글리세롤과 요소로부터 글리세롤카보네이트 합성에서 이온성액체의 촉매 특성

김동우; 박경아; 김민지; 박대원; Dong-Woo Kim; Kyung-Ah Park; Min-Ji Kim; Dae-Won Park

Korean Chemical Engineering Research, Vol.51, No.3, 347-351, June, 2013

Export Citation

글리세롤과 요소로부터 글리세롤카보네이트 합성에서 이온성액체의 촉매 특성

Catalytic Performance of Ionic Liquids in the Synthesis of Glycerol Carbonate from Glycerol and Urea

김동우, 박경아, 김민지, 박대원 ^†

부산대학교 화공생명공학부, 609-735 부산광역시 금정구 장전동 산 30번지

Dong-Woo Kim, Kyung-Ah Park, Min-Ji Kim, and Dae-Won Park^†

School of Chemical and Biomolecular Engineering, Pusan National University, San 30 Jangjun-dong, Gumjeong-gu, Busan 609-735, Korea

E-mail:

초록

글리세롤과 요소의 카르보닐화 반응에 의한 글리세롤카보네이트(GC)의 제조반응에 대하여 이온성 액체 촉매의 특성을 조사한 결과 사용된 4급암모늄염 촉매와 이미다졸염 촉매의 알킬기의 길이가 짧을수록, 할로겐 음이온의 친핵성이 클수록 촉매의 활성은 증가하였다. TBAC 촉매에 대해서 반응변수인 반응온도, 반응시간, 진공도가 반응에 미치는 영향을 고찰하였다. ZnCl2를 조촉매로 사용한 경우 각각 촉매의 활성보다 더 높은 활성을 나타내어 시너지 효과가 관찰되었으며, 이것은 혼합촉매의 산-염기적 특성에 기인하는 것으로 판단된다.

The preparation of glycerol carbonate (GC) from urea through carbonylation with renewable glycerol was investigated by using ionic liquid catalysts. It was found that quaternary ammonium salt and imidazolium salt ionic liquids with a shorter alkyl chain length and higher nucleophilic anion showed better catalytic performance. The effects of reaction temperature, reaction time and degree of vacuum on the reactivity of TBAC catalyst ware discussed. Zinc chloride (ZnCl2) was used as co-catalyst with the ionic liquid catalyst. The mixed catalyst showed a synergy effect on the glycerol conversion and GC yield probably due to the acid-base properties of the catalysts.

Keywords:Glycerol;Urea;Glycerol Carbonate;Ionic Liquid Catalyst

[References]

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Zhang Y, Zhang N, Tang ZR, Xu YJ, Chem. Sci., 4, 1820 (2013)
Behr A, Eilting J, Irawadi K, Leschinski J, Lindner F, Green Chem., 10, 13 (2008)
Aresta M, Dibenedetto A, Nocito F, Ferragina C, J. Catal., 268(1), 106 (2009)
Randall D, De VR, “Chemical Blowing Agent,” E.U. Patent, EP419114 (1991)
Sonnati MO, Amigoni S, Givenchy EPTD, Darmanin T, Choulet O, Guittard F, Green Chem., 15, 283 (2013)
Mittelbach M, Remschmidt C, “Biodiesel-The Comprehensive Handbook,” Graz, Austria (2004)
Plasma V, Caulier T, Boulos N, Plast. Addit.Compd., 7(2), 30 (2005)
Zhou CH, Beltramini JN, Fan YX, Lu GQ, Chem. Soc. Rev., 37, 527 (2008)
Simao AC, Pukleviciene BL, Rousseau C, Tatibouet A, Cassel S, Sackus A, Rauter AP, Rollin P, Lett. Org. Chem., 3, 744 (2006)
Clements JH, Ind. Eng. Chem. Res., US663-674, 42 (2003)
Teles JH, Rieber, N. and Harder, W., “Preparation of Glycerol Carbonate,” U.S. Patent, 5359094 (1994)
Dibenedetto A, Pastore C, Aresta M, Catal. Today, 115(1-4), 88 (2006)
Vieville C, Yoo JW, Pelet S, Mouloungui Z, Catal. Lett., 56(4), 245 (1998)
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Climent MJ, Corma A, De Frutos P, Iborra S, Noy M, Velty A, Concepcion P, J. Catal., 269(1), 140 (2010)
Ceri H, Jose ALS, Mohd HAR, Nikolaos D, Robert LJ, Albert FC, Qian H, Christopher JK, David WK, Graham JH, Dalton Trans., 40, 3927 (2011)
Sheldon R, Chem. Commun., 2399 (2001)
Zhao DB, Wu M, Kou Y, Min E, Catal. Today, 74(1-2), 157 (2002)
Wasserscheid P, Keim W, Angew. Chem. Int. Ed., 39(21), 3772 (2000)
Dupont J, de Souza RF, Suarez PAZ, Chem. Rev., 102(10), 3667 (2002)
Marsh KN, Deev A, Wu ACT, Tran E, Klamt A, Korean J. Chem. Eng., 19(3), 357 (2002)
Song CE, Shim WH, Roh EJ, Choi JH, Chem. Commun., 1695 (2000)
Mun NY, Kim KH, Park DW, Choe Y, Kim I, Korean J. Chem. Eng., 22(4), 556 (2005)
Lee EH, Cha SW, Dharma MM, Choe Y, Ahn JY, Park DW, Korean J. Chem. Eng., 24(3), 547 (2007)
Manju MD, Ahn JY, Lee MK, Shim HL, Kim KH, Kim I, Park DW, Green Chem., 10(6), 678 (2008)
Peter B, Heinz F, Walter H, Angew. Chem., Int. Ed. Engl., 19, 718 (1980)
Udaya SU, Park SW, Park DW, Choi BS, Catal. Commun., 9, 1563 (2008)

[Referenced By]

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[1] Pagliaro M, Ciriminna R, Kimura H, Rossi M, Pina CD, Angew. Chem. Int. Ed., 46, 4434 (2007)

[2] Zhang Y, Zhang N, Tang ZR, Xu YJ, Chem. Sci., 4, 1820 (2013)

[3] Behr A, Eilting J, Irawadi K, Leschinski J, Lindner F, Green Chem., 10, 13 (2008)

[4] Aresta M, Dibenedetto A, Nocito F, Ferragina C, J. Catal., 268(1), 106 (2009)

[5] Randall D, De VR, “Chemical Blowing Agent,” E.U. Patent, EP419114 (1991)

[6] Sonnati MO, Amigoni S, Givenchy EPTD, Darmanin T, Choulet O, Guittard F, Green Chem., 15, 283 (2013)

[7] Mittelbach M, Remschmidt C, “Biodiesel-The Comprehensive Handbook,” Graz, Austria (2004)

[8] Plasma V, Caulier T, Boulos N, Plast. Addit.Compd., 7(2), 30 (2005)

[9] Zhou CH, Beltramini JN, Fan YX, Lu GQ, Chem. Soc. Rev., 37, 527 (2008)

[10] Simao AC, Pukleviciene BL, Rousseau C, Tatibouet A, Cassel S, Sackus A, Rauter AP, Rollin P, Lett. Org. Chem., 3, 744 (2006)

[11] Clements JH, Ind. Eng. Chem. Res., US663-674, 42 (2003)

[12] Teles JH, Rieber, N. and Harder, W., “Preparation of Glycerol Carbonate,” U.S. Patent, 5359094 (1994)

[13] Dibenedetto A, Pastore C, Aresta M, Catal. Today, 115(1-4), 88 (2006)

[14] Vieville C, Yoo JW, Pelet S, Mouloungui Z, Catal. Lett., 56(4), 245 (1998)

[15] Mouloungui Z, Yoo JW, Gachen CA, Gaset A, “Process for the Preparation of Glycerol Carbonate from Glycerol and a Cyclic Organic Carbonate, Especially Ethylene or Propylene Carbonate,” E.U. Patent, EP0739888 (1996)

[16] Climent MJ, Corma A, De Frutos P, Iborra S, Noy M, Velty A, Concepcion P, J. Catal., 269(1), 140 (2010)

[17] Ceri H, Jose ALS, Mohd HAR, Nikolaos D, Robert LJ, Albert FC, Qian H, Christopher JK, David WK, Graham JH, Dalton Trans., 40, 3927 (2011)

[18] Sheldon R, Chem. Commun., 2399 (2001)

[19] Zhao DB, Wu M, Kou Y, Min E, Catal. Today, 74(1-2), 157 (2002)

[20] Wasserscheid P, Keim W, Angew. Chem. Int. Ed., 39(21), 3772 (2000)

[21] Dupont J, de Souza RF, Suarez PAZ, Chem. Rev., 102(10), 3667 (2002)

[22] Marsh KN, Deev A, Wu ACT, Tran E, Klamt A, Korean J. Chem. Eng., 19(3), 357 (2002)

[23] Song CE, Shim WH, Roh EJ, Choi JH, Chem. Commun., 1695 (2000)

[24] Mun NY, Kim KH, Park DW, Choe Y, Kim I, Korean J. Chem. Eng., 22(4), 556 (2005)

[25] Lee EH, Cha SW, Dharma MM, Choe Y, Ahn JY, Park DW, Korean J. Chem. Eng., 24(3), 547 (2007)

[26] Manju MD, Ahn JY, Lee MK, Shim HL, Kim KH, Kim I, Park DW, Green Chem., 10(6), 678 (2008)

[27] Peter B, Heinz F, Walter H, Angew. Chem., Int. Ed. Engl., 19, 718 (1980)

[28] Udaya SU, Park SW, Park DW, Choi BS, Catal. Commun., 9, 1563 (2008)