아세틴 촉매상에서 글리세롤로부터 디클로로프로판올의 직접 제조

송선호; 박동률; 우성율; 송원섭; 권명숙; 송인규; Sun Ho Song; Dong Ryu1 Park; Sung Yul Woo; Won Seob Song; Myong Suk Kwon; In Kyu Song

Clean Technology, Vol.15, No.1, 42-46, March, 2009

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아세틴 촉매상에서 글리세롤로부터 디클로로프로판올의 직접 제조

Direct Preparation of Dichloropropanol from Glycerol over Acetin Catalyst

송선호, 박동률, 우성율¹, 송원섭¹, 권명숙¹, 송인규 ^†

서울대학교 화학생물공학부, 151-744 서울시 관악구 관악로 599
¹(주)삼성정밀화학, 680-090 울산광역시 남구 여천동 190

Sun Ho Song, Dong Ryu1 Park, Sung Yul Woo¹, Won Seob Song¹, Myong Suk Kwon¹, and In Kyu Song^†

School of Chemical and Biological Engineering, Seoul National University, 599 Gwanak-ro, Gwanak-gu, Seoul 15 1-744, Korea
¹Samsung Fine Chemicals Corporation, 190 Yeochun-dong, Nam-gu, Ulsan 680-090, Korea

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초록

아세틴 촉매상에서 글리세롤(바이오디젤 제조과정의 부산물)과 염화수소 가스로부터 무용매 상태로 디클로로프로판올(DCP)을 직접 제조하는 반응을 기상-액상 회분식 반응기에서 수행하였다. 이를 위해 균일계 아세틴 촉매로 아세틴 혼합물(acetin mixture)과 트리아세틴을 사용하였다. 아세틴 촉매의 활성을 동일한 반응조건(110℃, 3 bar, 3시간)에서 수행된 무촉매 상태에서의 반응성과 비교하였다. 무촉매 반응에 비해 아세틴촉매를 사용한 반응에서 글리세롤의 전환율은 3%정도 증가하였으며 디클로로프로판올의 선택도는 50%가량 증가하였다. 또한 아세틴 혼합물보다는 트리아세틴의 촉매활성이 2% 정도 우수한 것으로 나타났다.

Solvent-free direct preparation of dichloropropanol (DCP) from glycerol (by-product of bio-diesel production) and hydrochloric acid gas was carried out over acetin catalyst in a gas-liquid batch reactor. For this purpose, acetin mixture and triacetin were used as a homogeneous acetin catalyst. Performance in the acetin-catalyzed reaction was compared to that in the non-catalytic reaction under the same reaction conditions (110℃, 3 bar, 3 h). Conversion of glycerol in the acetin-catalyzed reactions was ca. 3% higher than that in the non-catalytic reaction, and selectivity for dichloropropanol in the acetin-catalyzed reactions was ca. 50% higher than that in the non-catalytic reaction. It was also revealed that the catalytic performance of triacetin was ca. 2% higher than that of acetic mixture.

Keywords:글리세롤;디클로로프로판올;아세틴 촉매;염화수소;Glycerol;Dichloropropanol;Acetin catalyst;Hydrochloric acid

[References]

Bak YC, Choi JH, Kim SB, Kang DW, Korean J. Chem. Eng., 13(3), 242 (1996)
Gongalves VLC, Pinto BP, Silva JC, Mota CJA, Catal. Today, 133, 673 (2008)
Atia H, Armbmster U, Martin A, J. Catal., 258, 71 (2008)
Kubicek P, Sladek P, Buricova I, "Method of Preparing Dichloropropanols from Clycerine," PCT Patent W02005/021476 A1 (2005)
Balaraju M, Rekha V, Sai Prasad PS, Prabhavathi Devi BLA, Prasad RBN, Lingaiah N, Appl. Catal. A, 354, 82 (2009)
Pagliaro M, Ciriminna E, Kimura H, Rossi M, Pina CD, Angew. Chem. Int. Ed., 46, 2 (2007)
Lee SH, Park DR, Kim H, Lee J, Jung JC, Woo SY, Song WS, Kwon MS, Song IK, Catal. Commurn., 9, 1920 (2008)
Lee SH, Park DR, Kim H, Lee J, Jung JC, Park S, Cho KM, Song IK, React. Kinet. Catal. Lett., 94, 71 (2008)
Lee SH, Song SH, Park DR, Jung JC, Song JH, Woo SY, Song WS, Kwon MS, Song IK, Catal. Commum., 10, 160 (2008)
Nagato N, Mori H, Maki K, Ishioka R, "Process for Production of Epichlorohydrin," US Patent 4,634,784 (1987)
Bremus N, Dieckelmann G, Jeromin L, Rupilius W, Schiitt H, "Process for the Continuous Production of Triacetin," US Patent 228,452 (1981)
Ferreira P, Fonseca IM, Ramos AM, Vital J, Castanheiro JE, Catal. Commurn., 10, 481 (2009)

[Related Articles]

[1] Bak YC, Choi JH, Kim SB, Kang DW, Korean J. Chem. Eng., 13(3), 242 (1996)

[2] Gongalves VLC, Pinto BP, Silva JC, Mota CJA, Catal. Today, 133, 673 (2008)

[3] Atia H, Armbmster U, Martin A, J. Catal., 258, 71 (2008)

[4] Kubicek P, Sladek P, Buricova I, "Method of Preparing Dichloropropanols from Clycerine," PCT Patent W02005/021476 A1 (2005)

[5] Balaraju M, Rekha V, Sai Prasad PS, Prabhavathi Devi BLA, Prasad RBN, Lingaiah N, Appl. Catal. A, 354, 82 (2009)

[6] Pagliaro M, Ciriminna E, Kimura H, Rossi M, Pina CD, Angew. Chem. Int. Ed., 46, 2 (2007)

[7] Lee SH, Park DR, Kim H, Lee J, Jung JC, Woo SY, Song WS, Kwon MS, Song IK, Catal. Commurn., 9, 1920 (2008)

[8] Lee SH, Park DR, Kim H, Lee J, Jung JC, Park S, Cho KM, Song IK, React. Kinet. Catal. Lett., 94, 71 (2008)

[9] Lee SH, Song SH, Park DR, Jung JC, Song JH, Woo SY, Song WS, Kwon MS, Song IK, Catal. Commum., 10, 160 (2008)

[10] Nagato N, Mori H, Maki K, Ishioka R, "Process for Production of Epichlorohydrin," US Patent 4,634,784 (1987)

[11] Bremus N, Dieckelmann G, Jeromin L, Rupilius W, Schiitt H, "Process for the Continuous Production of Triacetin," US Patent 228,452 (1981)

[12] Ferreira P, Fonseca IM, Ramos AM, Vital J, Castanheiro JE, Catal. Commurn., 10, 481 (2009)