Synthesis of CaCO3 from Limestone using a Batch-type Microwave Kiln

doi:10.12972/ksmer.2013.50.4.451

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2013 Vol.50, Issue 4 Preview Page Next Page

Research Paper

Synthesis of CaCO3 from Limestone using a Batch-type Microwave Kiln 회분식 마이크로웨이브 소성로를 활용한 석회석으로부터 탄산칼슘 합성: 황대주 · 유영환 · 석병태 · 조계홍 · 안지환 · 한 춘 · 이종대
Dae-Ju Hwang, Young-Hwan Yu, Byeong-Tae Seok, Kye-Hong Cho, Ji-Whan Ahn, Choon Han, Jong-Dae Lee

31 August 2013. pp. 451-469

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Abstract

An energy-efficient, batch-type microwave kiln was used to form CaO from domestic limestone. All CaCO3 was converted to CaO, which was used for the synthesis of precipitated calcium carbonate(PCC) through the carbonation and hydrothermal processes. After Ca(OH)2 solution(0.3 M) was prepared, carbonation reactions were ended at pH 6.0 at a flow rate of 200 cc CO2/min. As the preparation temperature increased from 25 to 80℃, the form of PCC changed from colloidal-shaped to spindle-shaped by self assembly of cubic-shaped PCC. In the CaO-(H2O:CH3OH(2:8v/v%))-CO2 system, cubic-shaped and spherical-shaped PCC were prepared by depending on the suction of CH3OH solution. On the other hand, hexagonal-shaped aragonite PCC was prepared by the hydrothermal process. In this process, colloidal-shaped PCC from the carbonation process reacted with CO2 to form supersaturated Ca(HCO3)2 solution. Then, the solution was fed to hot water as liquid droplets(size:2 mm).

Keywords

Limestone

Calcination

Carbonation

Microwave kiln

Precipitated calcium carbonate

국내 석회석을 에너지효율이 높은 회분식 마이크로웨이브 소성로로 소성하여 CaO를 제조하고, 탄산화반응과 열수반응으로 침강성탄산칼슘(PCC, precipitated calcium carbonate)을 합성하였다. 탄산화 반응시 수용액내에서 Ca(OH)2 0.3 M, CO2 가스량 200 cc/분의 조건하에서, pH가 12에서 6까지 변화 될 때 종결하였다. 이 때 합성온도를 25℃에서 80℃로 상승시키면 칼사이트의 결정상인 교질 형태에서 자기 조립에 의한 방추형의 PCC로 합성되었다. 수용액 대신 메탄올용액 내에서 탄산화반응 유도 시 메탄올 용액(H2O:CH3OH(2:8v/v%))의 산도를 pH 12에서 7까지 변화될 때 종결하였으며, 메탄올 용액의 흡입건조방식에 따라 칼사이트의 결정상인 입방형 PCC와 바테라이트의 결정상인 구형 PCC를 합성할 수 있었다. 열수 반응에서는 제조된 교질탄산칼슘 형태의 PCC를 이용하여 Ca(HCO3)2 과포화용액을 제조하고, 끓는물에 방울 크기 2 mm로 투입하여 아라고나이트의 결정상인 육각기둥 형태인 PCC를 합성할 수 있었다.

키워드

석회석

소성

탄산화

마이크로웨이브 소성로

침강성탄산칼슘

References

Bes, A. M., 2006, “Process simulation of limestone calcination in normal shaft kilns,” Dr thesis, Otto-von-Guericke University Magdeburg, Germany.
Clemens, J. and Saltiel, C., 1996, “Numerical modeling of materials processing in microwave furnaces,” International J. Heat and Mass Transfer, Vol. 39, No. 8, pp. 1665-1675.
Changhong, D., Xianpeng, Z. and Jinsong, Z., 1997, “The synthesis of ultrafine SiC powder by the microwave heating technique,” J. of Materials Science, Vol. 32, pp. 2469-2472.
Chatterjee, A., Basak, T. and Ayappa, K. G., 1998, “Analysis of microwave sintering of ceramics,” J. AIChE. Vol. 44, No. 10, pp. 2302-2311.
Choi, K.S., Park, J.K. and Ahn, J.W., 2004, “Formation mechanism of aragonite by substitute of Mg²⁺ ions,” J. of the Korean Ceramic Society, Vol. 41, No. 12, pp. 889-892.
Das, S. and Mukhopadhyay, A. K., 2009, “Prospects of microwave processing : an overview,” Bull. Mater. Sci, Vol. 32, No. 1, pp. 1-13.
Garcia-Carmona, J. and Gomez-Morales, J., 2003, “Morphological characteristics and aggregation of calcite crystals obtained by bubbling CO₂ through a Ca(OH)₂ suspension in the presence of additives,” Powder Technology, Vol. 130, pp. 307-315.
Hua, Z., Shao, M. and Li, H., 2009a, “Synthesis of needlelike aragonite crystals in the presence of magnesium chloride and their application in papermaking,,” Advanced Composite Materials, Vol. 18, pp. 315-326.
Hua, Z., Shao, M. and Cai, Q., 2009b, “Synthesis of Needlelike Aragonite from Limestone without Calcinations in the Presence of Magnesium Sulfate,” Advanced Composite Materials, Vol. 18, pp. 187-195.
Hwang, D.J., Cho, K.H. and Choi, M.K., 2011, “Effects of sodium dodecyl benzenesulfonic acid (SDBS) on the morphology and the crystal phase of CaCO₃,” Korean J. Chem. Eng, Vol. 28, No. 9, pp. 1927-1935.
Hwang, D.J., Ryu, J.Y. and Park, J.H., 2012, “Calcination of mega-crystalline calcite using microwave and electric furnaces,” J. of Industrial and Engineering Chemistry, Vol. 18 No. 6, pp. 1956-1963.
Hwang, D.J., Ryu, J.Y. and Park, J.H., 2013, “Preparation of CaCO₃ using mega-crystalline calcite in electrical furnace and batch type microwave kiln,” J. of Industrial and Engineering Chemistry, DOI 10.1016/j.jiec. 2013.01.017.
Hwang, D.J., 2013, “Synthesis of CaCO₃ from natural carbonate minerals using microwave kiln,” Dr thesis, Department of Chemical Engineering, Chungbuk National University, Korea.
Juvekar, V.A. and Sharma, M.M., 1973, “Absorption of CO₂ in a suspension of lime,” Chemical Engineering Science, Vol. 28, pp. 825-837.
Kenkre, V. M., Skala, L. and Weiser, M. W., 1991, “Theory of microwave interactions in ceramic materials : the phenomenon of thermal runaway,” J. Materials Science, Vol. 26, pp. 2483-2489.
Koo, B.K. and Min, K.S., 1992, “Synthesis of calcium carbonate fine powders in Ca(OH)₂-C₂H₅OH-CO₂ system,” Taejeon National University of Technology, Vol. 9, No. 1, pp. 539-550.
Kristen, H., 2003, “Microwave sintering of alumina at 2.45GHz,” J. Am. Ceram. Soc, Vol. 86, No. 8, pp. 1307- 1312.
Kim, K.H., Han, G.C. and You, K.S., 2009, “ Effect of SrCO₃ and MgCl₂・6H₂O addition on synthesis of aragonite in Ca(OH)₂-CO₂-H₂O system at low temperature,” Geosystem Engineering, Vol. 12, No. 2, pp. 45-55.
Lee, J.J. and park, J.L., 2001, “Manufacture of precipitated calcium carbonate from pungchon limestone,” J. of Advanced Mineral Aggregate Composites, Vol. 21, pp. 251-256.
Lee, J.J. and Park, J.L., 2002, “Manufacture and dispersion of calcite type calcium carbonate using limestone,” J. of Advanced Mineral Aggregate Composites, Vol. 7, pp. 19-25.
Lee, J.J., Park, C.L. and Kim, H.K., 2003, “Study on the synthesis and characterization of vaterite using limestone,” J. of Advanced Mineral Aggregate Composites, Vol. 8, pp. 19-28.
Metaxas, A. C., 1991, “Microwave heating,” J. Power Engineering, Vol. 5, No. 5, pp. 237-247.
Noh, J.H. and Choi, J.H., 2002, “Evaluation method of grade and quality for limestone,” J. Miner. Soc. Korea (Mineral & industry), Vol. 15, No. 1, pp. 1-14.
Ohutama Kogyo Co., ltd. 2005,, “Hollow columnar calcium carbonate and method of manufacturing the same,” JP patent, 200,282.
Ohutama Kogyo Co., ltd., 2007, “Tubular calcium carbonate,” JP patent, 176,776.
Park, J.L., Choi, S.K. and Kim, B.G., 2002, “Effect of temperature on the formation of vaterite in Ca(OH)₂-CH₃OH- H₂O-CO₂ System,” J. of the Korean Ceramic Society, Vol. 39, No. 12, 1143-1148.
Park, J.K., Park, H.S. and Ahn, J.W., 2004, “Synthesis of aragonite precipitated calcium carbonate by homogeneous precipitate reaction of Ca(OH)₂ and Na₂CO₃,” J. of the Korean Crystal Growth and Crystal Technology, Vol. 14, No. 3, pp. 110-114.
Panda, S.S., Singh, V. and Upadhyaya, A., 2006, “Sintering response of austenitic(316L) and ferritic(434L) stainless steel consolidated in conventional and microwave furnaces,” Scripta Materialia., Vol. 54, pp. 2179-2183.
Sung, I.Y. and Oum, J.H., 1999, “A study on manufacture of precipitated calcium carbonate used the pungchon limestone,” J. of Advanced Mineral Aggregate Composites, Vol. 4, pp. 71-104.
Shin, B.C., 2001, “Preparation of colloidal calcium carbonate by carbonation process,” Ms thesis, Department of Chemical Engineering Graduate School, Kangwon National University, Korea.
Siddarth, G., 2007, “Comparison of solid-State microwave annealing with conventional furnace annealing of ionimplanted SiC,” J. Electronic Materials, Vol. 36, No. 4, pp. 423-331.
Zhao, C. and Vleugels, J., 2000, “Hybrid sintering with a tubular susceptor in a cylindrical single-mode microwave furnace,” Acta Mater, Vol. 48, pp. 3795-3801.

Information

Publisher :The Korean Society of Mineral and Energy Resources Engineers
Publisher(Ko) :한국자원공학회
Journal Title :Journal of the Korean Society of Mineral and Energy Resources Engineers
Journal Title(Ko) :한국자원공학회지
Volume : 50
No :4
Pages :451-469
DOI :https://doi.org/10.12972/ksmer.2013.50.4.451

[1] Bes, A. M., 2006, “Process simulation of limestone calcination in normal shaft kilns,” Dr thesis, Otto-von-Guericke University Magdeburg, Germany.

[2] Clemens, J. and Saltiel, C., 1996, “Numerical modeling of materials processing in microwave furnaces,” International J. Heat and Mass Transfer, Vol. 39, No. 8, pp. 1665-1675.

[3] Changhong, D., Xianpeng, Z. and Jinsong, Z., 1997, “The synthesis of ultrafine SiC powder by the microwave heating technique,” J. of Materials Science, Vol. 32, pp. 2469-2472.

[4] Chatterjee, A., Basak, T. and Ayappa, K. G., 1998, “Analysis of microwave sintering of ceramics,” J. AIChE. Vol. 44, No. 10, pp. 2302-2311.

[5] Choi, K.S., Park, J.K. and Ahn, J.W., 2004, “Formation mechanism of aragonite by substitute of Mg²⁺ ions,” J. of the Korean Ceramic Society, Vol. 41, No. 12, pp. 889-892.

[6] Das, S. and Mukhopadhyay, A. K., 2009, “Prospects of microwave processing : an overview,” Bull. Mater. Sci, Vol. 32, No. 1, pp. 1-13.

[7] Garcia-Carmona, J. and Gomez-Morales, J., 2003, “Morphological characteristics and aggregation of calcite crystals obtained by bubbling CO₂ through a Ca(OH)₂ suspension in the presence of additives,” Powder Technology, Vol. 130, pp. 307-315.

[8] Hua, Z., Shao, M. and Li, H., 2009a, “Synthesis of needlelike aragonite crystals in the presence of magnesium chloride and their application in papermaking,,” Advanced Composite Materials, Vol. 18, pp. 315-326.

[9] Hua, Z., Shao, M. and Cai, Q., 2009b, “Synthesis of Needlelike Aragonite from Limestone without Calcinations in the Presence of Magnesium Sulfate,” Advanced Composite Materials, Vol. 18, pp. 187-195.

[10] Hwang, D.J., Cho, K.H. and Choi, M.K., 2011, “Effects of sodium dodecyl benzenesulfonic acid (SDBS) on the morphology and the crystal phase of CaCO₃,” Korean J. Chem. Eng, Vol. 28, No. 9, pp. 1927-1935.

[11] Hwang, D.J., Ryu, J.Y. and Park, J.H., 2012, “Calcination of mega-crystalline calcite using microwave and electric furnaces,” J. of Industrial and Engineering Chemistry, Vol. 18 No. 6, pp. 1956-1963.

[12] Hwang, D.J., Ryu, J.Y. and Park, J.H., 2013, “Preparation of CaCO₃ using mega-crystalline calcite in electrical furnace and batch type microwave kiln,” J. of Industrial and Engineering Chemistry, DOI 10.1016/j.jiec. 2013.01.017.

[13] Hwang, D.J., 2013, “Synthesis of CaCO₃ from natural carbonate minerals using microwave kiln,” Dr thesis, Department of Chemical Engineering, Chungbuk National University, Korea.

[14] Juvekar, V.A. and Sharma, M.M., 1973, “Absorption of CO₂ in a suspension of lime,” Chemical Engineering Science, Vol. 28, pp. 825-837.

[15] Kenkre, V. M., Skala, L. and Weiser, M. W., 1991, “Theory of microwave interactions in ceramic materials : the phenomenon of thermal runaway,” J. Materials Science, Vol. 26, pp. 2483-2489.

[16] Koo, B.K. and Min, K.S., 1992, “Synthesis of calcium carbonate fine powders in Ca(OH)₂-C₂H₅OH-CO₂ system,” Taejeon National University of Technology, Vol. 9, No. 1, pp. 539-550.

[17] Kristen, H., 2003, “Microwave sintering of alumina at 2.45GHz,” J. Am. Ceram. Soc, Vol. 86, No. 8, pp. 1307- 1312.

[18] Kim, K.H., Han, G.C. and You, K.S., 2009, “ Effect of SrCO₃ and MgCl₂・6H₂O addition on synthesis of aragonite in Ca(OH)₂-CO₂-H₂O system at low temperature,” Geosystem Engineering, Vol. 12, No. 2, pp. 45-55.

[19] Lee, J.J. and park, J.L., 2001, “Manufacture of precipitated calcium carbonate from pungchon limestone,” J. of Advanced Mineral Aggregate Composites, Vol. 21, pp. 251-256.

[20] Lee, J.J. and Park, J.L., 2002, “Manufacture and dispersion of calcite type calcium carbonate using limestone,” J. of Advanced Mineral Aggregate Composites, Vol. 7, pp. 19-25.

[21] Lee, J.J., Park, C.L. and Kim, H.K., 2003, “Study on the synthesis and characterization of vaterite using limestone,” J. of Advanced Mineral Aggregate Composites, Vol. 8, pp. 19-28.

[22] Metaxas, A. C., 1991, “Microwave heating,” J. Power Engineering, Vol. 5, No. 5, pp. 237-247.

[23] Noh, J.H. and Choi, J.H., 2002, “Evaluation method of grade and quality for limestone,” J. Miner. Soc. Korea (Mineral & industry), Vol. 15, No. 1, pp. 1-14.

[24] Ohutama Kogyo Co., ltd. 2005,, “Hollow columnar calcium carbonate and method of manufacturing the same,” JP patent, 200,282.

[25] Ohutama Kogyo Co., ltd., 2007, “Tubular calcium carbonate,” JP patent, 176,776.

[26] Park, J.L., Choi, S.K. and Kim, B.G., 2002, “Effect of temperature on the formation of vaterite in Ca(OH)₂-CH₃OH- H₂O-CO₂ System,” J. of the Korean Ceramic Society, Vol. 39, No. 12, 1143-1148.

[27] Park, J.K., Park, H.S. and Ahn, J.W., 2004, “Synthesis of aragonite precipitated calcium carbonate by homogeneous precipitate reaction of Ca(OH)₂ and Na₂CO₃,” J. of the Korean Crystal Growth and Crystal Technology, Vol. 14, No. 3, pp. 110-114.

[28] Panda, S.S., Singh, V. and Upadhyaya, A., 2006, “Sintering response of austenitic(316L) and ferritic(434L) stainless steel consolidated in conventional and microwave furnaces,” Scripta Materialia., Vol. 54, pp. 2179-2183.

[29] Sung, I.Y. and Oum, J.H., 1999, “A study on manufacture of precipitated calcium carbonate used the pungchon limestone,” J. of Advanced Mineral Aggregate Composites, Vol. 4, pp. 71-104.

[30] Shin, B.C., 2001, “Preparation of colloidal calcium carbonate by carbonation process,” Ms thesis, Department of Chemical Engineering Graduate School, Kangwon National University, Korea.

[31] Siddarth, G., 2007, “Comparison of solid-State microwave annealing with conventional furnace annealing of ionimplanted SiC,” J. Electronic Materials, Vol. 36, No. 4, pp. 423-331.

[32] Zhao, C. and Vleugels, J., 2000, “Hybrid sintering with a tubular susceptor in a cylindrical single-mode microwave furnace,” Acta Mater, Vol. 48, pp. 3795-3801.

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