Catalysis Letters

, Volume 149, Issue 1, pp 248–258 | Cite as

Alkylation of Benzene by Methanol: Thermodynamics Analysis for Designing and Designing for Enhancing the Selectivity of Toluene and Para-Xylene

  • Peng Dong
  • Zeyu Li
  • Dongliang Wang
  • Xiaorui Wang
  • Yongqi Guo
  • Guixian LiEmail author
  • Dongqiang Zhang


The process of benzene/methanol alkylation reaction was studied thermodynamically based on functional group contribution method of Benson. Results show that ortho-xylene (OX), Ethyl-benzene (EB) and tri-methylbenzene (TMB) are the main byproduct in alkylation of benzene by methanol and the suppression of OX, EB and TMB over hierarchical porous HZSM-5 or other types of acidic solid catalysts still remains a great challenge. To overcome these limitations, we modified hierarchical ZSM-5 with ruthenium (Ru) to evaluate the alkylation of benzene with methanol in a fixed-bed continuous flow reactor. It was found that the presence of a small amount of Ru in ZSM-5 catalyst would largely suppress the formation of EB, reduce the selectivity of OX and TMB, and also extend greatly the live time of the catalyst. Alkylation of benzene by methanol: thermodynamics analysis for designing and designing for enhancing the selectivity of toluene and para-xylene.

Graphical Abstract

Alkylation of benzene by methanol: thermodynamics analysis for designing and designing for enhancing the selectivity of toluene and para-xylene


Benzene alkylation OX, EB and TMB suppression Ru/HZSM-5 Catalyst stability Thermodynamics analysis 



We acknowledge financial support from the Science and Technology Support Project of Gansu Province (Grant. No. 1604GKCD026) and the National Nature Science Foundation of China (Grant Nos. 212006065; 21666018).


  1. 1.
    Wang XM, Jun X, Qi GD (2013) Alkylation of benzene with methane over ZnZSM-5 Zeolites studied with solid-state NMR spectroscopy. J Phys Chem 117:4018–4023Google Scholar
  2. 2.
    Hu HL, Zhang QF, Cen J, Li XN (2014) High suppression of the formation of ethylbenzene in benzene alkylation. Catal Commun 57:129–133CrossRefGoogle Scholar
  3. 3.
    Alabi W, Atanda L, Jermy R (2012) Kinetics of toluene alkylation with methanol catalyzed by pure and hybridized HZSM-5 catalysts. Chem Eng J 195–196:276–288CrossRefGoogle Scholar
  4. 4.
    Wu HY, Liu M, Tan W (2014) Effect of ZSM-5 zeolite morphology on the catalytic performance of the alkylation of toluene with methanol. J Energy Chem 23:491–497CrossRefGoogle Scholar
  5. 5.
    Rownaghi AA, Hedlund J (2011) Methanol to gasoline-rang hydrocarbon: influence of nanocrystal size and mesoporosity on catalytic performance and product distribution of ZSM-5. Ind Eng Chem Res 50:11872–11878CrossRefGoogle Scholar
  6. 6.
    Schmidt F, Hoffmann C, Giordanino F (2013) Coke location in microporous and hierarchical ZSM-5 and the impact on the MTH reaction. J Catal 307:238–245CrossRefGoogle Scholar
  7. 7.
    Osman M, Hossain MM, Al-Khattaf S (2013) Kinetics study of ethylbenzene alkylation with ethanol over medium and large pore zeolites. Ind Eng Chem Res 52:13613–13621CrossRefGoogle Scholar
  8. 8.
    Odedairo T, Al-Khattaf S (2013) Comparative study of zeolite catalyzed alkylation of benzene with alcohols of different chain length: H-ZSM-5 versus mordenite. Catal Today 204:73–84CrossRefGoogle Scholar
  9. 9.
    Hu HL, Lyu JH, Rui JY (2016) The effect of Si/Al ratio on the catalytic performance of hierarchical porous ZSM-5 for catalyzing benzene alkylation with methanol. Catal Sci Technol 6:2647CrossRefGoogle Scholar
  10. 10.
    Tan W, Liu M, Zhao Y (2014) Para-selective methylation of toluene with methanol over nano-sized ZSM-5 catalysts: synergistic effects of surface modifications with SiO2, P2O5 and MgO. Microporous Mesoporous Mater 196:18–30CrossRefGoogle Scholar
  11. 11.
    Adebajo MO, Howe RF, Long MA (2000) Methylation of benzene with methanol over zeolite catalysts in a low pressure flow reactor. Catal Today 63:471–478CrossRefGoogle Scholar
  12. 12.
    Adebajo MO, Long MA (2003) The contribution of the methanol-to-aromatics reaction to benzene methylation over ZSM-5 catalysts. Catal Commun 4:71–76CrossRefGoogle Scholar
  13. 13.
    Adebajo MO, Long MA, Frost RL (2004) Further evidence for the oxidative methylation of benzene with methane over zeolite catalysts. Catal Commun 5:125–130CrossRefGoogle Scholar
  14. 14.
    Zhao Y, Tan W, Wu HY (2011) Effect of Pt on stability of nano-scale ZSM-5 catalyst for toluene alkylation with methanol into p-xylene. Catal Today 160:179–183CrossRefGoogle Scholar
  15. 15.
    Anderson JR, Mole T, Christov V (1980) Mechanism of some conversions over ZSM-5 catalyst. J Catal 61:477–484CrossRefGoogle Scholar
  16. 16.
    Hu HL, Zhang QF (2015) Catalytic activity of Pt modified hierarchical ZSM-5 catalysts in benzene alkylation with methanol. Catal Lett 145:715–722CrossRefGoogle Scholar
  17. 17.
    Ma PS (2006) The experimental data manual of organic compound. Chemical Industry Press, Beijing, pp 418–567Google Scholar
  18. 18.
    Dung VV, Miyamoto M, Nishiyama N (2006) Selective formation of para-xylene over H-ZSM-5 coated with polycrystalline silicalite crystals. J Catal 243:389–394CrossRefGoogle Scholar
  19. 19.
    Koningsveld HV, Jansen JC, Bekkum HV (1990) The monoclinic framework structure of zeolite H-ZSM-5. Comparison with the orthorhombic framework of as-synthesized ZSM-5. Zeolites 10:235–242CrossRefGoogle Scholar
  20. 20.
    Gervasini A (1999) Characterization of the textural properties of metal loaded ZSM-5 zeolites. Appl Catal A 180:71–82CrossRefGoogle Scholar
  21. 21.
    Zhang HL, Zhang MJ, Li HW, Chou YJ, Chen Y (2001) Studies on structure, acidity and catalytic properties of mordenites changed by chemical surface modification. J Wuhan Uni Sci Tech 24:361–364Google Scholar
  22. 22.
    Wang GR (2015) Catalyst and catalysis. Dalian University of Technology Press, Dalian, pp 104–110Google Scholar
  23. 23.
    Pauling L (1960) The nature of the chemical bond. Cornell University Press, New YorkGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  • Peng Dong
    • 1
    • 2
  • Zeyu Li
    • 3
  • Dongliang Wang
    • 1
  • Xiaorui Wang
    • 2
  • Yongqi Guo
    • 1
  • Guixian Li
    • 1
    Email author
  • Dongqiang Zhang
    • 1
  1. 1.College of Petrochemical TechnologyLanzhou University of TechnologyLanzhouPeople’s Republic of China
  2. 2.Lanzhou Petrochemical College of Vocational TechnologyLanzhouPeople’s Republic of China
  3. 3.School of Chemical EngineeringLanzhou UniversityLanzhouPeople’s Republic of China

Personalised recommendations