DOI: https://doi.org/10.9767/bcrec.20667

Catalytic Aromatization of Propane-Butane Fractions over Polyfunctional Zeolite Catalysts: Effect of Process Parameters

1Shakarim University, Glinki, 20, Semey, Kazakhstan

2Al-Farabi Kazakh National University, Al-Farabi 71, 050040, Almaty, Kazakhstan

3Satbayev University, Satbayev Str. 22, Almaty, 050000, Kazakhstan

4 Chouaïb Doukkali University, Faculty of Sciences, 24000 El Jadida, Morocco

View all affiliations
Received: 10 Feb 2026; Revised: 29 May 2026; Accepted: 29 May 2026; Available online: 29 Jun 2026; Published: 29 Oct 2026.
Editor(s): Istadi Istadi
Open Access Copyright (c) 2026 by Authors, Published by BCREC Publishing Group
Creative Commons License This work is licensed under a Creative Commons Attribution-ShareAlike 4.0 International License.
Fulltext View|Download

Citation Format:
Cover Image
Abstract

The catalytic conversion of a propane–butane fraction into aromatic hydrocarbons was investigated over ZnLaFe/ZSM-5 and phosphorus-modified ZnLaFeP/ZSM-5 catalysts. The catalysts were characterized by N₂ adsorption–desorption, X-ray diffraction, SEM-EDX, TEM, and NH₃-TPD analyses. Textural and structural studies confirmed the preservation of the MFI framework after metal and phosphorus incorporation, while acidity measurements revealed that phosphorus modification significantly reduced the concentration of medium-strong and strong Brønsted acid sites, leading to a moderated acid strength distribution. Catalytic performance tests demonstrated that ZnLaFe/ZSM-5 exhibits high PBF conversion over a wide temperature range, whereas ZnLaFeP/ZSM-5 delivers substantially higher aromatic yields, reaching up to 59.7% at 550 °C and a gas hourly space velocity (GHSV) of 350 h⁻¹. The enhanced aromatization performance of the phosphorus-containing catalyst is attributed to the synergistic interaction between moderated Brønsted acidity and Zn–phosphate Lewis acid sites, which promote dehydrogenation, cyclization, and aromatization while suppressing excessive cracking and coke formation. Stability tests over 11 h confirmed the superior resistance of ZnLaFeP/ZSM-5 to deactivation, with only minor losses in conversion and aromatic yield and a stable product distribution dominated by benzene and toluene. Pilot-scale experiments using larger catalyst beds (100 and 500 mL) further demonstrated that the optimized acidity and catalytic functionality are retained upon scale-up.

Keywords: propane-butane fraction; liquefied petroleum gas; ZSM-5; aromatic compound.

Article Metrics:

Article Info
Section: Original Research Articles
Language : EN
Recent articles
Role of Ni and Zn Dopants in Modulating the Structure and Photocatalytic Activity of Mesoporous Silica–Cu Catalysts for Methylene Blue Degradation Catalytic Aromatization of Propane-Butane Fractions over Polyfunctional Zeolite Catalysts: Effect of Process Parameters The Incorporation of Hemin Catalysts and Alumina Nanoparticles in a Medium of Spondias mombin Leaf Extract of A Sulfonated Polysulfone-Polyaniline_Alumina Membrane Electrode Assembly for Fuel Cell Technologies Tailoring the Structural Evolution of Co-Supported Fibrous ZSM-5 via Hydrothermal Aging for Syngas Production in Ethanol Dry Reforming Apparent Reaction Kinetics of Crude Palm Oil Dechlorination Using Sodium Silicate Solution More recent articles
  1. Akhtar, M.N., Jermy, B.R., Ahmad, N. (2025). Catalytic performance of sustainable bifunctional GaZn/ZSM-5 catalyst for LPG Aromatization. Molecular Catalysis, 584, 115298. DOI: 10.1016/J.MCAT.2025.115298
  2. Dehertog, W.J.H., Fromen, G.F. (1999). A catalytic route for aromatics production from LPG. Applied Catalysis A: General, 189(1), 63–75. DOI: 10.1016/S0926-860X(99)00252-5
  3. Ghosh, A.C., Patil, G.S., Dutta, N.N. (1994). Liquid membrane permeation of aromatic hydrocarbons in LPG condensate. Fuel Processing Technology, 38(1), 17–30. DOI: 10.1016/0378-3820(94)90040-X
  4. Kaltschmitt, T., Deutschmann, O. (2012). Fuel Processing for Fuel Cells. Advances in Chemical Engineering, 41, 1–64. DOI: 10.1016/B978-0-12-386874-9.00001-4
  5. Egazariyants, S. V., Karakhanova, N.K. (2009). Determination of aromatic hydrocarbons in petroleum jet fuels by capillary gas chromatography and high-performance liquid chromatography. Moscow University Chemistry Bulletin 2009 64:1, 64(1), 32–37. DOI: 10.3103/S0027131409010076
  6. Wang, H., Nguyen, T.D., Tsilomelekis, G. Propane oxidative dehydrogenation using CO2 over CrOx/Fe-CeO2 catalysts ARTICLE Propane oxidative dehydrogenation using CO2 over CrOx /Fe-CeO2 catalysts. https://doi.org/10.1039/x0xx00000x
  7. Fridman, V.Z., Xing, R. (2017). Deactivation Studies of the CrOx/Al2O3 Dehydrogenation Catalysts under Cyclic Redox Conditions. Industrial and Engineering Chemistry Research, 56(28), 7937–7947. DOI: 10.1021/ACS.IECR.7B01638
  8. Jin, D., Xu, H., Zhu, J., Cheng, D. (2023). Activation of Cr2O3 for propane dehydrogenation by doping with Pt single-atom promotor. Molecular Catalysis, 551, 113624. DOI: 10.1016/J.MCAT.2023.113624
  9. Shan, Y., Hu, H., Fan, X., Zhao, Z. (2023). Recent progress in catalytic dehydrogenation of propane over Pt-based catalysts. Physical Chemistry Chemical Physics, 25(28), 18609–18622. DOI: 10.1039/D3CP01659E
  10. Sun, M., Zhai, S., Weng, C., Wang, H., Yuan, Z.Y. (2024). Pt-based catalysts for direct propane dehydrogenation: Mechanisms revelation, advanced design, and challenges. Molecular Catalysis, 558, 114029. DOI: 10.1016/J.MCAT.2024.114029
  11. Pan, J., Bru, G., Carbó, J.J., Godard, C., Ricart, J.M. (2025). Propane Dehydrogenation Catalyzed by Pt Clusters (Pt2–Pt6) in Gas Phase and Supported on g-C3N4 and γ-Al2O3: A Theoretical Study. ACS Omega, 10(39), 46105–46114. DOI: 10.1021/ACSOMEGA.5C07626
  12. Nerl, H.C., Plodinec, M., Götsch, T., Skorupska, K., Schlögl, R., Jones, T.E., Lunkenbein, T. (2024). In Situ Formation of Platinum-Carbon Catalysts in Propane Dehydrogenation. Angewandte Chemie - International Edition, 63(24), e202319887. DOI: 10.1002/ANIE.202319887;PAGE:STRING:ARTICLE/CHAPTER
  13. Zhou, H., Li, H., Wang, L., Chu, S., Liu, L., Liu, L., Qi, J., Ren, Z., Cai, A., Hui, Y., Qin, Y., Song, L., Qin, X., Shi, J., Hou, J., Ding, Y., Ma, J., Xu, S., Tao, X., Li, L., Yang, Q., Hu, B., Liu, X., Chen, L., Xiao, J., Xiao, F.S. (2025). Cobaltosilicate zeolite beyond platinum catalysts for propane dehydrogenation. Nature Catalysis 2025 8:4, 8(4), 357–367. DOI: 10.1038/s41929-025-01320-x
  14. Sattler, J.J.H.B., Ruiz-Martinez, J., Santillan-Jimenez, E., Weckhuysen, B.M. (2014). Catalytic Dehydrogenation of Light Alkanes on Metals and Metal Oxides. Chemical Reviews, 114(20), 10613–10653. DOI: 10.1021/CR5002436
  15. Liu, D., Cao, L., Zhang, G., Zhao, L., Gao, J., Xu, C. (2021). Catalytic conversion of light alkanes to aromatics by metal-containing HZSM-5 zeolite catalysts—A review. Fuel Processing Technology, 216, 106770. DOI: 10.1016/J.FUPROC.2021.106770
  16. Ono, Y. (1992). Transformation of Lower Alkanes into Aromatic Hydrocarbons over ZSM-5 Zeolites. Catalysis Reviews, 34(3), 179–226. DOI: 10.1080/01614949208020306
  17. Wang, H., Shiju, N.R. (2025). A mini review on aromatization of n-alkanes. Reaction Chemistry & Engineering, 10(4), 768–776. DOI: 10.1039/D4RE00384E
  18. Geng, R., Liu, Y., Gao, J., Guo, Y., Dong, M., Wang, S., Fan, W., Wang, J., Qin, Z. (2022). The migration of Zn species on Zn/ZSM-5 catalyst during the process of ethylene aromatization. Catalysis Science & Technology, 12(13), 4201–4210. DOI: 10.1039/D2CY00661H
  19. Barzallo, D., Reinoso, M.A., Miranda, G., Romero, T., Franco, M., Palmay, P. (2024). Bifunctional Catalytic Performance of Zn/ZSM-5 in the Aromatization of LPG and the Conversion of Pyrolytic Gases from Recycled Polypropylene. ChemEngineering 2024, Vol 8, Page 108, 8(6), 108. DOI: 10.3390/CHEMENGINEERING8060108
  20. Pan, T., Ge, S., Yu, M., Ju, Y., Zhang, R., Wu, P., Zhou, K., Wu, Z. (2022). Synthesis and consequence of Zn modified ZSM-5 zeolite supported Ni catalyst for catalytic aromatization of olefin/paraffin. Fuel, 311, 122629. DOI: 10.1016/J.FUEL.2021.122629
  21. Ishihara, A., Kanamori, S., Hashimoto, T. (2021). Effects of Zn Addition into ZSM-5 Zeolite on Dehydrocyclization-Cracking of Soybean Oil Using Hierarchical Zeolite-Al2O3 Composite-Supported Pt/NiMo Sulfided Catalysts. ACS Omega, 6(8), 5509–5517. DOI: 10.1021/ACSOMEGA.0C05855
  22. Dauda, I.B., Yusuf, M., Gbadamasi, S., Bello, M., Atta, A.Y., Aderemi, B.O., Jibril, B.Y. (2020). Highly Selective Hierarchical ZnO/ZSM-5 Catalysts for Propane Aromatization. ACS Omega, 5(6), 2725–2733. DOI: 10.1021/ACSOMEGA.9B03343
  23. Oseke, G.G., Atta, A.Y., Mukhtar, B., El-Yakubu, B.J., Aderemi, B.O. (2022). Synergistic effect of Zn with Ni on ZSM-5 as propane aromatization catalyst: effect of temperature and feed flowrate. Journal of Porous Materials 2022 29:6, 29(6), 1839–1852. DOI: 10.1007/S10934-022-01294-2
  24. Kumar, N., Byggningsbacka, R., Lindfors, L.E. (1997). Aromatization ofn-butane over Ni-ZSM-5 and Cu-ZSM-5 zeolite catalysts prepared by using Ni and Cu impregnated silica, fiber. Reaction Kinetics and Catalysis Letters 1997 61:2, 61(2), 297–305. DOI: 10.1007/BF02478386
  25. Zhang, Y., Wang, J., Zhang, L., Wang, W., Li, J. (2024). Synthesis of Hollow Zn/ZSM-5 Nanosheets via Different Alkali Treatments with ZIF-8 as a Zn Source for Efficient Aromatization of Methanol. Langmuir, 40(52), 27455–27469. DOI: 10.1021/ACS.LANGMUIR.4C03739
  26. Song, S., Li, T., Ju, Y., Li, Y., Lv, Z., Zheng, P., Duan, A., Wu, P., Wang, X. (2022). Lanthanum/Gallium-Modified Zn/ZSM-5 Zeolite for Efficient Isomerization/Aromatization of FCC Light Gasoline. Industrial & Engineering Chemistry Research, 61(27), 9667–9677. DOI: 10.1021/ACS.IECR.2C01104
  27. Oseke, G. G., Atta, A. Y., Mukhtar, B., Jibril, B. Y., Aderemi, B. O. (2020). Highly selective and stable Zn–Fe/ZSM-5 catalyst for aromatization of propane. Applied Petrochemical Research 2020 10:2, 10(2), 55–65. DOI: 10.1007/S13203-020-00245-9
  28. Abdelsayed, V., Shekhawat, D., Smith, M.W. (2015). Effect of Fe and Zn promoters on Mo/HZSM-5 catalyst for methane dehydroaromatization. Fuel, 139, 401–410. DOI: 10.1016/j.fuel.2014.08.064
  29. Fan, H., Nie, X., Song, C., Guo, X. (2025). Identification of the synergistic promotion of P and CO2 on propane dehydrogenation and aromatization over the Zn/P-ZSM-5 catalyst. Catalysis Science & Technology, 15(17), 5076–5089. DOI: 10.1039/D5CY00607D
  30. Song, L., Navarro de Miguel, J.C., Komaty, S., Chung, S.H., Ruiz-Martínez, J. (2025). Role of Phosphorus on ZSM-5 Zeolite for the Methanol-to-Hydrocarbon Reaction. ACS Catalysis, 15(7), 5623–5639. DOI: 10.1021/ACSCATAL.4C07064
  31. Hajimirzaee, S., Soleimani Mehr, A., Kianfar, E. (2022). Modified ZSM-5 Zeolite for Conversion of LPG to Aromatics. Polycyclic Aromatic Compounds, 42(5), 2334–2347. DOI: 10.1080/10406638.2020.1833048;SUBPAGE:STRING:ACCESS
  32. Treacy, M.M.J., Higgins, J.B. (2007). Collection of Simulated XRD Powder Patterns for Zeolites, Fifth Edition. Collection of Simulated XRD Powder Patterns for Zeolites, Fifth Edition, 1–485. DOI: 10.1016/B978-0-444-53067-7.X5470-7
  33. Blasco, T., Corma, A., Martínez-Triguero, J. (2006). Hydrothermal stabilization of ZSM-5 catalytic-cracking additives by phosphorus addition. Journal of Catalysis, 237(2), 267–277. DOI: 10.1016/J.JCAT.2005.11.011
  34. Abubakar, S.M., Marcus, D.M., Lee, J.C., Ehresmann, J.O., Chen, C.Y., Kletnieks, P.W., Guenther, D.R., Hayman, M.J., Pavlova, M., Nicholas, J.B., Haw, J.F. (2006). Structural and Mechanistic Investigation of a Phosphate-Modified HZSM-5 Catalyst for Methanol Conversion. Langmuir, 22(10), 4846–4852. DOI: 10.1021/LA0534367
  35. Rodríguez-González, L., Hermes, F., Bertmer, M., Rodríguez-Castellón, E., Jiménez-López, A., Simon, U. (2007). The acid properties of H-ZSM-5 as studied by NH3-TPD and 27Al-MAS-NMR spectroscopy. Applied Catalysis A: General, 328(2), 174–182. DOI: 10.1016/J.APCATA.2007.06.003
  36. Li, J., Ma, H., Sun, Q., Ying, W., Fang, D. (2015). Effect of iron and phosphorus on HZSM-5 in catalytic cracking of 1-butene. Fuel Processing Technology, 134, 32–38. DOI: 10.1016/J.FUPROC.2014.11.026
  37. Jiang, S., Chang, C.W., Swann, W.A., Li, C.W., Miller, J.T. (2024). Pt3Mn/SiO2 + ZSM-5 Bifunctional Catalyst for Ethane Dehydroaromatization. Catalysts, 14(6), 365. DOI: 10.3390/CATAL14060365/S1
  38. Wang, X., Li, C., Yang, J., Liu, Y., Hei, J., Huang, S., Gao, D. (2024). Production of aromatic hydrocarbons from catalytic fast pyrolysis of microalgae over Fe-modified HZSM-5 catalysts. RSC Advances, 14(50), 36970–36979. DOI: 10.1039/D4RA06815G
  39. Zhao, G., Teng, J., Xie, Z., Jin, W., Yang, W., Chen, Q., Tang, Y. (2007). Effect of phosphorus on HZSM-5 catalyst for C4-olefin cracking reactions to produce propylene. Journal of Catalysis, 248(1), 29–37. DOI: 10.1016/J.JCAT.2007.02.027
  40. Huyen, P.T., Trinh, V.D., Teresa Portilla, M., Martínez, C. (2021). Influence of boron promotion on the physico-chemical properties and catalytic behavior of Zn/ZSM-5 in the aromatization of n-hexane. Catalysis Today, 366, 97–102. DOI: 10.1016/J.CATTOD.2020.03.030
  41. Védrine, J.C., Auroux, A., Dejaifve, P., Ducarme, V., Hoser, H., Zhou, S. (1982). Catalytic and physical properties of phosphorus-modified ZSM-5 zeolite. Journal of Catalysis, 73(1), 147–160. DOI: 10.1016/0021-9517(82)90089-6
  42. Liu, J., He, N., Zhou, W., Lin, L., Liu, G., Liu, C., Wang, J., Xin, Q., Xiong, G., Guo, H. (2018). Isobutane aromatization over a complete Lewis acid Zn/HZSM-5 zeolite catalyst: performance and mechanism. Catalysis Science & Technology, 8(16), 4018–4029. DOI: 10.1039/C8CY00917A
  43. Nguyen, L.H., Vazhnova, T., Kolaczkowski, S.T., Lukyanov, D.B. (2006). Combined experimental and kinetic modelling studies of the pathways of propane and n-butane aromatization over H-ZSM-5 catalyst. Chemical Engineering Science, 61(17), 5881–5894. DOI: 10.1016/J.CES.2006.05.017
  44. Bai, Y., Niu, X., Du, Y.E., Chen, Y. (2023). Conversion of Methanol to Para-Xylene over ZSM-5 Zeolites Modified by Zinc and Phosphorus. Molecules 2023, Vol 28, 28(13) DOI: 10.3390/MOLECULES28134890
  45. Long, H., Jin, F., Xiong, G., Wang, X. (2014). Effect of lanthanum and phosphorus on the aromatization activity of Zn/ZSM-5 in FCC gasoline upgrading. Microporous and Mesoporous Materials, 198, 29–34. DOI: 10.1016/J.MICROMESO.2014.07.016
  46. Teimouri Sendesi, S.M., Towfighi, J., Keyvanloo, K. (2012). The effect of Fe, P and Si/Al molar ratio on stability of HZSM-5 catalyst in naphtha thermal-catalytic cracking to light olefins. Catalysis Communications, 27, 114–118. DOI: 10.1016/J.CATCOM.2012.06.013
  47. Liu, R.L., Zhu, H.Q., Wu, Z.W., Qin, Z.F., Fan, W. Bin, Wang, J.G. (2015). Aromatization of propane over Ga-modified ZSM-5 catalysts. Journal of Fuel Chemistry and Technology, 43(8), 961–969. DOI: 10.1016/S1872-5813(15)30027-X
  48. Shou, H., Dasari, P.R., Broekhuis, R.R., Mondal, A., Patel, A., Nguyen, C., Fickel, D.W. (2022). Cracking of Butane on a Pt/H-ZSM-5 Catalyst in the Presence of Hydrogen. Industrial & Engineering Chemistry Research, 61(14), 4763–4773. DOI: 10.1021/ACS.IECR.1C04545
  49. Uslamin, E.A., Saito, H., Sekine, Y., Hensen, E.J.M., Kosinov, N. (2021). Different mechanisms of ethane aromatization over Mo/ZSM-5 and Ga/ZSM-5 catalysts. Catalysis Today, 369, 184–192. DOI: 10.1016/J.CATTOD.2020.04.021
  50. Gou, M.L., Wang, R., Qiao, Q., Yang, X. (2014). Effect of phosphorus on acidity and performance of HZSM-5 for the isomerization of styrene oxide to phenylacetaldehyde. Applied Catalysis A: General, 482, 1–7. DOI: 10.1016/J.APCATA.2014.05.023
  51. Gao, X., Tang, Z., Zhang, H., Liu, C., Zhang, Z., Lu, G., Ji, D. (2010). High performance phosphorus-modified ZSM-5 zeolite for butene catalytic cracking. Korean Journal of Chemical Engineering 2010 27:3, 27(3), 812–815. DOI: 10.1007/S11814-010-0134-6

Last update:

No citation recorded.

Last update:

No citation recorded.