냉각에 의한 용액결정화에서 용매선정

김광주; 곽원식; 박소진; Kwang-Joo Kim; Won-Sik Gwak; So-Jin Park

Journal of the Korean Industrial and Engineering Chemistry, Vol.15, No.1, 86-91, February, 2004

Export Citation

냉각에 의한 용액결정화에서 용매선정

Selection of Solvents for Cooling Crystallization in Solution

김광주 ^†, 곽원식, 박소진 ¹

한국화학연구원 미세공정기술연구센터 결정화공정실험실, 대전 305-600
¹충남대학교 공과대학 화학공학과, 대전 305-764

Kwang-Joo Kim^†, Won-Sik Gwak, and So-Jin Park¹

Crystallization Process & Engineering Lab., Fine Chemical Process & Engineering Center, Korea Research Institute of Chemical Technology, Daejeon 305-600, Korea
¹Department of Chem. Eng., Chungnam National University, Daejeon 305-764, Korea

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초록

Retinol 중간체인 C₁₅ sulfone의 냉각에 의한 용액결정화에서 적합한 용매 선정을 위한 연구가 수행되었다. 결정크기, 형상 및 수율에 미치는 용해도, 용해도 매개변수, 준안정영역의 넓이, 온도의 의존성과 혼합열의 영향이 고려되었다. C₁₅ sulfone에 대한 용해도의 온도 의존성은 methanol > ethanol > heptane > hexane > ethyl acetate > acetone > DMF > toluene > dichloromethane > THF 이었으며 용질의 용해도 매개변수 값과 차이가 큰 용매에서 큼을 알 수 있었다. 용해도와 준안정영역은 C₁₅ sulfone의 용해도 매개변수 값과 유사한 용매에서 최대였다. 입도는 준안정영역의 넓이가 증가함에 따라 감소하였다. 입자 형상은 C₁₅ sulfone의 용해도 매개변수 값과 차이가 큰 용매에서 긴 침상형을 보였다. 냉각결정화에 의한 C₁₅ sulfone을 분리정제하기 위해 알맞은 용매는 hexane이었다.

Selection of solvent for the cooling crystallization of a retinol intermediate like C₁₅ sulfone was explored. Effects of solubility, solubility parameter, metastable zone width, temperature and heat of mixing on yield, and crystal size and crystal shape were investigated for various solvents. The temperature dependence of C₁₅ sulfone on solubilities was in the order of methanol > ethanol > heptane > hexane > ethyl acetate > acetone > DMF > toluene > dichloromethane > THF, which depended on the difference between solvent parameters of solute and solvent. Solubility and metastable zone width were the highest when solubility parameter of solvent was similar to that of C₁₅ sulfone. The wider metastable zone width leaded to the larger crystal size. The higher difference between solubility parameters of C₁₅ sulfone and solvents leaded to the higher aspect ratio of needle-like crystals. Eventually, hexane was an appropriate solvent in cooling crystallization of C₁₅ sulfone.

Keywords:solubility parameter;solution crystallization;selection of solvent

[References]

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Mersmann A, Crystallization Technology Handbook, Marcel Dekker, Inc., New York (1994)
Kim KJ, Kim MJ, Lee JM, Kim SH, Kim HS, Park BS, J. Chem. Eng. Data, 43(1), 65 (1998)
Kim KJ, Lee CH, Ryu SK, Ind. Eng. Chem. Res., 33(1), 118 (1994)
Kim KJ, Lee CH, Ryu SK, J. Chem. Eng. Data, 39(2), 228 (1994)
Barton AF, CRC Handbook of Solubility Parameters and other Cohesion Parameters, CRC Press, Florida (1983)
Kolar P, Shen JW, Tsuboi A, Ishikawa T, Fluid Phase Equilib., 194, 771 (2002)
Arce A, Blanco M, Soto A, Fluid Phase Equilib., 146(1-2), 161 (1998)
Roy SD, Flynn GL, Pharm. Res., 5(9), 580 (1998)
Kim KJ, Kim KM, Lee JM, Han MW, Kim HS, Park BS, J. Korean Ind. Eng. Chem., 11(5), 546 (2000)
김광주, 한국공업화학회, 4(4), 1 (2001)

[Related Articles]

[1] Oliver J, Palou A, J. Chromatogr. A, 881, 543 (2000)

[2] http://www.medcity.com/chat/shop/vitamin/vitamina.html

[3] 박영훈, 서원택, 김선원, 베타-카로텐의 생산방법, 대한민국 특허 43270 (1998)

[4] Manchand PS, Rosenberger M, Saucy G, Wehril PA, Wong H, Chambers L, Ferro MP, Jackson W, Helv. Chim. Acta, 59, 43 (1976)

[5] vandenBerg EPG, Greertman RM, Bennema P, 12th Symposium on Industrial Crystallization Proceedings, Warsaw, Poland, 3 (1993)

[6] terHorst JH, Geertman RM, vanderHeijden AE, vanRosmalen GM, Proceedings of 13th Symposium on Industrial Crystallization, Toulouse, France, 1 (1996)

[7] Mersmann A, Crystallization Technology Handbook, Marcel Dekker, Inc., New York (1994)

[8] Kim KJ, Kim MJ, Lee JM, Kim SH, Kim HS, Park BS, J. Chem. Eng. Data, 43(1), 65 (1998)

[9] Kim KJ, Lee CH, Ryu SK, Ind. Eng. Chem. Res., 33(1), 118 (1994)

[10] Kim KJ, Lee CH, Ryu SK, J. Chem. Eng. Data, 39(2), 228 (1994)

[11] Barton AF, CRC Handbook of Solubility Parameters and other Cohesion Parameters, CRC Press, Florida (1983)

[12] Kolar P, Shen JW, Tsuboi A, Ishikawa T, Fluid Phase Equilib., 194, 771 (2002)

[13] Arce A, Blanco M, Soto A, Fluid Phase Equilib., 146(1-2), 161 (1998)

[14] Roy SD, Flynn GL, Pharm. Res., 5(9), 580 (1998)

[15] Kim KJ, Kim KM, Lee JM, Han MW, Kim HS, Park BS, J. Korean Ind. Eng. Chem., 11(5), 546 (2000)

[16] 김광주, 한국공업화학회, 4(4), 1 (2001)