Effect of Bifunctional Pt-Containing Al2O3-FeY Nanocatalysts on Ethylbenzene Transformation

Document Type : Research Paper


1 Department of Petrochemical, Iran Polymer and Petrochemical Institute, (IPPI) Tehran, Iran

2 School of Chemical Engineering, College of Engineering, University of Tehran, Tehran, Iran


Transformation of ethylbenzene can provide valuable isomers as a raw material for the petrochemical industry. This work explored the transformation of ethylbenzene (EB) over nanozeolite Y with the Si/Al ratio of 5. Fe ion exchange was carried out to modify the acidity of zeolites. The influence of platinum was investigated by the introduction of Pt-Al2O3. XRD, SEM, ICP, BET, FTIR, 27Al MAS NMR, NH3-TPD, and TG tests were applied for the characterization of physicochemical properties of prepared nanocatalysts. The slight decrease in the surface area of synthesized Fe-Y nanocatalysts indicated that the major part of iron was deposited in the catalyst structure.  The addition of iron to the nanocatalyst structure resulted in increased strong acid sites and decreased weak acid sites. Reduction in weak acidity led to a lower coke formation rate and higher stability of FeY nanocatalysts. Results illustrated that the intensity of Lewis acidity decreased for all prepared nanocatalysts by increasing the iron content while the number of Bronsted acid sites increased. The addition of platinum-Al2O3 to the FeY nanocatalysts illustrated higher EB conversion and the same catalyst stability as FeY nanocatalysts. Nanozeolite Pt/Fe-Y composed of 0.1 wt.% platinum and 1.0 wt.% iron was obtained to be effective catalyst for EB transformation reaction. The prepared catalyst indicated adequate degree of EB conversion (61%) as well as 77.2% EB isomerization, 3.3% EB disproportionation, 1.4% EB dealkylation, 3.1% EB cracking, 14.8% EB hydrogenation and 0.2% EB transalkylation. 


  1. Al-Khattaf S, Rabiu S, Tukur N, Alnaizy R (2008) Kinetics of toluene methylation over USY-zeolite catalyst in a riser simulator, Chemical Engineering Journal, 139: 622-630.##
  2. Gonçalves JC, Rodrigues AE (2013) Thermodynamic equilibrium of xylene isomerization in the liquid phase, Journal of Chemical and Engineering Data, 58: 1425-1428. ##
  3. Min HK, Cha SH, Hong SB (2012) Mechanistic insights into the zeolite-catalyzed isomerization and disproportionation of m-xylene, ACS Catalysis, 2: 971-981. ##
  4. Shah J, Jan MR (2015) Effect of polyethylene terephthalate on the catalytic pyrolysis of polystyrene: Investigation of the liquid products, Journal of the Taiwan Institute of Chemical Engineers, 51: 96-102. ##
  5. Tukur NM, Al-Khattaf S (2011) Comparison studies of xylene isomerization and disproportionation reactions between SSZ-33, TNU-9, mordenite and ZSM-5 zeolite catalysts, Chemical Engineering Journal, 166: 348-357. ##
  6. Rasouli M, Yaghobi N, Allahgholipour F, Atashi H (2014) Para-xylene adsorption separation process using nano-zeolite Ba-X, Chemical Engineering Research and Design, 92: 1192-1199. ##
  7. Rasouli M, Yaghobi N, Chitsazan S, Sayyar MH (2012) Influence of monovalent cations ion-exchange on zeolite ZSM-5 in separation of para-xylene from xylene mixture, Microporous and Mesoporous Materials, 150: 47-54. ##
  8. Rasouli M, Yaghobi N, Gilani SZM, Atashi H, Rasouli M (2015) Influence of monovalent alkaline metal cations on binder-free nano-zeolite X in para-xylene separation, Chinese Journal of Chemical Engineering, 23: 64-70. ##
  9. Aboul-Gheit AK, Aboul-Fotouh SM (2012) Insight in cyclohexene hydroconversion process using catalysts containing 0.35% Pt on amorphous and zeolite supports, Journal of the Taiwan Institute of Chemical Engineering, 43: 711-717. ##
  10. Daramola M, Burger A, Giroir-Fendler A (2011) Modelling and sensitivity analysis of a nanocomposite MFI-alumina based extractor-type zeolite catalytic membrane reactor for m-Xylene isomerization over Pt-HZSM-5 catalyst, Chemical Engineering Journal, 171: 618-627. ##
  11. Guillon E, Lacombe S, Sozinho T (2009) How to improve the selectivity of zeolitic catalysts in C8 aromatic cut isomerization, Oil and Gas Science and Technology-Revue de l’IFP, 64: 731-744. ##
  12. Tarach KA, Gołąbek K, Choi M, Góra-Marek K (2017) Quantitative infrared spectroscopic studies and 2D COS analysis of xylenes isomerization over hierarchical zeolites, Catalysis Today, 283: 158-171. ##
  13. Moreau F, Moreau P, Gnep NS (2006) Ethylbenzene isomerization over bifunctional platinum alumina–EUO catalysts: Location of the active sites, Microporous and Mesoporous Materials, 90: 327-338. ##
  14. Iskandar F, Afifah Zen N, Rona Mayangsari T, Hasdi Aimon A, Astra Pramana A (2019) Development of faujasite-type zeolite and iron oxide as mixed catalyst for aquathermolysis reaction of heavy oil, Materials Research Express, 6. ##
  15. Shekarian E, Jafari Nasr MR, Mohammadi T, Bakhtiari O, Javanbakht M (2019) Preparation of 4A zeolite coated polypropylene membrane for lithium-ion batteries separator, Journal of Applied Polymer Science, 136: 47841. ##
  16. Jia X, Han L, Ma Y, Che S (2018) Additive-free synthesis of mesoporous FAU-type zeolite with intergrown structure, Science China Materials, 61: 1095-1100. ##
  17. Wang L, Xiao FS (2018) A significant enhancement of catalytic performance by adjusting catalyst wettability, Science China Materials, 61: 1137-1142. ##
  18. Farahani SH, Alavi SM, Falamaki C (2017) Improved performance of HZSM-5 for the ethylbenzene/xylene isomerization reaction under industrial operating conditions, RSC Advances, 7: 34012-34022. ##
  19. Farshadi M, Falamaki C (2018) Ethylbenzene disproportionation and p-xylene selectivity enhancement in xylene isomerization using high crystallinity desilicated H-ZSM-5, Chinese Journal of Chemical Engineering, 26: 116-126. ##
  20. Shi Q, Gonçalves JC, Ferreira AF, Plaza MG, Rodrigues AE (2018) Xylene isomerization side reactions over Beta zeolite: Disproportionation and transalkylation of C8 aromatics and toluene, Applied Catalysis A: General, 562: 198-205. ##
  21. Shi Q, Gonçalves JC, Ferreira AF, Plaza MG, Rodrigues AE (2018) Xylene Isomerization over Beta Zeolites in Liquid Phase, Industrial & Engineering Chemistry Research, 57: 5568-5579. ##
  22. Yanna L, Jingyang X, Lijun J, Yunming F, Haoquan H (2009) Synthesis and modification of zeolite NaA adsorbents for separation of hydrogen and methane, Asia-Pacific Journal of Chemical Engineering, 4: 666-671. ##
  23. Moreau F, Bernard S, Gnep NS, Lacombe S, Merlen E, Guisnet M (2001) Ethylbenzene isomerization on bifunctional platinum alumina–mordenite catalysts 1. Influence of the mordenite Si/Al Ratio, Journal of Catalysis, 202: 402-412. ##
  24. Geetha Bhavani A, Pandurangan A (2007) Hydroisomerization of ethylbenzene over bimetallic bifunctional zeolite catalysts, Journal of Molecular Catalysis A: Chemical, 267: 209–217. ##
  25. Tsai TC, Wang I, Huang CK, Liu SD (2007) Study on ethylbenzene and xylene conversion over modified ZSM-5, Applied Catalysis A: General, 321: 125–134. ##
  26. Rasouli M, Yaghobi N, Chitsazan S, Sayyar MH (2012) Effect of nanocrystalline zeolite Na-Y on meta-xylene separation, Microporous and Mesoporous Materials, 152: 141-147. ##
  27. Ruiping W, Maiping G, Jun W (2009) Preparation, characterization and catalytic behavior of 12-molybdophosphoric acid encapsulated in the supercage of Cs+-exchanged Y zeolite, Chinese Journal of Chemical Engineering, 17: 58-63. ##
  28. Liu SQ, Cheng S, Feng LR, Wang XM, Chen ZG (2010) Effect of alkali cations on heterogeneous photo-Fenton process mediated by Prussian blue colloids, Journal of hazardous materials, 182: 665-671. ##
  29. Haghighi Asl M, Sargolzaei J, Moosavi F (2015) Identification of the coke deposited on 13X industrial zeolite molecular sieves during mercaptan removal process, Asia-Pacifif Journal of Chemical Engineering 11: 164-178. ##
  30. Sanaeepur H, Kargari A, Nasernejad B, Amooghin AE, Omidkhah M (2016) A novel Co2+ exchanged zeolite Y/cellulose acetate mixed matrix membrane for CO2/N2 separation, Journal of the Taiwan Institute of Chemical Engineers, 60: 403-413. ##
  31. [31] Jian Z, Zhicheng L, Liyuan L (2013) Hierarchical mesoporous ZSM-5 zeolite with increased external surface acid sites and high catalytic performance in o-xylene isomerization, Chinese Journal of Catalysis, 34: 1429-1433. ##
  32. Toch K, Thybaut J, Vandegehuchte B (2012) A Single-Event MicroKinetic model for ethylbenzene dealkylation/xylene isomerization on Pt/H-ZSM-5 zeolite catalyst, Applied Catalysis A: General., 425: 130-144. ##
  33. Haji S, Khalaf M, Shukrallah M, Abdullah J, Ahmed S (2015) A kinetic comparative study of azo dye decolorization by catalytic wet peroxide oxidation using Fe–Y zeolite/H2O2 and photooxidation using UV/H2O2, Reaction Kinetics, Mechanisms and Catalysis, 114: 795-815. ##
  34. Rostamizadeh M, Yaripour F (2016) Bifunctional and bimetallic Fe/ZSM-5 nanocatalysts for methanol to olefin reaction, Fuel., 181: 537-546. ##
  35. Kondru AK, Kumar P, Chand S (2009) Catalytic wet peroxide oxidation of azo dye (Congo red) using modified Y zeolite as catalyst, Journal of Hazardous Materials, 166: 342-347. ##
  36. Aravindhan R, Fathima NN, Rao JR, Nair BU (2006) Wet oxidation of acid brown dye by hydrogen peroxide using heterogeneous catalyst Mn-salen-Y zeolite: a potential catalyst, Journal Hazard Mater, 138: 152-159. ##
  37. Heuchel M, Dörr C, Boldushevskii R (2018) The influence of porosity and active sites of zeolites Y and beta on the co-cracking of n-decane and 2-ethylphenol, Applied Catalysis A: General, 553: 91-106.
  38. Soltanali S, Hajjar Z, Bahadoran F (2019) The possibility of phase change in amorphous silica-alumina synthesis to FAU zeolite using carbon nano structures, Materials Research Express, 6. ##
  39. Wang JQ, Huang YX, Pan Y, Mi JX (2016) New hydrothermal route for the synthesis of high purity nanoparticles of zeolite Y from kaolin and quartz, Microporous and Mesoporous Materials, 232: 77-85. ##
  40. Pedrosa AMG, Souza MJ, Melo DM, Araujo AS (2006) Cobalt and nickel supported on HY zeolite: Synthesis, characterization and catalytic properties, Materials Research Bulletin. 41: 1105-1111. ##
  41. Cui Q, Wang S, Wei Q (2019) Synthesis and characterization of Zr incorporated small crystal size Y zeolite supported NiW catalysts for hydrocracking of vacuum gas oil, Fuel., 237: 597-605. ##
  42. Qu Z, Roduner E (2009) In situ ESR study of gold supported on NaY zeolite, Asia-Pacific Journal of Chemical Engineering, 4: 602-606. ##
  43. Hosseinpour N, Khodadadi AA, Mortazavi Y, Bazyari A (2009) Nano-ceria–zirconia promoter effects on enhanced coke combustion and oxidation of CO formed in regeneration of silica–alumina coked during cracking of triisopropylbenzene, Applied Catalysis A: General, 353: 271-281. ##
  44. Chu Y, Yi X, Li C, Sun X, Zheng A (2018) Brønsted/Lewis acid sites synergistically promote the initial C–C bond formation in the MTO reaction, Chemical science, 9: 6470-6479. ##
  45. Lee S, Choi M (2019) Unveiling coke formationmechanism in MFI zeolites during methanol-to-hydrocarbons conversion, Journal of Catalysis 375, 183-192. ##
  46. Dai J, Zhang H (2019) Recent advances in selective CC bond coupling for ethanol upgrading over balanced Lewis acid-base catalysts, Science China Materials, 1-13. ##
  47. Du H, Olson DH (2002) Surface acidic properties of a HMCM-22 zeolite: Collidine poisoning and hydrocarbon adsorption studies, The Journal of Physical Chemistry B, 106: 395-400. ##
  48. McCaulay DA, Lien AP (1953) Disproportionation of alkylbenzenes.II. Mechanism of alkyl-group transfer, Journal of American Chemical Society, 75, 10: 2411–2413. ##
  49. Silva J, Ribeiro M, Ribeiro FR, Benazzi F, Guisnet M (1995) Transformation of an ethylbenzene-o-xylene mixture on HMOR and Pt-HMOR catalysts. Comparison with ZSM-5 catalysts, Applied Catalysis A: General, 125: 15-27. ##
  50. Bhavani AG, Pandurangan A (2007) Hydroisomerization of ethylbenzene over bimetallic bifunctional zeolite catalysts, Journal of Molecular Catalysis A: Chemical, 267: 209-217. ##
  51. Rasouli M, Yaghobi N (2018) Synthesis and characterization of platinum impregnated Zn-Zsm5 nanocatalysts for xylene isomerization reactions, Catalysis Letters, 148: 2325-2336. ##
  52. Gnep N, de Armando MM, Guisnet M (1983) O-Xylene transformation on acid catalysts: influence of hydrogen activated on metallic sites, studies in surface science and catalysis, Elsevier, 17: 309-318. ##
  53. Moreau F, Bernard S, Gnep N (2001) Ethylbenzene isomerization on bifunctional platinum alumina–mordenite catalysts: 1. Influence of the mordenite Si/Al ratio, Journal of Catalysis, 202: 402-412. ##
  54. Moreau F, Gnep N, Lacombe S, Merlen E, Guisnet M (2002) Ethylbenzene transformation on bifunctional Pt/Al2O3-NaHMOR catalysts: Influence of Na exchange on their activity and selectivity in ethylbenzene isomerization, Applied Catalysis A: General, 230: 253-262. ##
  55. Moreau P, Gnep N, Magnoux P (2008) Influence of zeolite structure on ethylbenzene transformation, Studies in Surface Science and Catalysis, Elsevier, 174:  1179-1182. ##