화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Journal of Industrial and Engineering Chemistry, Vol.88, 167-177, August, 2020
DOI10.1016/j.jiec.2020.04.009  Export Citation
Synthesis of hierarchical Y and ZSM-5 zeolites using post-treatment approach to maximize catalytic cracking performance
Amin Talebian-Kiakalaieh, and Sara Tarighi†
  • Faculty of Petrochemicals, Iran Polymer and Petrochemical Institute (IPPI), P.O. Box 14975-112, Tehran, Iran
E-mail:
Hierarchical zeolites have been recently investigated as catalyst by micro-mesoporous framework to improve the physical transport of large reactants molecules by eliminating the diffusion limitations. In this study, controlled mesoporosity was applied to synthesize two types of hierarchical zeolites by acid/ base leaching and surfactant templating followed by steaming. The physico-chemical characteristics of the synthesized parent (NaY and ZSM-5) and hierarchical (UHR/Y and HR/ZSM-5) samples were extensively characterized by XRD, FTIR, TGA, SEM, NH3-TPD, ICP, N2-ads/desorption techniques. The ICP results revealed that post-synthesis approaches successfully washed off Al and Si atoms from the zeolites framework and increased the SiO2/Al2O3 ratios from 3.13 to 6.20 and from 65.55 to 86.34 in UHR/Y and HR/ZSM-5 samples, respectively. Also, the BET analysis showed significant increase in the average pore diameter (DP) size for UHR/Y (31%) and HR/ZSM-5 (153%) compared to their parent ones. Similarly, mesoporous pore volume (Vmeso) exhibited notable surge of 100% and 700% for UHR/Y and HR/ZSM-5, respectively in comparison with their parent forms. The synthesized parent and hierarchical zeolites were used in preparation of fluid catalytic cracking (FCC) catalyst. Catalyst performance was examined in vacuum gas oil (VGO) cracking through a micro-activity test (MAT) unit. Products of interest including gasoline, propylene, and total olefins exhibited significant yield increase from 29.80 to 50.87, 3.93 to 16.41, and 7.36 to 24.98 wt%, respectively over the FCC-4 catalysts which prepared by hierarchical (UHR/Y and HR/ZSM-5) zeolites. The enhanced catalytic activity can be attributed to the absence of diffusion problems and more accessibility of the acid sites in the hierarchical zeolite structure.
Keywords:Hierarchical zeolite;Catalytic cracking;Surfactant templating;Acid/base leaching;Propylene;Gasoline
  1. Ertl G, Knozinger H, Schuth F, Weitkamp J, Handbook of Heterogeneous Catalysis, 2nd ed., Wiley-VCH, Weinheim, Germany, 2008.
  2. Roth WJ, Kubicka D, Cejka J, The Royal Society of Chemistry, Cambridge, United Kingdom, pp.77 2015.
  3. Primo A, Garcia H, Chem. Soc. Rev., 43, 7548 (2014)
  4. Na K, Choi M, Ryoo R, Microporous Mesoporous Mater., 166, 3 (2013)
  5. Ahmed MHM, Muraza O, Nakaoka S, Jamil AK, Mayoral A, Sebastian V, Yamani ZH, Masuda T, Energy Fuel (2017).
  6. Yue Y, Guo X, Liu T, Liu H, Wang T, Yuan P, Zhu H, Bai Z, Bao X, Microporous Mesoporous Mater. (2019).
  7. Carati A, Montanari E, Zanardi S, Millini R, Bellussi G, Appl. Catal. A: Gen., 504, 171 (2015)
  8. Kasneryk VI, Shamzhy MV, Opanasenko MV, J. Energy Chem., 25, 318 (2016)
  9. Zecevic J, Gommes CJ, Friedrich H, de Jongh PE, de Jong KP, Angew. Chem.-Int. Edit., 51, 4213 (2012)
  10. Corma A, Dıaz-Cabanas MJ, Martınez-Triguero J, Rey F, Rius J, Nature, 418, 514 (2002)
  11. Sun J, Bonneau C, Cantın C, Corma A, Dıaz-Cabana MJ, Moliner M, Zhang D, Li M, Zou X, Nature, 458, 1154 (2009)
  12. Corma A, Dıaz-Cabanas MJ, Jiang J, Afeworki M, Dorset DL, Soled SL, Strohmaier KG, Proc. Natl. Acad. Sci. U.S.A., 107, 13997 (2010)
  13. Zhao DY, Feng JL, Huo QS, Melosh N, Fredrickson GH, Chmelka BF, Stucky GD, Science, 279(5350), 548 (1998)
  14. Corma A, Daz-Cabacas MJ, Martnez-Triguero J, Rey F, Rius J, Nature, 418, 514 (2002)
  15. Wang X, Gao X, Dong M, Zhao H, Huang W, J. Energy Chem., 24, 490 (2015)
  16. Vuong GT, Hoang VT, Nguyen DT, Do TO, Appl. Catal. A: Gen., 382(2), 231 (2010)
  17. Prech J, Pizarro P, Serrano DP, Chem. Soc. Rev., 47, 8263 (2018)
  18. Groen JC, Zhu WD, Brouwer S, Huynink SJ, Kapteijn F, Moulijn JA, Perez-Ramirez J, J. Am. Chem. Soc., 129(2), 355 (2007)
  19. Feliczak-Guzik A, Microporous Mesoporous Mater., 259, 33 (2018)
  20. Garcia-Martinez J, Johnson M, Valla J, Li K, Ying JY, Catal. Sci. Technol., 2, 987 (2012)
  21. Valtchev V, Majano G, Mintova S, Perez-Ramirez J, Chem. Soc. Rev., 42, 263 (2013)
  22. Lutz W, Shutilov RA, Gavrilov VY, Anorg Z, Allg. Chem., 640, 577 (2014)
  23. Ibarra A, Hita I, Azkoiti MJ, Arandes JM, Bilbao J, J. Ind. Eng. Chem., 78, 372 (2019)
  24. Agudelo JL, Mezari B, Hensen EJM, Giraldo SA, Hoyos LJ, Appl. Catal. A: Gen., 488, 219 (2014)
  25. Ahmed MHM, Muraza O, Al-Amer AM, Miyake K, Nishiyama N, Appl. Catal. A: Gen., 497, 127 (2015)
  26. Tangale NP, Sonar SK, Niphadkar PS, Joshi PN, J. Ind. Eng. Chem., 40, 128 (2016)
  27. Qiao K, Shi X, Zhou F, Chen H, Fu J, Ma HX, Huang H, Appl. Catal. A: Gen., 547, 274 (2017)
  28. Liu Z, Liu L, Song H, Wang C, Xing W, Komarneni S, Mater. Lett., 154, 116 (2015)
  29. Kim MY, Lee K, Choi M, J. Catal., 319, 232 (2014)
  30. White RJ, Fischer A, Goebel C, Thomas A, J. Am. Chem. Soc., 136(7), 2715 (2014)
  31. Jiao WQ, Fu WH, Liang XM, Wang YM, He MY, RSC Adv., 4, 58596 (2014)
  32. Talebian-Kiakalaieh A, Tarighi S, J. Ind. Eng. Chem., 79, 452 (2019)
  33. Kore R, Srivastava R, Satpati B, Appl. Catal. A: Gen., 493, 129 (2015)
  34. Guo D, Shen B, Qin Y, Sun J, Guo Q, Ren FS, Microporous Mesoporous Mater., 211, 192 (2015)
  35. Holtzclaw H, Inorganic Synthesis, vol. 8l, McGraw-Hill, NewYork, 1966.
  36. Hussain AI, Aitani AM, Kubu M, Cejka J, Al-Khattaf S, Fuel, 167, 226 (2016)
  37. Garcia JR, Falco M, Sedran U, Catal. Today, 296, 247 (2017)
  38. Garcia JR, Falco M, Sedran U, Top. Catal., 59, 268 (2016)
  39. Mante OD, Agblevor FA, Oyama ST, McClung R, Appl. Catal. A: Gen., 445-446, 312 (2012)
  40. Wallenstein D, Kanz B, Haas A, Appl. Catal. A: Gen., 192(1), 105 (2000)
  41. Feng R, Yan X, Hu X, Qiao K, Yan Z, Rood MJ, Microporous Mesoporous Mater., 243, 319 (2017)
  42. Rodriguez E, Elordi G, Valecillos J, Izaddoust S, Bilbao J, Arandes JM, Castano P, Fuel Proc. Technol., 192, 130 (2019)
  43. Chen WZ, Han DM, Sun XH, Li CY, Fuel, 106, 498 (2013)
  44. den Hollander MA, Wissink M, Makkee M, Moulijn JA, Appl. Catal. A: Gen., 223(1-2), 85 (2002)
  45. Awayssa O, Al-Yassir N, Aitani A, Al-Khattaf S, Appl. Catal. A: Gen., 477, 172 (2014)
  46. Ebrahimi AA, Tarighi S, Pet. Sci. Technol., 33, 415 (2015)
  47. Bastiani R, Lam YL, Henriques CA, da Silva VT, Fuel, 107, 680 (2013)
  48. Bellussi G, Perego G, Carati A, Gomaro U, Fatore V, Innovation in Material Science, Elsevier, Amsterdam, 1988.
  49. Xia B, Cao L, Luo K, Zhao L, Wang X, Gao J, Xu C, Energy Fuel (2019).
  50. Itoh T, U.S. Patent No. 6, 214,211 (U.S. Patent and Trademark Ofce, Washington, DC, 2001).
  51. Stamires D, O’connor P, Laheij EJ, Vadovic C, U.S. Patent No. 9,381,502 (U.S. Patent and Trade-mark Ofce, Washington, DC, 2016).
  52. Ebrahimi A, Tarighi S, Ani A, Kinet. Catal., 57, 610 (2016)
  53. He L, Zheng A, Ren S, Yu HK, Zhang JC, Petrol. Chem., 57, 60 (2017)
  54. Etim UJ, Xu BJ, Zhang Z, Zhong ZY, Bai P, Qiao K, Yan ZF, Fuel, 178, 243 (2016)
  55. Mohamed RM, Mkhalid LA, Barakat MA, Arab. J. Chem., 8, 48 (2015)
  56. Ding J, Liu H, Yuan P, Shi G, Bao X, Chem. Cat. Chem. (2013).
  57. Li HY, Wang YQ, Fan CY, Sun C, Wang X, Wang C, Zhang X, Wang SH, Appl. Catal. A: Gen., 551, 34 (2018)
  58. Medeiros-Costa IC, Laroche C, Perez-Pellitero J, Coasne B, Microporous Mesoporous Mater., 287, 167 (2019)
  59. Shi Y, Li X, Hu J, Lu J, Ma Y, Zhang Y, J. Mater. Chem., 21, 16223 (2011)
  60. Ferreira C, Araujo A, Calvino-Casilda V, Cutrufello MG, Rombi E, Fonseca AM, Microporous Mesoporous Mater., 271, 243 (2018)
  61. Miao P, Li K, Fan J, Xu N, Zhu X, Li C, Energy Fuel (2019).
  62. Tonetto GM, Ferreira ML, Atias JA, de Lasa HI, AlChE J., 52, 754 (2006)
  63. Feliczak-Guzik A, Sprynskyy M, Nowak I, Buszewski B, Microporous Mesoporous Mater. (2019).
  64. Verboekend D, Milina M, Mitchell S, Perez-Ramirez J, Cryst. Growth Des., 13, 5025 (2013)
  65. Feng A, Yu Y, Mi L, Cao Y, Yu Y, Song L, Microporous Mesoporous Mater., 280, 211 (2019)
  66. Chai SH, Wang HP, Liang Y, Xu BQ, Green Chem., 10, 1087 (2008)
  67. Arandes JM, Torre I, Azkoiti MJ, Erena J, Olazar M, Bilbao J, Energy Fuels, 23, 4215 (2009)
  68. Bunmai K, Osakoo N, Deekamwong K, Rongchapo W, Keawkumay C, Chanlek N, Prayoonpokarach S, Wittayakun J, J. Taiwan Inst. Chem. Eng. (2017).
  69. Nichterwitz M, Gratz S, Nickel W, Borchardt L, J. Mater. Chem. A, 5, 221 (2017)
  70. Jia YM, Wang JW, Zhang K, Chen GL, Yang YF, Liu SB, Ding CM, Meng YY, Liu P, Powder Technol., 328, 415 (2018)
  71. Jia Y, Wang J, Zhang K, Feng W, Liu S, Ding C, Liu P, Microporous Mesoporous Mater., 247, 103 (2017)
  72. Xue T, Liu H, Zhang Y, Wu H, Wu P, He M, Microporous Mesoporous Mater., 242, 190 (2017)
  73. Mohamed RM, Fouad OA, Ismail AA, Ibrahim IA, Mater. Lett., 59, 3441 (2005)
  74. Costa AE, Cerqueira HS, Ferreira JMM, Ruiz NMS, Menezes SMC, Appl. Catal. A: Gen., 319, 137 (2007)
  75. Corma A, Martinez-Triguero J, Valencia S, Benazzi E, Lacombe S, J. Catal., 206(1), 125 (2002)
  76. Garcia-Martinez J, Sendrov E, Hinchey R. U.S. patent US9580328 B2 (2012).
  77. Garcia-Martinez J, Senderov E, Hinchey R. U.S. Patent US2012,0258852 A1.
  78. Zon MVD, Hilgers JH, U.S. Patent 2008, US2008/0146436 A1.
  79. Zeng P, Liang Y, Ji S, Shen B, Liu H, Wang B, Zhao H, Li M, J. Energy Chem., 23, 193 (2014)
  80. Han D, Sun N, Liu J, Li C, Shan H, Yang C, J. Energy Chem., 23, 519 (2014)
  81. Liu Z, Chen S, Ge X, Dong P, Gao J, Xu Z, Energy Fuels, 24, 2825 (2010)
  82. Hussain AI, Palani A, Aitani AM, Cejka J, Shamzhy M, Kubu M, Al-Khattaf SS, Fuel Proc. Technol., 161, 23 (2017)
  83. Al-Khattaf S, Energy Fuels, 17(1), 62 (2003)
  84. Etim UJ, Wu P, Bai P, Xing W, Ullah R, Subhan F, Yan Z, Energy Fuel (2016).
  85. Kim SW, Yeo CE, Lee DY, Energies, 12, 293 (2019)
  86. Wheeler A, Adv. Catal., 3, 249 (1951)
  87. Jeon HJ, Park SK, Woo SH, Appl. Catal. A: Gen., 306, 1 (2006)
  88. Hartmann M, Angew. Chem.-Int. Edit., 43, 5880 (2004)
  89. Liu H, Bao X, Wei W, Shi G, Microporous Mesoporous Mater., 66, 117 (2003)
  90. Fan Y, Xiao H, Shi G, Liu HY, Bao XJ, J. Catal., 285(1), 251 (2012)