Skip to main content
SpringerLink
Log in

A novel approach of methane dehydroaromatization using group VIB metals (Cr, Mo, W) supported on sulfated zirconia

  • Articles
  • Published:
MRS Advances Aims and scope Submit manuscript

Abstract

Methane dehydroaromatization (MDHA) is a direct activation approach to covert methane to value-added chemicals in a single step. This requires no intermediate step, making it a commercially economic approach. Mo supported on HZSM-5/MCM-22 is a well-studied catalyst for this reaction, where Mo sites are responsible for activating methane to C2Hy dimers, which can oligomerize on HZSM-5 Bronsted acid sites to produce aromatics. Challenges for these bifunctional catalysts involve rapid coking and low product yield. In this study, a novel catalytic approach is introduced using group VIB metals (Cr, Mo, W) supported on sulfated zirconia (SZ) solid acid. It is believed that the Bronsted acidity of SZ should help to convert the dimers generated from metal sites to ethylene and aromatics like benzene.

Here, fresh Mo, W and Cr were doped into SZ and characterized using pyridine DRIFTS, ammonia TPD, BET and SEM-EDS.. Catalytic activity for MDHA was ranked as Mo>W>Cr. Mo/SZ showed greater selectivity towards ethylene and benzene, followed by W/SZ, which was selective primarily towards ethylene. Cr/SZ showed the least activity under similar reaction conditions, producing only a small amount of ethylene. Higher catalytic activity for Mo/SZ was possibly due to reduced Mo oxide sites, found from XANES analysis, as well as higher acidity, observed from TPD. Deactivation was mainly due to coking, observed from subsequent TPO analysis. Further investigation is necessary to enhance the activity of this novel catalytic approach before considering for potential industrial applications.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. H. Chen, L. Li, J. Hu, Upgrading of stranded gas via non-oxidative conversion processes, Catal. Today, (2017) Ahead of Print.

    Google Scholar 

  2. J.J. Spivey, G. Hutchings, Catalytic aromatization of methane, Chem Soc Rev, 43 (2014) 792–803.

    Article  CAS  Google Scholar 

  3. X. Cai, Y.H. Hu, Advances in catalytic conversion of methane and carbon dioxide to highly valuable products, Energy Science & Engineering, 7 (2019) 4–29.

    Article  CAS  Google Scholar 

  4. S. Bhattar, M.A. Abedin, D. Shekhawat, D.J. Haynes, J.J. Spivey, The effect of La substitution by Sr- and Ca- in Ni substituted Lanthanum Zirconate pyrochlore catalysts for dry reforming of methane, Applied Catalysis A: General, 602 (2020) 117721.

    Article  CAS  Google Scholar 

  5. C. Karakaya, R.J. Kee, Progress in the direct catalytic conversion of methane to fuels and chemicals, Progress in Energy and Combustion Science, 55 (2016) 60–97.

    Article  Google Scholar 

  6. B.M. Weckhuysen, D. Wang, M.P. Rosynek, J.H. Lunsford, Conversion of Methane to Benzene over Transition Metal Ion ZSM-5 Zeolites: I. Catalytic Characterization, Journal of Catalysis, 175 (1998) 338–346.

    Article  CAS  Google Scholar 

  7. N. Kosinov, F.J.A.G. Coumans, G. Li, E. Uslamin, B. Mezari, A.S.G. Wijpkema, E.A. Pidko, E.J.M. Hensen, Stable Mo/HZSM-5 methane dehydroaromatization catalysts optimized for high-temperature calcination-regeneration, Journal of Catalysis, 346 (2017) 125–133.

    Article  CAS  Google Scholar 

  8. M. Rahman, A. Sridhar, S.J. Khatib, Impact of the presence of Mo carbide species prepared ex situ in Mo/HZSM-5 on the catalytic properties in methane aromatization, Applied Catalysis A: General, 558 (2018) 67–80.

    Article  CAS  Google Scholar 

  9. T.E. Tshabalala, N.J. Coville, J.A. Anderson, M.S. Scurrell, Dehydroaromatization of methane over Sn–Pt modified Mo/H-ZSM-5 zeolite catalysts: Effect of preparation method, Applied Catalysis A: General, 503 (2015) 218–226.

    Article  CAS  Google Scholar 

  10. M.A. Abedin, S. Kanitkar, N. Kumar, Z. Wang, K. Ding, G. Hutchings, J.J. Spivey, Probing the Surface Acidity of Supported Aluminum Bromide Catalysts, Catalysts, 10 (2020) 869.

    Article  CAS  Google Scholar 

  11. A. Corma, Solid acid catalysts, Current Opinion in Solid State and Materials Science, 2 (1997) 63–75.

    Article  CAS  Google Scholar 

  12. A. Corma, Inorganic solid acids and their use in acid-catalyzed hydrocarbon reactions, Chemical Reviews, 95 (1995) 559–614.

    Article  CAS  Google Scholar 

  13. B.M. Reddy, M.K. Patil, Organic Syntheses and Transformations Catalyzed by Sulfated Zirconia, Chemical Reviews, 109 (2009) 2185–2208.

    Article  CAS  Google Scholar 

  14. A. Rabee, G. Mekhemer, A. Osatiashtiani, M. Isaacs, A. Lee, K. Wilson, M. Zaki, Acidity-Reactivity Relationships in Catalytic Esterification over Ammonium Sulfate-Derived Sulfated Zirconia, Catalysts, 7 (2017) 204.

    Article  Google Scholar 

  15. S. Kanitkar, A. Abedin, S. Bhattar, J. Spivey, Effect of Mo content in methane dehydroaromatization using sulfated zirconia supported Mo2C catalysts, ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, AMER CHEMICAL SOC 1155 16TH ST, NW, WASHINGTON, DC 20036 USA, 2018.

    Google Scholar 

  16. D. Fraenkel, Methane conversion over sulfated zirconia, Catalysis Letters, 58 (1999) 123–125.

    Article  CAS  Google Scholar 

  17. M.A. Abedin, S. Kanitkar, S. Bhattar, J.J. Spivey, Mo oxide supported on sulfated hafnia: Novel solid acid catalyst for direct activation of ethane & propane, Applied Catalysis A: General, 602 (2020) 117696.

    Article  Google Scholar 

  18. M.A. Abedin, S. Kanitkar, S. Bhattar, J.J. Spivey, Promotional Effect of Cr in Sulfated Zirconia-Based Mo Catalyst for Methane Dehydroaromatization, Energy Technology, 8 (2020) 1900555.

    Article  CAS  Google Scholar 

  19. F.F. Oloye, A.J. McCue, J.A. Anderson, n-Heptane hydroconversion over sulfated-zirconia-supported molybdenum carbide catalysts, Applied Petrochemical Research, 6 (2016) 341–352.

    Article  CAS  Google Scholar 

  20. J.B. Claridge, A.P.E. York, A.J. Brungs, C. Marquez-Alvarez, J. Sloan, S.C. Tsang, M.L.H. Green, New Catalysts for the Conversion of Methane to Synthesis Gas: Molybdenum and Tungsten Carbide, Journal of Catalysis, 180 (1998) 85–100.

    Article  CAS  Google Scholar 

  21. S. Kanitkar, M.A. Abedin, S. Bhattar, J.J. Spivey, Methane dehydroaromatization over molybdenum supported on sulfated zirconia catalysts, Applied Catalysis A: General, 575 (2019) 25–37.

    Article  CAS  Google Scholar 

  22. K. Arata, Solid Superacids, in: D.D. Eley, H. Pines, P.B. Weisz (Eds.) Advances in Catalysis, Academic Press 1990, pp. 165–211.

  23. E.P. Parry, An Infrared Study of Pyridine Adsorbed on Acidic Solids. Characterization of Surface Acidity, 1963.

    Google Scholar 

  24. W.-H. Chen, H.-H. Ko, A. Sakthivel, S.-J. Huang, S.-H. Liu, A.-Y. Lo, T.-C. Tsai, S.-B. Liu, A solid-state NMR, FT-IR and TPD study on acid properties of sulfated and metal-promoted zirconia: Influence of promoter and sulfation treatment, Catalysis Today, 116 (2006) 111–120.

    Article  CAS  Google Scholar 

  25. P.M. Bijani, M. Sohrabi, S. Sahebdelfar, Thermodynamic Analysis of Nonoxidative Dehydroaromatization of Methane, Chemical Engineering & Technology, 35 (2012) 1825–1832.

    Article  Google Scholar 

  26. S.J. George, O.B. Drury, J. Fu, S. Friedrich, C.J. Doonan, G.N. George, J.M. White, C.G. Young, S.P. Cramer, Molybdenum X-ray absorption edges from 200 to 20,000eV: The benefits of soft X-ray spectroscopy for chemical speciation, Journal of Inorganic Biochemistry, 103 (2009) 157–167.

    Article  CAS  Google Scholar 

  27. E.J. Lede, F.G. Requejo, B. Pawelec, J.L.G. Fierro, XANES Mo L-Edges and XPS Study of Mo Loaded in HY Zeolite, The Journal of Physical Chemistry B, 106 (2002) 7824–7831.

    Article  CAS  Google Scholar 

  28. M.A. Abedin, S. Kanitkar, S. Bhattar, J.J. Spivey, Methane dehydroaromatization using Mo supported on sulfated zirconia catalyst: Effect of promoters, Catalysis Today, (2020).

    Google Scholar 

  29. C.A. Querini, Coke characterization, in: J.J. Spivey, G.W. Roberts (Eds.) Catalysis: Volume 17, The Royal Society of Chemistry 2004, pp. 166–209.

    Google Scholar 

  30. W. Liu, Y. Xu, Methane Dehydrogenation and Aromatization over Mo/HZSM-5: In Situ FT–IR Characterization of Its Acidity and the Interaction between Mo Species and HZSM-5, Journal of Catalysis, 185 (1999) 386–392.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemical Engineering, Louisiana State University, Baton Rouge, LA, 70803, USA

    Md Ashraful Abedin, Swarom Kanitkar & James J. Spivey

Authors
  1. Md Ashraful Abedin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Swarom Kanitkar
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. James J. Spivey
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to James J. Spivey.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Abedin, M.A., Kanitkar, S. & Spivey, J.J. A novel approach of methane dehydroaromatization using group VIB metals (Cr, Mo, W) supported on sulfated zirconia. MRS Advances 5, 3407–3417 (2020). https://doi.org/10.1557/adv.2020.368

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1557/adv.2020.368

Search

Navigation