등의 전자세라믹스용 및 의약용으로 사용되는 초고순도 칼슘계화합물을 용이하게 제조할 수 있다.As described above, according to the present invention, by effectively using waste resources and using shells that can be easily purchased in nature as the main raw materials, sodium, strontium, etc., which are present as impurities in the shells, are selectively removed for electronic ceramics such as dielectrics and piezoelectrics. It is possible to easily prepare ultra-high purity calcium-based compounds for use in medicine.
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Cited By (6)
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| WO2009096795A1 (en) * | 2008-01-30 | 2009-08-06 | Elkem Solar As | Method for production of calcium compounds. |
| WO2016190718A3 (en) * | 2015-05-28 | 2017-01-12 | 한밭대학교 산학협력단 | Method for producing fine fragments from shells, and material produced using fine shell fragments |
| KR101827456B1 (en) * | 2017-01-12 | 2018-02-08 | 안상익 | Method and apparatus for producing natural calcium from oyster shells |
| US20180148343A1 (en) * | 2015-05-28 | 2018-05-31 | Hanbat National University Industry-Acdemic Cooperatioon Foundation | Method for producing microplates from shells, and material produced by using the microplates |
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| KR20240029864A (en) * | 2022-08-29 | 2024-03-07 | 이혜영 | Method of Producing Calcium Carbonate |
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| KR100232567B1 (en) * | 1997-11-07 | 1999-12-01 | 김판채 | Manufacturing method of high purity lime powder based on shells |
| KR100283527B1 (en) * | 1998-05-26 | 2001-03-02 | 권기만 | Method of preparing calcium carbonate |
| KR100284943B1 (en) * | 1998-12-26 | 2001-03-15 | 차정우 | Method for producing sedimentary calcium carbonate using shell |
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| WO2009096795A1 (en) * | 2008-01-30 | 2009-08-06 | Elkem Solar As | Method for production of calcium compounds. |
| JP2011513163A (en) * | 2008-01-30 | 2011-04-28 | エルケム ソウラー アクシエセルスカプ | Method for producing calcium compound |
| EA016672B1 (en) * | 2008-01-30 | 2012-06-29 | Элкем Солар Ас | Method for production of calcium compounds |
| US8268280B2 (en) | 2008-01-30 | 2012-09-18 | Elkem Solar As | Method for production of calcium compounds |
| KR101325091B1 (en) * | 2008-01-30 | 2013-11-06 | 엘켐 솔라 에이에스 | How to produce calcium compounds |
| WO2016190718A3 (en) * | 2015-05-28 | 2017-01-12 | 한밭대학교 산학협력단 | Method for producing fine fragments from shells, and material produced using fine shell fragments |
| US20180148343A1 (en) * | 2015-05-28 | 2018-05-31 | Hanbat National University Industry-Acdemic Cooperatioon Foundation | Method for producing microplates from shells, and material produced by using the microplates |
| KR101827456B1 (en) * | 2017-01-12 | 2018-02-08 | 안상익 | Method and apparatus for producing natural calcium from oyster shells |
| KR20210007617A (en) * | 2019-07-12 | 2021-01-20 | 경상대학교산학협력단 | Method of preparing calcium peroxide via acid-base replacement reactions from recylced shell powder |
| KR20240029864A (en) * | 2022-08-29 | 2024-03-07 | 이혜영 | Method of Producing Calcium Carbonate |
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