KR20040026383A - A Method for Preparing Calcium Carbonate From Steel-Making Slag and Corbon Dioxide - Google Patents

A Method for Preparing Calcium Carbonate From Steel-Making Slag and Corbon Dioxide Download PDF

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KR20040026383A
KR20040026383A KR1020020057836A KR20020057836A KR20040026383A KR 20040026383 A KR20040026383 A KR 20040026383A KR 1020020057836 A KR1020020057836 A KR 1020020057836A KR 20020057836 A KR20020057836 A KR 20020057836A KR 20040026383 A KR20040026383 A KR 20040026383A
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slag
calcium
carbon dioxide
calcium carbonate
eluate
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KR100922563B1 (en
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김형석
한기현
변태봉
이학봉
배우현
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재단법인 포항산업과학연구원
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    • 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
    • C01F11/18—Carbonates
    • C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
    • 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
    • C01F11/005—Preparation involving liquid-liquid extraction, absorption or ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • 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
    • Y02W30/20—Waste processing or separation
    • 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
    • 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
    • Y02W30/52—Mechanical processing of waste for the recovery of materials, e.g. crushing, shredding, separation or disassembly

Abstract

PURPOSE: Provided is a method for preparing calcium carbonate with a high purity, which is an environmental-friendly method by using waste resources, i.e., a steel making slag and carbon dioxide or CO2-containing exhaust gas. CONSTITUTION: The method comprises the steps of: crushing steel making slag into a size of 45 micrometers or less and introducing water thereto to adjust the pH to 12 or higher, and separating undissolved powder from the eluted solution by filtration to obtain a calcium-eluted solution having a pH of 12 or higher; and reacting the calcium-eluted solution with CO2 or CO2-containing exhaust gas under a pH of 7 or higher. In particular, the steel making slag comprises 20-52 wt% of calcium oxide.

Description

재강슬래그와 이산화탄소를 이용한 탄산칼슘 제조방법{A Method for Preparing Calcium Carbonate From Steel-Making Slag and Corbon Dioxide}A Method for Preparing Calcium Carbonate From Steel-Making Slag and Corbon Dioxide}

본 발명은 제강슬래그와 이산화탄소(CO2)를 이용하여 탄산칼슘(CaCO3)을 제조하는 방법에 관한 것이며, 보다 상세하게는 재강슬래그의 칼슘 용출액과 이산화탄소 함유 배가스를 이용한 탄산칼슘 제조방법에 관한 것이다.The present invention relates to a method for producing calcium carbonate (CaCO 3 ) using steelmaking slag and carbon dioxide (CO 2 ), and more particularly to a method for producing calcium carbonate using calcium eluate of ash steel slag and carbon dioxide-containing flue gas. .

제철소에서 대량으로 발생되는 제강슬래그로는 용선예비처리 슬래그, 전로슬래그, 스테인레스 슬래그, 전기로 슬래그 등이 있다. 제강슬래그는 시멘트 및 도로용 및 토목 공사시 채움용 골재로 대부분 활용되고 있으며, 제강슬래그의 화학성분은 하기 표 1에 나타낸 바와 같다.Steelmaking slag generated in large quantities in steel mills include molten iron preliminary slag, converter slag, stainless slag and electric furnace slag. Steelmaking slag is mostly used as a filling aggregate for cement and road and civil works, the chemical composition of steelmaking slag is shown in Table 1 below.

[표 1] 각종 제강슬래그의 화학성분(무게%)[Table 1] Chemical Composition (Weight%) of Various Steelmaking Slags

CaOCaO SiO2SiO2 T-FeT-Fe Al2O3Al2O3 MgOMgO MnOMnO P2O5P2O5 전로converter 40.8040.80 12.6112.61 22.8122.81 2.572.57 7.447.44 4.054.05 1.701.70 탈인Dein 51.651.6 20.020.0 2.92.9 3.43.4 7.27.2 탈규Deregulation 20.220.2 48.548.5 4.54.5 5.15.1 3.23.2 스테인레스stainless 37.237.2 15.015.0 3.93.9 19.819.8 12.112.1 전기로산화기Electric furnace 33.8533.85 16.7916.79 20.120.1 11.6111.61 2.682.68 5.845.84 0.380.38 전기로환원기Furnace Reduction Machine 51.8251.82 4.854.85 0.10.1 35.1535.15 6.506.50 0.10.1 0.010.01

(기타 산화철 및 수산화칼슘등의 잔부 포함)(Including the balance of other iron oxide and calcium hydroxide)

이들 제강슬래그는 그 화학성분중 산화칼슘을 다량 함유하고 있어 높은 염기도를 나타내며, 제강슬래그를 물에 넣으면 산화칼슘중의 일부가 용출되어 알칼리성을 나타낸다.These steelmaking slag contains a large amount of calcium oxide in the chemical composition, and shows high basicity. When steelmaking slag is put in water, part of the calcium oxide elutes to show alkalinity.

한편, 지구온난화의 원인인 이산화탄소 배출량을 저감시키기 위해, 배가스중의 이산화탄소 가스를 효과적으로 분리하는 방법 그리고 분리된 이산화탄소의 활용방법으로 이산화탄소를 메탄올 제조에 사용하는 방법등 이산화탄소의 분리 및 활용에 대한 여러가지 방법이 연구되어 왔다. 그러나, 아직 경제적이고 실용성이 있는 활용방법은 없는 실정이다.Meanwhile, in order to reduce carbon dioxide emissions, which are the cause of global warming, various methods for the separation and utilization of carbon dioxide, such as effectively separating carbon dioxide gas from flue gas and using carbon dioxide in methanol production using the separated carbon dioxide method. This has been studied. However, there is no economic and practical method of utilization yet.

침강성 탄산칼슘의 제조방법으로는 탄산가스 화합방법, 석회소다방법 및 소다방법등으로 있으며, 일본 특개평 11-31495 및 일본 특개 2001-270713 등과 같이 주로 탄산가스 화합방법으로 제조되어 왔다. 즉 석회석(CaCO3)을 소성하여 생석회(CaO)를 만들고, 이 생석회(CaO)와 물(H2O)을 반응시켜 소석회유(Ca(OH)2)를 제조하고, 이 소석회유(Ca(OH)2)에 이산화탄소 기체를 불어 넣어 반응시킴으로써 침강성 탄산칼슘(CaCO3)을 석출시킨다. 이러한, 화합방법에서는 탄산칼슘 석출에 필요한 칼슘성분은 석회석을 열분해 시켜 만든 소석회를 사용하고 탄산가스는 석회석 분해시에 발생된 탄산가스를 회수하여 사용하지만, 반응율이 100%가 될 수 없으므로 일부는 반응 중에 대기중으로 방출될 것이다. 즉, 석회석을 원료로 사용할 경우 소성 공정에서 이산화탄소가 발생한다. 따라서, 환경 오염을 야기할 뿐만 아니라 제조공정이 복잡하고 석회석을 1000oC 이상의 고온으로 소성하여 중간 물질인 생석회를 제조함으로, 고가의 제조비용이 소요된다.The precipitation method of precipitated calcium carbonate includes a carbon dioxide gas compounding method, a lime soda method and a soda method, and has been mainly produced by a carbon dioxide gas compounding method such as Japanese Patent Laid-Open No. 11-31495 and Japanese Patent Laid-Open 2001-270713. That is, calcined limestone (CaCO 3 ) to form quicklime (CaO), and reacted with the quicklime (CaO) and water (H 2 O) to prepare calcareous oil (Ca (OH) 2 ), this calcareous oil (Ca ( OH) 2 ) precipitates precipitated calcium carbonate (CaCO 3 ) by blowing carbon dioxide gas into the reaction. In the compounding method, calcium components required for calcium carbonate precipitation use slaked lime made by pyrolysis of limestone and carbon dioxide is used to recover carbon dioxide generated during limestone decomposition, but the reaction rate cannot be 100%. Will be released into the atmosphere. That is, when limestone is used as a raw material, carbon dioxide is generated in the firing process. Therefore, not only does it cause environmental pollution, and the manufacturing process is complicated, and calcined limestone at a high temperature of 1000 ° C. or higher to prepare quicklime, an intermediate material, and thus requires expensive manufacturing cost.

따라서, 이산화탄소 발생량을 저감하기 위해서는 칼슘성분을 석회석에서 공급해서는 안되고 이산화탄소와 결합하지 않은 칼슘원을 사용하여야한다. 이와 같은 칼슘원으로는 염화칼슘, 질산칼슘 등이 있지만 이들 약품 또한 고가이다.Therefore, in order to reduce the amount of carbon dioxide generated, calcium components should not be supplied from limestone and calcium sources not combined with carbon dioxide should be used. Such calcium sources include calcium chloride and calcium nitrate, but these drugs are also expensive.

이외에도 제철소 스텐인레스강 정련공장의 부원료분진과 탄산가스를 이용하여 탄산칼슘을 제조하는 방법이 대한민국 특허출원 98-54120호로 출원된 바 있다. 상기 특허에서는 제철소에서 스테인레스강을 정련할 때 사용하는 생석회, 돌로마이트와 같은 부원료의 저장 또는 이송 중에 발생하는 분진을 집진설비를 이용하여 집진한 부원료 분진으로 현탁액을 제조한 후, 탄산가스의 탄산화 반응으로 탄산칼슘을 제조하는데, 이 경우 현탁액은 소석회유(Ca(OH)2)이며, 현탁액 내의 소석회가 탄산가스와 반응하여 탄산칼슘을 생성한다. 그러나, 이때 생성되는 탄산칼슘과 현탁액 내의 미반응 소석회 입자는 모두 백색 입자로써 구별이 용이하지 않으며, 반응 종점에서 일부 미반응 소석회가 존재할 경우 이는 최종물에서 불순물로 작용하여 최종물의 순도가 떨어지는 문제가 있다.In addition, a method for producing calcium carbonate using secondary raw material dust and carbon dioxide gas in a stainless steel refinery of a steel mill has been filed in Korean Patent Application No. 98-54120. In the above patent, a suspension is prepared by using a dust collecting facility in which dust generated during storage or transportation of auxiliary raw materials such as quicklime and dolomite used in refining stainless steel in a steel mill is collected using a dust collecting facility, and then, by carbonation reaction of carbon dioxide gas. Calcium carbonate is prepared, in which case the suspension is hydrated lime oil (Ca (OH) 2 ) and the hydrated lime in the suspension reacts with carbon dioxide to produce calcium carbonate. However, the calcium carbonate produced and the unreacted limestone particles in the suspension are not easily distinguishable as white particles, and when some unreacted limestone is present at the reaction end point, it acts as an impurity in the final product, resulting in a lower purity of the final product. have.

이에 본 발명의 목적은 제강슬래그의 칼슘 이온 용출액과 이산화탄소 혹은 이산화탄소 함유 배가스를 이용한 고순도 탄산칼슘 제조방법을 제공하는 것이다.Accordingly, an object of the present invention is to provide a method for producing high purity calcium carbonate using calcium ion eluate of steelmaking slag and carbon dioxide or carbon dioxide-containing flue gas.

본 발명의 다른 목적은 제강 슬래그 및 이산화탄소 함유 배가스등 폐자원을 활용한 고순도의 탄산칼슘 제조방법을 제공하는 것이다.Another object of the present invention is to provide a high purity calcium carbonate production method utilizing waste resources such as steelmaking slag and carbon dioxide-containing flue gas.

도 1 내지 도 4는 본 발명에 의한 실시예 1 내지 4에 의한 시간 경과에 따른 pH변화로써 탄산칼슘의 형성을 확인하는 그래프이다.1 to 4 are graphs confirming the formation of calcium carbonate as the pH changes over time by Examples 1 to 4 according to the present invention.

본 발명에 의하면,According to the invention,

제강슬래그를 45㎛이하로 분쇄한 다음 물을 주입하여 pH 12 이상이 되도록 조정하고, 미용해분과 용출액을 여과분리하여 pH 12이상의 칼슘이온 용출액을 얻는 단계; 및Grinding the steel slag to 45 μm or less and then adjusting the water to inject pH 12 or more, and separating the undissolved powder and the eluate by filtration to obtain a calcium ion eluate having a pH of 12 or more; And

상기 칼슘 이온 용출액과 이산화탄소 또는 이산화탄소 함유 배가스를 pH 7이상으로 유지되도록 반응시키는 단계;Reacting the calcium ion eluate with carbon dioxide or carbon dioxide-containing flue gas to be maintained at pH 7 or higher;

를 포함하는 탄산칼슘 제조방법이 제공된다.There is provided a method for producing calcium carbonate comprising a.

이하, 본 발명에 대하여 상세히 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

재강슬래그에는 상기 표 1에 나타낸 바와 같이 다량의 CaO가 함유되어 있으나, 유리 CaO(free CaO)는 수 %에 지나지 않으며, 대부분 CaO는 다른 성분과 화합물을 형성하고 있어서 비교적 안정한 상태임으로 이용이 용이하지 않았다.The steel slag contains a large amount of CaO as shown in Table 1, but only a few% of free CaO (free CaO), and most of CaO forms a compound with other components, which is relatively stable and therefore not easy to use. Did.

본 발명에서는 제강슬래그의 칼슘 이온 용출액을 이용함으로 고순도의 탄산칼슘이 제조된다. 또한, 탄산칼슘의 제조에 이산화탄소를 함유하는 배가스가 사용됨으로, 대기중으로 방출되는 유해한 탄산가스의 함량이 감소된다.In the present invention, high purity calcium carbonate is prepared by using calcium ion eluate of steelmaking slag. In addition, since exhaust gas containing carbon dioxide is used in the production of calcium carbonate, the content of harmful carbon dioxide gas released into the atmosphere is reduced.

나아가, 제강슬래그의 칼슘 이온 용출액과 이산화탄소 함유 배가스를 반응시켜 침강 탄산칼슘을 석출시키는데 있어서, 배가스중의 이산화탄소를 분리할 필요 없이 배가스를 이산화탄소 함유 배가스를 그대로 사용가능한 것이다. 또한, 배가스중의 이산화탄소를 분리하여 사용할 수도 있다.Furthermore, in depositing precipitated calcium carbonate by reacting a calcium ion eluate of steelmaking slag with a carbon dioxide-containing flue gas, the flue gas can be used as it is without the separation of carbon dioxide in the flue gas. It is also possible to separate and use carbon dioxide in the flue gas.

본 발명에서, 칼슘공급원으로서 칼슘이 산화칼슘으로 존재하는 제철소 부생 제강슬래그가 사용된다. 제강 슬래그를 미분쇄하여 물과 반응시키면 불순물이 적고, 유리 칼슘이온이 용해되어 있는 강알칼리성 칼슘 용출액이 얻어진다. 이때, 칼슘 성분이 효과적으로 용출될 수 있도록 제강슬래그를 45㎛이하의 입자 크기로 분쇄한다. 45㎛이하인 경우, 칼슘성분이 보다 신속하고 효과적으로 용출된다.In the present invention, as a source of calcium, iron by-product steelmaking slag in which calcium is present as calcium oxide is used. When steelmaking slag is pulverized and reacted with water, a strong alkaline calcium eluate is obtained in which impurities are few and free calcium ions are dissolved. At this time, the steelmaking slag is pulverized to a particle size of 45㎛ or less so that the calcium component can be effectively eluted. When it is 45 micrometers or less, a calcium component elutes more quickly and effectively.

제강슬래그로는 전로슬래그, 탈인슬래그, 탈규슬래그, 스테인레스 슬레그, 전기로산화기 슬래그 및 전기로 환원기슬래그등이 사용될 수 있다. 나아가, 산화칼슘이 20~52중량%를 포함하는 어떠한 제강슬래그가 사용될 수 있다.For steelmaking slag, converter slag, dephosphorization slag, de-silica slag, stainless slag, furnace oxidizer slag and furnace reducer slag can be used. Furthermore, any steelmaking slag containing 20 to 52% by weight of calcium oxide can be used.

칼슘 이온 용출시, 입자 크기가 45㎛이하인 제강슬래그를 물에 첨가하고 pH 12이상인 고알칼리성이 되도록 조정하여 pH 12이상의 칼슘 이온 용출액을 제조한다.When calcium ion is eluted, a steel ion slag having a particle size of 45 µm or less is added to water and adjusted to a high alkalinity of pH 12 or more to prepare a calcium ion eluate having a pH of 12 or more.

상기 강알칼리성 칼슘 이온 용출액에 이산화탄소 가스 혹은 이산화탄소 가스를 함유하는 배가스를 산기관을 통하여 잘 순산시키면서 취입하여 반응시키면, 흰색 침전물인 탄산칼슘이 생성되어 반응액이 우유빛으로 변한다. 이 때 얻어지는 백색 침전을 분리하여 탄산칼슘을 얻는다.When the strongly alkaline calcium ion eluate is blown and reacted with carbon dioxide gas or flue gas containing carbon dioxide gas well through an acid pipe, a white precipitate of calcium carbonate is produced and the reaction solution turns milky. The white precipitate obtained at this time is separated to obtain calcium carbonate.

그러나, 이때 우유빛으로 변한 용액내에 이산화탄소 혹은 이산화탄소 함유 배가스를 계속 주입하여 pH가 7 미만으로 낮아지면서 생성된 탄산칼슘은 중탄산칼슘으로재용해되어, 탄산칼슘 침전이 없어지면서 맑은 용액이 된다. 따라서, 중탄산칼슘으로 전환하지 않은 상태, 즉 탄산칼슘으로 존재하는 pH 영역에서 칼슘 이온 용출액과 이산화탄소 혹은 이산화탄소 함유 배가스를 반응시키고 침전을 분리하여야 한다. 즉, 칼슘 이온 용출액과 이산화탄소 혹은 이산화탄소 함유 배가스의 반응시 pH를 pH 7이상, 바람직하게는 8이상으로 유지하여야 한다.However, at this time, the calcium carbonate produced by continuously injecting carbon dioxide or carbon dioxide-containing flue gas into a milky color solution is lowered to less than 7, so that the calcium carbonate is re-dissolved into calcium bicarbonate, and the calcium carbonate precipitates to become a clear solution. Therefore, the calcium ion eluate and the carbon dioxide or carbon dioxide-containing flue-gas must be reacted and the precipitate is separated in the pH range which is not converted to calcium bicarbonate, that is, calcium carbonate. That is, when the calcium ion eluate reacts with the carbon dioxide or carbon dioxide-containing flue gas, the pH should be maintained at pH 7 or higher, preferably 8 or higher.

본 발명에서는 제강슬래그를 사용하여 강알칼리성 칼슘 이온 용출액을 제조함으로 종래 석회석에서 소석회유 제조시 발생되는 이산화탄소 가스가 발생되지 않으며, 칼슘이온 용출액을 이용하여 탄산칼슘을 제조함으로 불순물의 혼입이 없는 99.9%이상의 고순도의 탄산칼슘을 얻을 수 있다.In the present invention, by producing a strong alkaline calcium ion eluate using steelmaking slag, carbon dioxide gas generated during the manufacture of calcined lime oil is not generated in conventional limestone, and 99.9% of impurities are not mixed by preparing calcium carbonate using the calcium ion eluate. The above-mentioned high purity calcium carbonate can be obtained.

이하 실시예를 통하여 본 발명을 보다 자세히 설명한다.The present invention will be described in more detail with reference to the following examples.

<실시예 1><Example 1>

전로 슬래그를 45㎛이하로 분쇄한 다음 물을 반응물의 pH가 12이상이 될때까지 주입한 후 미용해분과 용출액을 여과 분리하여 전로 슬래그의 칼슘 이온 용출액을 제조하였다.The converter slag was pulverized to 45 μm or less, and water was injected until the pH of the reactant was 12 or more. Then, the undissolved fraction and the eluate were separated by filtration to prepare a calcium ion eluate of the converter slag.

pH가 12 이상인 칼슘 이온 용출액 200㎖을 비이커에 넣고 탄산가스를 분당 0.5ℓ로 취입하였다. 취입하자마자 흰색 탄산칼슘 침전물이 생성되어 pH 프로브(probe)가 보이지 않을 정도의 백탁으로 되었다.200 ml of calcium ion eluate having a pH of 12 or more was placed in a beaker and carbon dioxide gas was blown at 0.5 L per minute. Upon ingestion, a white calcium carbonate precipitate was formed which resulted in a white cloud where the pH probe was invisible.

이때, 백탁용액에 계속 탄산가스를 취입하면 pH 약 7 이하에서 탄산칼슘이 중탄산칼슘으로 재용해되어 백탁이 엷어지기 시작하였다. 이는 pH 7이하에서 탄산칼슘이 중탄산 칼슘으로 전환됨을 나타내는 것이다.(도 1 설명바랍니다.) 따라서, 반응시 pH를 약 8정도로 유지하였다.At this time, if carbon dioxide was continuously injected into the cloudy solution, the calcium carbonate was re-dissolved into calcium bicarbonate at a pH of about 7 or less, and the cloudiness began to thin. This indicates that the calcium carbonate is converted to calcium bicarbonate below pH 7. (Explain in FIG. 1) Therefore, the pH was maintained at about 8 during the reaction.

백색 탄산칼슘 침전물을 여과하여 탄산칼슘을 얻었다. 순도는 99.9%이상 이었다.The white calcium carbonate precipitate was filtered off to obtain calcium carbonate. Purity was over 99.9%.

<실시예2>Example 2

실시예 1과 동일한 방법으로 제강슬래그의 칼슘 이온 용출액을 제조하였다.A calcium ion eluate of steelmaking slag was prepared in the same manner as in Example 1.

pH가 12이상의 칼슘 이온 용출액 200㎖을 비이커에 넣고 탄산가스를 분당 0.2ℓ로 취입하였으며, 이에 따라 백색 침전물이 형성되었다. 반응시, pH를 약 8로 유지하였다. 백색 탄산칼슘 침전물을 여과하여 탄산칼슘을 얻었으며, 순도는 99.9%이상 이었다.200 ml of calcium ion eluate having a pH of 12 or more was placed in a beaker, and carbon dioxide gas was blown at 0.2 L per minute, thereby forming a white precipitate. During the reaction, the pH was maintained at about 8. The white calcium carbonate precipitate was filtered to obtain calcium carbonate, and the purity was over 99.9%.

<실시예 3><Example 3>

실시예 1과 동일한 방법으로 제강슬래그의 칼슘 이온 용출액을 제조하였다.A calcium ion eluate of steelmaking slag was prepared in the same manner as in Example 1.

pH가 12이상의 칼슘 이온 용출액 200㎖을 비이커에 넣고 탄산가스를 분당 0.3ℓ로 취입하였으며, 이에 따라 백색 침전물이 형성되었다. 반응시, pH를 약 8로 유지하였다. 백색 탄산칼슘 침전물을 여과하여 탄산칼슘을 얻었으며, 순도는 99.9%이상 이었다.200 ml of calcium ion eluate having a pH of 12 or more was placed in a beaker, and carbon dioxide gas was blown at 0.3 L per minute, thereby forming a white precipitate. During the reaction, the pH was maintained at about 8. The white calcium carbonate precipitate was filtered to obtain calcium carbonate, and the purity was over 99.9%.

<실시예 4><Example 4>

실시예 1과 동일한 방법으로 제강슬래그의 칼슘 이온 용출액을 제조하였다.A calcium ion eluate of steelmaking slag was prepared in the same manner as in Example 1.

pH가 12이상의 칼슘 이온 용출액 200㎖을 비이커에 넣고 질소가스와 탄산가스를 9:1 중량비로 혼합한 인공 배가스를 분당 0.2ℓ로 취입하였으며, 이에 따라 백색 침전물이 형성되었다. 반응시, pH를 약 8로 유지하였다. 백색 탄산칼슘 침전물을 여과하여 탄산칼슘을 얻었으며, 순도는 99.9%이상 이었다.200 ml of calcium ion eluate having a pH of 12 or more was placed in a beaker, and an artificial flue gas mixed with nitrogen gas and carbon dioxide gas in a 9: 1 weight ratio was blown at 0.2 L per minute, thereby forming a white precipitate. During the reaction, the pH was maintained at about 8. The white calcium carbonate precipitate was filtered to obtain calcium carbonate, and the purity was over 99.9%.

도 1 내지 4에 실시예 1 내지 4에 해당하는 시간경과에 따른 슬래그 용출액과 탄사가스와의 반응시 pH변화를 도시하였다. 반응이 진행됨에 따라 탄산칼슘이 생성되고, pH 7 부근에서 용출액내의 칼슘이온이 거의 소진되어 탄산칼슘화됨을 알 수 있다.1 to 4 illustrate the pH change during the reaction between the slag eluate and the carbon dioxide gas over time corresponding to Examples 1 to 4. As the reaction proceeds, calcium carbonate is formed, and the calcium ions in the eluate are almost consumed at about pH 7.

본 발명에 의하면 폐기처분되고 있는 제강슬래그를 이용하여 고순도의 탄산칼슘이 제조된다. 또한, 이산화탄소 함유 배가스가 이용됨으로 배가스의 배출이 감소된다.According to the present invention, calcium carbonate of high purity is produced by using steelmaking slag that is disposed of. In addition, the emission of exhaust gas is reduced by the use of carbon dioxide-containing exhaust gas.

Claims (3)

제강슬래그를 45㎛이하로 분쇄한 다음 물을 주입하여 pH 12 이상이 되도록 조정한 후 미용해분과 용출액을 여과 분리하여 pH 12이상의 칼슘이온 용출액을 얻는 단계; 및Grinding steelmaking slag to 45 μm or less, adjusting water to inject pH 12 or more, and then separating the undissolved powder and the eluate to obtain a calcium ion eluate having a pH of 12 or more; And 상기 칼슘 이온 용출액과 이산화탄소 또는 이산화탄소 함유 배가스를 pH 7이상으로 유지되도록 반응시키는 단계;Reacting the calcium ion eluate with carbon dioxide or carbon dioxide-containing flue gas to be maintained at pH 7 or higher; 를 포함하는 고순도 탄산칼슘 제조방법.High purity calcium carbonate production method comprising a. 제 1항에 있어서, 상기 제강슬래그로는 전로슬래그, 탈인슬래그, 탈규슬래그, 스테인레스 슬레그, 전기로산화기 슬래그 및 전기로 환원기슬래그로 구성되는 그룹으로부터 선택됨을 특징으로 하는 방법.The method of claim 1, wherein the steelmaking slag is selected from the group consisting of converter slag, dephosphorous slag, de-silica slag, stainless slag, electrooxidizer slag and furnace reducer slag. 제 1항 또는 제 2항에 있어서, 상기 제강슬래그는 산화칼슘을 20~52중량%포함하여 이루어짐을 특징으로 하는 방법.The method of claim 1 or 2, wherein the steelmaking slag comprises 20 to 52% by weight of calcium oxide.
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