화학공학소재연구정보센터
Clean Technology, Vol.16, No.3, 220-228, September, 2010
Keggin형 헤테로폴리산에 의한 과당의 5-하이드록시메틸퍼퓨랄로의 전환을 위한 탈수반응
Dehydration Reaction of Fructose to 5-Hydroxymethylfurfural over Various Keggin-type Heteropolyacids
E-mail:
초록
과당(fructose)로부터 간단한 공정을 통하여 바이오디젤보다 우수한 청정에너지 연료로 알려진 5-하이드 록시메틸퍼퓨랄(HMF)을 제조하는 청정공정을 개발하였다. 이 연구에서는 중심원소와 배위원소가 치환된 네 종류의 헤테로폴리산 HnXM12O40 (중심원소 X = P, Si, 배위원소 M = W, Mo.)을 과당으로부터 HMF로 전환하는 탈수반응에 적용하고, 그 반응활성을 비교하였다. 헤테로폴리산의 산 세기는 중심원소가 P, 배위원소가 W일 때 더 높았으며 산 점의 수는 이와 반대되는 경향을 보였다. 과당의 HMF로의 탈수반응은 헤테로폴리산의 산 특성과 음이온의 연성(softness)과 밀접한 관련이 있으며, 촉매 활성점과 전환율이 상쇄 작용하여 네 종류의 헤테로폴리산 촉매는 서로 비슷한 활성을 보였다. 또한 반응에 사용된 헤테로폴리산을 반응온도보다 높은 200℃에서 열처리한 후에도 그 결정구조가 유지되는 것을 확인하였으며, 이를 통하여 헤테로폴리산의 반응활성이 안정적으로 유지됨을 확인할 수 있었다.
Four Keggin-type heteropolyacids, HnXM12O40(X = P and Si, M = W and Mo) that were substituted with heteroatom and polyatom were applied to the dehydration reaction of fructose to 5-hydroxymethylfurfural(HMF). The results showed that the acid became stronger when the heteroatom and polyatom were substituted with P and W than the cases of Si and Mo, respectively. However, the amount of acidic sites increased with the decrease in the acid strength, resulting in the change of the catalytic activity of heteropolyacids in the dehydration reaction. The experimental results revealed that four different heteropolyacids produced similar amounts of HMF via the dehydration reaction of fructose due to the counterbalancing effect between the amount of active sites, which is related to the catalytic activityof heteropolyacids, and the softness of polyanion. In addition, it was observed that the prepared heteropolyacids showed good structural stability after heat treatment at 200℃.
  1. Penner SS, Energy, 31(1), 33 (2006)
  2. Graboski MS, McCormick RL, Prog. Energy Combust. Sci., 24(2), 125 (1998)
  3. Farrell AE, Plevin RJ, Turner BT, Jones AD, O’Hare M, Kammen DM, Science., 311, 506 (2006)
  4. Demirbas A, Energy Sources Part A-Recovery Util. Environ. Eff., 32(16), 1490 (2010)
  5. Roman-Leshkov Y, Chheda JN, Dumesic JA, Science., 312, 1933 (2006)
  6. Roman-Leshkov Y, Barrett CJ, Liu ZY, Dumesic JA, Nature., 447, 982 (2007)
  7. Qi X, Watanabe M, Aida TM, Smith RL Jr, Green Chem., 10, 799 (2008)
  8. Musau RM, Munavu RM, Biomass., 13, 67 (1987)
  9. Seri K, Inoue Y, Ishida H, Bull. Chem. Soc. Jpn., 74, 1145 (2001)
  10. Zhao H, Holladay JE, Brown H, Zhang ZC, Science., 316, 1597 (2007)
  11. Jow J, Rorrer GL, Hawley MC, Biomass., 14, 185 (1987)
  12. Moreau C, Durand R, Razigade S, Duhamet J, Faugeras P, Rivalier P, Ros P, Avignon G, Appl. Catal. A: Gen., 145(1-2), 211 (1996)
  13. Qi XH, Watanabe M, Aida TM, Smith RL, Ind. Eng. Chem. Res., 47(23), 9234 (2008)
  14. Asghari FS, Yoshida H, Carbohydr. Res., 341, 2379 (2006)
  15. Carlini C, Patrono P, Galletti AMR, Sbrana G, Appl. Catal. A: Gen., 275(1-2), 111 (2004)
  16. Armaroli T, Busca G, Carlini C, Giuttari M, Galletti AMR, Sbrana G, J. Mol. Catal. A-Chem., 151(1-2), 233 (2000)
  17. Yan H, Yang Y, Tong D, Xiang X, Hu C, Catal. Commun., 10, 1558 (2009)
  18. Qi X, Watanabe M, Aida TM, Smith RL, Jr.,, Catal. Commun., 10, 1771 (2009)
  19. Shimizu KI, Uozumi R, Satsuma A, Catal. Commun., 10, 1849 (2009)
  20. Park GI, Barteau MA, Jung JC, Song IK, Korean Chem. Eng. Res., 47(2), 163 (2009)
  21. Kozhevnikov IV, Chem. Rev., 98(1), 171 (1998)
  22. Timofeeva MN, Appl. Catal. A: Gen., 256(1-2), 19 (2003)
  23. Dias AS, Pillinger M, Valente AA, Appl. Catal. A: Gen., 285(1-2), 126 (2005)
  24. Lee WY, Song IK, HWAHAK KONGHAK, 38(3), 317 (2000)
  25. Misono M, Catal. Rev. Sci. Eng., 29(2,3), 269 (1987)
  26. Kim H, Kim P, Lee KY, Yeom SH, Yi J, Song IK, Catal. Today, 111(3-4), 361 (2006)
  27. Kim H, Youn MH, Jung JC, Song IK, J. Mol. Catal. A-Chem., 252(1-2), 252 (2006)
  28. La KW, Jung JC, Kim H, Baeck SH, Song IK, J. Mol. Catal. A-Chem., 269(1-2), 41 (2007)
  29. Kim H, Jung JC, Song IK, Catal. Surv. Asia., 11, 114 (2007)
  30. Lee J, Kim H, La KW, Park DR, Jung JC, Lee SH, Song IK, Catal. Lett., 123(1-2), 90 (2008)
  31. Hong UG, Park DR, Park S, Seo JG, Bang Y, Hwang S, Youn MH, Song IK, Catal. Lett., 132(3-4), 377 (2009)
  32. Shimizu K, Furukawa H, Kobayashi N, Itaya Y, Satsuma A, Green Chem., 11, 1627 (2009)
  33. Wu HX, Zhou M, Qu YX, Li HX, Yin HB, Chin. J. Chem. Eng., 17(2), 200 (2009)
  34. Kozhevnikov IV, Catal. Rev.-Sci. Eng., 37(2), 311 (1995)
  35. Serwicka EM, Bruckman K, Haber J, Appl. Catal., 73, 153 (1991)
  36. Antal MJ, Mok WSL, Jr., Richards GN, Carbohydr. Res., 199, 91 (1990)
  37. Amarasekara AS, Williams LD, Ebede CC, Carbohydr. Res., 343, 3021 (2008)
  38. Bicker M, Kaiser D, Ott L, Vogel H, J. Supercrit. Fluids, 36(2), 118 (2005)
  39. Park DR, Lee SH, Lee J, Song SH, Kim H, Song JH, Song IK, Catal. Lett., 126(3-4), 308 (2008)
  40. Kozhevnikov IV, Catal. Rev.-Sci. Eng., 37(2), 311 (1995)
  41. Mioc UB, Dimitrijevic RZ, Davidovic M, Nedic ZP, Mitrovic MM, Colomban P, J. Mater. Sci., 29(14), 3705 (1994)
  42. Black JB, Clayden NJ, Gai PL, Scott JD, Serwicka EM, Goodenough JB, J. Catal., 106, 1 (1987)
  43. Xue J, Yin H, Li H, Zhang D, Jiang T, Yu L, Shen Y, Korean J. Chem. Eng., 26(3), 654 (2009)
  44. Marosi L, Platero EE, Cifre J, Arean CO, J. Mater. Chem., 10, 1949 (2000)