Hostname: page-component-76fb5796d-5g6vh Total loading time: 0 Render date: 2024-04-25T07:32:42.772Z Has data issue: false hasContentIssue false
  • English
  • Français

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

Published online by Cambridge University Press:  09 October 2020

Md Ashraful Abedin Open the ORCID record for Md Ashraful Abedin [Opens in a new window] ,
Swarom Kanitkar  and
James J. Spivey
Md Ashraful Abedin
Affiliation:
Department of Chemical Engineering, Louisiana State University, Baton Rouge, LA70803USA
Swarom Kanitkar
Affiliation:
Department of Chemical Engineering, Louisiana State University, Baton Rouge, LA70803USA
James J. Spivey*
Affiliation:
Department of Chemical Engineering, Louisiana State University, Baton Rouge, LA70803USA
*
*Corresponding author: J.J. Spivey, email: jjspivey@lsu.edu; Tel: +1-225-578-3690
Get access

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.

Type
Articles
Information
MRS Advances , Volume 5 , Issue 63: International Materials Research Congress XXIX , 2020 , pp. 3407 - 3417
Check for updates
Copyright
Copyright © The Author(s), 2020, published on behalf of Materials Research Society by Cambridge University Press

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Chen, H., Li, L., Hu, J., Upgrading of stranded gas via non-oxidative conversion processes, Catal. Today, (2017) Ahead of Print.Google Scholar
Spivey, J.J., Hutchings, G., Catalytic aromatization of methane, Chem Soc Rev, 43 (2014) 792-803.CrossRefGoogle ScholarPubMed
Cai, X., Hu, Y.H., Advances in catalytic conversion of methane and carbon dioxide to highly valuable products, Energy Science & Engineering, 7 (2019) 4-29.CrossRefGoogle Scholar
Bhattar, S., Abedin, M.A., Shekhawat, D., Haynes, D.J., Spivey, J.J., 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.CrossRefGoogle Scholar
Karakaya, C., Kee, R.J., Progress in the direct catalytic conversion of methane to fuels and chemicals, Progress in Energy and Combustion Science, 55 (2016) 60-97.CrossRefGoogle Scholar
Weckhuysen, B.M., Wang, D., Rosynek, M.P., Lunsford, J.H., Conversion of Methane to Benzene over Transition Metal Ion ZSM-5 Zeolites: I. Catalytic Characterization, Journal of Catalysis, 175 (1998) 338-346.CrossRefGoogle Scholar
Kosinov, N., Coumans, F.J.A.G., Li, G., Uslamin, E., Mezari, B., Wijpkema, A.S.G., Pidko, E.A., Hensen, E.J.M., Stable Mo/HZSM-5 methane dehydroaromatization catalysts optimized for high-temperature calcination-regeneration, Journal of Catalysis, 346 (2017) 125-133.CrossRefGoogle Scholar
Rahman, M., Sridhar, A., Khatib, S.J., 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.CrossRefGoogle Scholar
Tshabalala, T.E., Coville, N.J., Anderson, J.A., Scurrell, M.S., 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.CrossRefGoogle Scholar
Abedin, M.A., Kanitkar, S., Kumar, N., Wang, Z., Ding, K., Hutchings, G., Spivey, J.J., Probing the Surface Acidity of Supported Aluminum Bromide Catalysts, Catalysts, 10 (2020) 869.CrossRefGoogle Scholar
Corma, A., Solid acid catalysts, Current Opinion in Solid State and Materials Science, 2 (1997) 63-75.CrossRefGoogle Scholar
Corma, A., Inorganic solid acids and their use in acid-catalyzed hydrocarbon reactions, Chemical Reviews, 95 (1995) 559-614.CrossRefGoogle Scholar
Reddy, B.M., Patil, M.K., Organic Syntheses and Transformations Catalyzed by Sulfated Zirconia, Chemical Reviews, 109 (2009) 2185-2208.CrossRefGoogle ScholarPubMed
Rabee, A., Mekhemer, G., Osatiashtiani, A., Isaacs, M., Lee, A., Wilson, K., Zaki, M., Acidity-Reactivity Relationships in Catalytic Esterification over Ammonium Sulfate-Derived Sulfated Zirconia, Catalysts, 7 (2017) 204.CrossRefGoogle Scholar
Kanitkar, S., Abedin, A., Bhattar, S., Spivey, J., 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
Fraenkel, D., Methane conversion over sulfated zirconia, Catalysis Letters, 58 (1999) 123-125.CrossRefGoogle Scholar
Abedin, M.A., Kanitkar, S., Bhattar, S., Spivey, J.J., Mo oxide supported on sulfated hafnia: Novel solid acid catalyst for direct activation of ethane & propane, Applied Catalysis A: General, 602 (2020) 117696.CrossRefGoogle Scholar
Abedin, M.A., Kanitkar, S., Bhattar, S., Spivey, J.J., Promotional Effect of Cr in Sulfated Zirconia-Based Mo Catalyst for Methane Dehydroaromatization, Energy Technology, 8 (2020) 1900555.CrossRefGoogle Scholar
Oloye, F.F., McCue, A.J., Anderson, J.A., n-Heptane hydroconversion over sulfated-zirconia-supported molybdenum carbide catalysts, Applied Petrochemical Research, 6 (2016) 341-352.CrossRefGoogle Scholar
Claridge, J.B., York, A.P.E., Brungs, A.J., Marquez-Alvarez, C., Sloan, J., Tsang, S.C., Green, M.L.H., New Catalysts for the Conversion of Methane to Synthesis Gas: Molybdenum and Tungsten Carbide, Journal of Catalysis, 180 (1998) 85-100.CrossRefGoogle Scholar
Kanitkar, S., Abedin, M.A., Bhattar, S., Spivey, J.J., Methane dehydroaromatization over molybdenum supported on sulfated zirconia catalysts, Applied Catalysis A: General, 575 (2019) 25-37.CrossRefGoogle Scholar
Arata, K., Solid Superacids, in: Eley, D.D., Pines, H., Weisz, P.B. (Eds.) Advances in Catalysis, Academic Press 1990, pp. 165-211.Google Scholar
Parry, E.P., An Infrared Study of Pyridine Adsorbed on Acidic Solids. Characterization of Surface Acidity, 1963.CrossRefGoogle Scholar
Chen, W.-H., Ko, H.-H., Sakthivel, A., Huang, S.-J., Liu, S.-H., Lo, A.-Y., Tsai, T.-C., Liu, S.-B., 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.CrossRefGoogle Scholar
Bijani, P.M., Sohrabi, M., Sahebdelfar, S., Thermodynamic Analysis of Nonoxidative Dehydroaromatization of Methane, Chemical Engineering & Technology, 35 (2012) 1825-1832.CrossRefGoogle Scholar
George, S.J., Drury, O.B., Fu, J., Friedrich, S., Doonan, C.J., George, G.N., White, J.M., Young, C.G., Cramer, S.P., 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.CrossRefGoogle ScholarPubMed
Lede, E.J., Requejo, F.G., Pawelec, B., Fierro, J.L.G., XANES Mo L-Edges and XPS Study of Mo Loaded in HY Zeolite, The Journal of Physical Chemistry B, 106 (2002) 7824-7831.CrossRefGoogle Scholar
Abedin, M.A., Kanitkar, S., Bhattar, S., Spivey, J.J., Methane dehydroaromatization using Mo supported on sulfated zirconia catalyst: Effect of promoters, Catalysis Today, (2020).Google Scholar
Querini, C.A., Coke characterization, in: Spivey, J.J., Roberts, G.W. (Eds.) Catalysis: Volume 17, The Royal Society of Chemistry 2004, pp. 166-209.Google Scholar
Liu, W., Xu, Y., 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.CrossRefGoogle Scholar