화학공학소재연구정보센터
Journal of the Korean Industrial and Engineering Chemistry, Vol.15, No.6, 581-593, October, 2004
산 촉매에서 n-부텐의 골격이성화반응
Skeletal Isomerization of n-Butene over Acid Catalysts
E-mail:
초록
FER 제올라이트를 촉매로 사용하여 n-부텐에서 이소부텐을 제조하는 골격이성화공정은 1993년에 상업화되었다. 여러 종류의 산 촉매가 검토되었으나 이소부텐 수율이 낮고 촉매의 활성저하가 빨라 개발이 지연되었다. 산점의 종류, 세기, 농도, 위치 및 세공의 크기, 모양, 용적 등이 골격이성화반응과 경쟁반응인 중합에 이은 분해반응에 미치는 영향을 고찰하여 이소부텐에 대한 선택성 결정 인자를 정리하였다. 골격이성화반응의 기구로 제안된 두분자, 단분자, 의사단분자 반응기구를 소개하고 실험결과와 연관지어 단분자 반응기구의 타당성을 고찰하였다. 골격이성화반응에 활성과 선택성이 높은 촉매의 탐색과 전망을 서술하였다.
Skeletal isomerization process producing isobutene from n-butene was commercialized by using FER zeolite in 1993. The low yield of isobutene and rapid deactivation of various acid catalysts were main causes for its late development. The competition of the skeletal isomerization and dimerization followed by cracking over acid catalysts was explained and the determining factors for the selectivity to isobutene were deduced from the variation of catalytic performance with the nature, intensity, concentration and location of acid sites and the size, shape and volume of pores of zeolite catalysts. Suggested mechanisms for the skeletal isomerization such as bimolecular, monomolecular and pseudo-monomolecular mechanism were interpreted and the validity of the monomolecular mechanism was discussed based on experimental results. The development and prospect of highly active and selective catalysts for the skeletal isomerization of n-butene were also described.
  1. EU Patent 501,577 A1 (1992)
  2. Mooiweer HH, Dejong KP, Kraushaar-Czarnetzki B, Stork WHJ, Krutzen BCH, Stud. Surf. Sci. Catal., 84, 2327 (1994)
  3. C&EN "Catalyst provides new route to isobutene", 30 (Oct. 25) (1993)
  4. Choudhary VR, Ind. Dev., 32 (1974)
  5. Butler AC, Nicolaides CP, Catal. Today, 18, 443 (1993) 
  6. Houzvicka J, Ponec V, Catal. Rev.-Sci. Eng., 39(4), 319 (1997)
  7. Meriaudeau P, Naccache C, Adv. Catal., 44, 505 (1999)
  8. Cejka J, Wichtelova B, Sarv P, Appl. Catal. A: Gen., 179, 217 (1999) 
  9. Domokos L, Lefferts L, Seshan K, Lercher JA, J. Catal., 197(1), 68 (2001) 
  10. Houzvicka J, Skeletal isomerization of n-butene, Ph.D. dissertation, Leiden Univ., Nethelands (1998)
  11. Meriaudeau P, Tuan VA, Hung LN, Naccache C, Szabo G, J. Catal., 171, 329 (1997) 
  12. Seo G, Kim MY, Kim JH, Catal. Lett., 67(2-4), 207 (2000)
  13. Lee TH, Baeck SH, Lee WY, HWAHAK KONGHAK, 35(3), 451 (1997)
  14. Benitez VM, Querini CA, Figoli NS, Comelli RA, Appl. Catal. A: Gen., 178(2), 205 (1999) 
  15. Lopez-Salinas E, Hernandez-Cortez JG, Cortes-Jacome MA, Navarrete J, Llanos ME, Vazquez A, Armendariz H, Lopez T, Appl. Catal. A: Gen., 175(1-2), 43 (1998) 
  16. Onyestyak GY, Valyon J, Pal-Borbely G, Rees CVC, Appl. Catal. A: Gen., 196, 401 (2002)
  17. Seo G, Kim MW, Kim JH, Ahn BJ, Hong SB, Uh YS, Catal. Lett., 55(2), 105 (1998) 
  18. Canizares P, Carrero A, Sanchez P, Appl. Catal. A: Gen., 190(1-2), 93 (2000) 
  19. Seo G, Kim NH, Lee YH, Kim JH, Catal. Lett., 57(4), 209 (1999) 
  20. Asensi MA, Martinez A, Appl. Catal. A: Gen., 183(1), 155 (1999) 
  21. Stepanov AG, Luzgin MV, Arzumanov SS, Ernst H, Freude D, J. Catal., 211(1), 165 (2002)
  22. Seo G, Kim NH, Lee YH, Kim JH, Catal. Lett., 51(1-2), 101 (1998)
  23. Seo G, Jeong HS, Lee JM, Ahn BJ, Stud. Surf. Sci. Catal., 150, 1431 (1997)
  24. Seo G, Jeong HS, Jang DL, Cho DL, Hong SB, Catal. Lett., 41(3-4), 189 (1996) 
  25. Meunier FC, Domokos L, Seshan K, Lercher JA, J. Catal., 211(2), 366 (2002)
  26. Lee SH, Shin CH, Hong SB, J. Catal., 223(1), 200 (2004) 
  27. Onyestyak G, Pal-Borbely G, Rees LVC, Microporous Mesoporous Mater., 43, 73 (2001) 
  28. Nicolaides CP, Appl. Catal. A: Gen., 185(2), 211 (1999) 
  29. Wichterlova B, Zilkova N, Uvarova E, Cejka J, Sarv P, Paganini C, Lercher JA, Appl. Catal. A: Gen., 182(2), 297 (1999) 
  30. Baeck SH, Lee WY, Appl. Catal. A: Gen., 164(1-2), 291 (1997) 
  31. Houzvicka J, Nienhuis JG, Ponec V, Appl. Catal. A: Gen., 174(1-2), 207 (1998) 
  32. vandank S, Bus E, Broersma A, Bitter JH, dejong KP, Stud. Surf. Sci. Catal., 142, 573 (2002)
  33. Ferreira ML, Rueda EH, J. Mol. Catal., 178, 147 (2002) 
  34. Domokos L, Lefferts L, Seshan K, Lercher JA, J. Mol. Catal. A-Chem., 162, 147 (2000) 
  35. Kwak BS, Sung J, Catal. Lett., 53(1-2), 125 (1998)
  36. Byggningsbacka R, Kumar N, Lindfors LE, J. Catal., 178(2), 611 (1998) 
  37. Andy P, Martin D, Guisnet M, Bell RG, Catlow CRA, J. Phys. Chem. B, 104(20), 4827 (2000) 
  38. Ivanov P, Papp H, Appl. Surf. Sci., 179, 234 (2001) 
  39. Rutenbeck D, Papp H, Freude D, Schwieger W, Appl. Catal. A: Gen., 206(1), 57 (2001) 
  40. Philippou A, Dwyer J, Ghanbari-siahkali A, Paze C, Anderson MW, J. Mol. Catal. A-Chem., 174, 223 (2001) 
  41. Rutenbeck D, Papp H, Ernst H, Schwieger W, Appl. Catal. A: Gen., 208(1-2), 153 (2001) 
  42. Jeong HS, Skeletal isomerization of 1-butene over ferrierite catalyst, Ph.D. Dissertation, Chonnam National Univ. Gwangju Korea (1997)
  43. Kim NH, Kim JH, Seo G, HWAHAK KONGHAK, 36(4), 571 (1998)
  44. Seo G, Park SH, Kim JH, Catal. Today, 44(1-4), 215 (1998) 
  45. Andy P, Gnep NS, Guisnet M, Benazzi E, Travers C, J. Catal., 173(2), 322 (1998) 
  46. Guisnet M, J. Mol. Catal. A-Chem., 182, 67 (2002)
  47. Petkovic LM, Larsen G, J. Catal., 191(1), 1 (2000) 
  48. Houzvicka J, Hansildaar S, Nienhuis JG, Ponec V, Appl. Catal. A: Gen., 176(1), 83 (1999) 
  49. van Donk S, Bus E, Broersma A, Bitter JH, de Jong KR, J. Catal., 212(1), 86 (2002) 
  50. Woo HC, Lee KH, Lee JS, Appl. Catal. A: Gen., 134(1), 147 (1996) 
  51. Lee HC, Woo HC, Ryoo R, Lee KH, Lee JS, Appl. Catal. A: Gen., 196(1), 135 (2000) 
  52. Lee HC, Woo HC, Chung SH, Kim HJ, Lee KH, Lee JS, J. Catal., 211(1), 216 (2002)
  53. Baeck SH, Lee WY, Appl. Catal. A: Gen., 168(1), 171 (1998) 
  54. Byggningsbacka R, Kumar N, Lindfors LE, Catal. Lett., 58(4), 231 (1999) 
  55. Thoma SG, Trudell DE, Bonhomme F, Nenoff TM, Microporous Mesoporous Mater., 50, 33 (2001) 
  56. Asensi MA, Camblor MA, Martinez A, Microporous Mesoporous Mater., 28, 427 (1999) 
  57. Lee SH, Lee DK, Shin CH, Park YK, Wright PA, Lee WM, Hong SB, J. Catal., 215(1), 151 (2003) 
  58. Tian H, Li C, J. Mol. Catal. A-Chem., 149, 205 (1999) 
  59. Nieminen V, Kumar N, Heikkila T, Laine E, Villegas J, Salmi T, Yu D, Appl. Catal. A: Gen., 259, 227 (2004) 
  60. Yang SM, Lin JY, Guo DH, Liaw SG, Appl. Catal. A: Gen., 181(1), 113 (1999) 
  61. Sun Q, Gao ZX, Wen B, Sachtler WMH, Catal. Lett., 78(1-4), 1 (2002)
  62. Moreno-Castilla C, Maldonado-Hodar FJ, Rivera-Utrilla J, Rodriguez-Castellon E, Appl. Catal. A: Gen., 183(2), 345 (1999) 
  63. Alvarez-Merino MA, Carrasco-Marin F, Moreno-Castilla C, J. Catal., 192(2), 374 (2000) 
  64. Benitez VM, Querini CA, Figoli NS, Appl. Catal. A: Gen., 252(2), 427 (2003) 
  65. Benitez VM, Figoli NS, Catal. Commun., 4, 571 (2003) 
  66. Morenocastilla C, Perezcadenas AF, Maldonadohodar FJ, Carrascomarin F, Carbon, 41, 866 (2003)
  67. Finelli ZR, Querini CA, Figoli NS, Comelli RA, Appl. Catal. A: Gen., 216(1-2), 91 (2001) 
  68. Finelli ZR, Querini CA, Comelli RA, Appl. Catal. A: Gen., 247(1), 143 (2003) 
  69. Kim JG, J. Korean Ind. Eng. Chem., 7(5), 861 (1996)
  70. Kim JG, J. Korean Ind. Eng. Chem., 8(2), 191 (1997)
  71. Kim WG, Kim MW, Kim JH, Seo G, Microporous Mesoporous Mater., 57, 113 (2003) 
  72. Seo G, Jeong HS, Hong SB, Uh YS, Catal. Lett., 36(3-4), 249 (1996) 
  73. Davis RJ, J. Catal., 216(1-2), 396 (2003) 
  74. Hong SS, Woo HC, Lee GD, J. Korean Ind. Eng. Chem., 7(5), 902 (1996)
  75. Wu Z, Wang Q, Xu L, Xie S, Stud. Surf. Sci. Catal., 142, 747 (2002)