Methane Dehydroaromatization over Mo and W Catalysts Supported on ZSM-5

Document Type : Research Article


1 Department of Chemical Engineering, University of Hormozgan, Bandar Abbas, I.R. IRAN

2 Lavan Oil Refinary Company, Lavan. I.R. IRAN

3 Department of Chemical Engineering, Faculty of Engineering, Shahid Bahonar University of Kerman, Kerman, I.R. IRAN


Methane aromatization reaction to produce benzene using tungsten and molybdenum catalysts supported on ZSM-5 was investigated at 800 ºC. Catalysts were prepared by impregnating tungsten and molybdenum salts on ZSM-5 zeolite with various metal loadings in the range of 2-10 wt. %. To obtain the catalytic structures before and after the reaction, catalysts were characterized by XRD and FT-IR analysis. It was indicated from reactor tests that an increase in metal loading
on the catalyst surface leads to an increase in methane conversion (1.1% and 3.2% for 2W/ZSM-5 and 6 W/ZSM-5, and 2.4% and 4.8% for 2W/ZSM-5 and 6 W/ZSM-5, respectively, at the time of stream, equals 120 min). It was also concluded that Mo catalysts show higher activity and stability than W (methane conversion of 3.2 and 9 % using 10Mo/ ZSM-5 and 10 W/ZSM-5 catalysts respectively, at the time of stream equals 100 min). An increase in Mo loading leads to the enhancement of catalytic activity and methane conversion, indicating that methane's initial activation has occurred on metal sites of catalysts. This activation leads to occur the later reactions and production of final benzene. These conditions confirm the two-factor mechanism which includes two stages: i) hemolysis break of C-H bond and CH3 radical formation and then ethylene formation, and ii) cyclization of ethylene species in the presence of acidic sites within the zeolite channels. Investigations on mesoporous HMS support showed no aromatic production, which shows an increase in support channel diameter leads to reduce the possibility of ring formation.


Main Subjects

[1] Liu H., Hu S.Y.J., Shang F., Li Z., Xu C., Guan J., Kan Q., A Comparison Study of Mesoporous Mo/H-ZSM-5 and Conventional Mo/H-ZSM-5 Catalyst in Methane Non-Oxidative Aromatization, Fuel Processing Technology, 96: 195-202 (2012).
[2] Ibrahim A.A., Fakeeha A., Al-Fatesh A.S., Abasaeed A.E., Methane Decomposition over Iron Catalyst for Hydrogen Production, International Journal of Hydrogen Energy, 40:7593-7600 (2015).
[3] Schuth F., Making More from Methane, Science, 363: 1282-1283 (2019).
[4] Haynes C.A., Gonzalez R., Rethinking Biological Activation of Methane and Conversion to Liquid Fuels, Nature Chemical Biology, 10: 331-339 (2014). 
[5] Z. R. Ismagilov, E. V. Matus, L. T. Tsikoza, “Direct Conversion of Methane on Mo/ZSM-5 Catalysts to Produce Benzene and Hydrogen: Achievements and Perspectives”, Energy and Environmental Science, 1: 526-541 (2008).
[6] Cai C., Shi Y., Guo J., Tyson G.W., Hu S., Yuan Z., Acetate Production from Anaerobic Oxidation of Methane via Intracellular Storage Compounds, Environmental Science and Technology, 53: 7371-7479 (2019).
[7] Maier L., Schadel B., Delgado K.H., Tischer S., Deutschmann O., Steam Reforming of Methane over Nickel: Development of a Multi-Step Surface Reaction Mechanism, Topics in Catalysis, 54: 845-858 (2011).
[8] Meloni E., Martino M., Palma V., A Short Review in Ni Based Catalysts and Related Engineering Issues for Methane Steam Reforming, Catalysis, 10: 352 (2020).
[9] Nazari M., Heydarinasab A., Soltanieh M., Maddah B., Synthesis and Optimization of NixMn1-xFe2O4 Catalyst in Chemical Looping Steam Methane Reforming Process, Iran. J. Chem. and Chem. Eng. (IJCCE), 40(5): 1584-1606 (2021).
[10] Ozdemir H., Faruk Oksuzomer M.A., Gurkaynak M.A., Preparation and Characterization of Ni Based Catalysts for the Catalytic Partial Oxidation of Methane: Effect of Support Basicity on H2/CO Ratio and Carbon Deposition, International Journal of Hydrogen Energy, 35: 12147-12160 (2020).
[11] Elbadawi A.H., Ge L., Li Z., Liu S., Wang S., Zhu Z., Catalytic Partial Oxidation of Methane to Syngas: Review of Provskite Catalysts and Membrane Reactors, Catalysis Reviews, 63: 1-67 (2021).
[12] Shahnazari M.R., Lari H.R., Basharhagh M.Z., Simulation of Methane Partial Oxidation in Porous Media Reactor for Hydrogen Production, Iran. J. Chem. and Chem. Eng. (IJCCE), 38(1): 201-212 (2019).
[13] Rostrup-Nielsen J.R., New Aspects of Syngas Production and Use, Catalysis Today, 63: 159-164 (2000).
[14] Mohamedali M., Henni A., Ibrahim H., Recent Advances in Supported Metal Catalysts for Syngas Production from Methane, Chemical Engineering, 2: 9 (2018).
[15] Kurzina I.A., Kurina L.N., Tin-Containing Catalysts, Modified with Alkaline Earth Metals in the Oxidative Dimerization of Methane, Theoretical and Experimental Chemistry, 39: 64-69 (2003).
[16] Zhao Z-J., Kulkarni A., Vilella L., Norskov J.K., Studt F., Theoretical Insights into the Selective Oxidation of Methane to Methanol in Copper-Exchanged Mordenite, ACS Catalysis, 6: 3760-3766 (2016).
[17] Yin T., Wang H., Li S., Lu B., Zhao J., Cai Q., Copper Vanadate Nanowires on g-C3N4 Toward Highly Selective Oxidation of Methanol to Dimethoxymethane, Applied Surface Science, 548: 149180 (2021).
[18] Spivey J.J., Hutchings G., Catalytic Aromatization of Methane, Chemical Society Reviews, 43: 792-803 (2014).
[19] Ren D., Wang X, Li G., Cheng X., Long H., Chen L., Methane Aromatization in the Absence of Oxygen over Extruded and Molded MoO3/ZSM-5 Catalysts: Influences of Binder and Molding Method, Journal of Gas Chemistry, 19: 646-652 (2010).
[20] Masiero S.S., Marcilio N.R., Prez-Lopez O.W., Aromatization of Methane over Mo-Fe/ZSM-5 Catalysts, Catalysis Letters, 131: 194-202 (2009).
[21] Razdan N.K., Kumar A., Foley B.L., Bhan A., Influence of Ethylene and Acetylene on the Rate and Reversibility of Methane Dehydroaromatization on Mo/H-ZSM-5 Catalysts, Journal of Catalysis, 381: 261-270 (2020).
[22] Ha V.T.T., Tiep L.V., Meriaudeau P., Naccache C., Aromatization of Methane Over Zeolite Supported Molybdenum: Active Sites and Reaction Mechanism, Journal of Molecular Catalysis A: Chemical, 181: 283-290 (2002).
[23] Tessonnier J-P., Louis B., Rigolet S., Ledoux M.J., Pham-Huu C., Methane Dehydro-Aromatization on Mo/ZSM-5: About the Hidden Role of Bronsted Acid Sites, Applied Catalysis A: General, 336: 79-88 (2008).
[24] Abedin M.A., Kanitkar S., Bhattar S., Spivey J.J., Methane Dehydroaromatization Using Mo Supported on Sulfated Zirconia Catalyst: Effect of Promoter, Catalysis Today, 365: 71-79 (2021). 
[25] Yaghinirad E., Aghdasinia H., Naghizadeh A., Niaei A., Non-Oxidative Conversion of Methane to Aromatics Over Modified Zeolite Catalysts by Transitional Metals, Iranian Journal of Catalysis, 9: 147-154 (2019).
[26] Vosmerikoc A.V., Echevsky G.V., Korobitsyna L.L., Arbuzova N.V., Velichkina L.M., Zhurakov S.P., Barbashin Y.Y., Kodenev Y.G., Acidic and Catalytic Properties of Mo-Containing Zeolite Catalysts for Non-Oxidative Methane Conversion, Eurasian Chemico-Technological Journal, 6: 201-206 (2004).
[27] Denardin F., Prez-Lopez O.W., Tuning the Acidity and Reducibility of Fe/ZSM-5 Catalysts for Methane Dehydroaromatization, Fuel, 236: 1293-1300 (2019).
[28] Rahman M., Infantes-Molina A., Hoffman A.S., Bare S.R., Emerson K.L., Khatib S.J., Effect of Si/Al Ratio of ZSM-5 Support on Structure and Activity of Mo Species in Methane Dehydroaromatization, Fuel, 278: 118290 (2020).
[29] Kosinov N., Uslamin E.A., Coumans F.J.A.G., Wijpkema A.S.G., Roling R.Y., Hensen E.J.M., Structure and Evolution of Confined Carbon Species During Methane Dehydroaromatization over Mo/ZSM-5, ACS Catalysis, 8: 8459-8467 (2018).
[30] Kozlov V.V., Zaikovskii V.I., Vosmerikov A.V., Korobitsyna L.L., Echevskii G.V., Active Sites of the Methane Dehydroaromatization Catalyst W-ZSM-5: An HRTEM Study, Kinetics and Catalysis, 49: 114 (2008).
[31] Wang L., Tao L., Xie M., Xu G., Huang J., Xu Y., Dehydrogenation and Aromatization of Methane under Non-Oxidizing Conditions, Catalysis Letters, 2: 35-41 (1993).
[32] Wang D., Lunsford J.H., Rosynek M.P., Catalytic Conversion of Methane to Benzene over Mo/ZSM-5, Topics in Catalysis, 3: 289-297 (1996).
[33] Temoelman C.H.L., Hensen E.J.M., On the Deactivation of Mo/HZSM-5 in the Methane Dehydroaromatization Reaction, Applied Catalysis B: Environmental, 176-177: 731-739 (2015).
[34] Abdelsayed V., Shekhawat D., Smith M.W., Effect of Fe and Zn on Mo/HZSM-5 Catalyst for Methane Dehydroaromatization, Fuel, 139: 401-410 (2015).
[35] Zhang C-L., Li S., Yuan Y., Zhang W-X., Wu T-H., Lin Li-W., Aromatization of Methane in the Absence of Oxygen over Mo-based Catalysts Supported on Different Types of Zeolites, Catalysis Letters, 56: 207-213 (1998).
[36] Liu B.S., Leung J.W.H., Li L., Au C.T., Cheng A.S.-C., TOF-MS Investigation on Methane Aromatization over 3%Mo/HZSM-5 Catalyst under Supersonic Jet Expansion Condition, Chemical Physics Letters, 430: 210-214 (2006).
[37] Kozlov V.V., Zaikovskii V.I., Vosmerikov A.V., Korobitsyna L.L., Echevskii G.V., Active Sites of the Methane Dehydroaromatization Catalyst W-ZSM-5: An HRTEM Study, Kinetics and Catalysis, 49: 110-114 (2008).
[38] Yang J., Deng F., Zhang M., Luo Q., Ye C., W/HZSM-5 Catalyst for Methane Dehydroaromatization: A Multinuclear MAS NMR Study, Journal of Molecular Catalysis A: Chemical, 202: 239-246 (2003).
[40] Oseke G.G., Atta A.Y., Mukhtar B., El-Yakubu B.J., Aderemi B.O., Increasing the Catalytic Stability of Microporous Zn/ZSM-5 with Copper for Enhanced Propane Aromatization, Journal of Kings and University-Engineering Sciences, [In Press], Corrected Proof, (2020).
[41] Cheng X., Yan P., Zhang X., Yang F., Dai C., Li D., Enhanced Methane Dehydroaromatization in the Presence of CO2 over Fe- and Mg-Modified Mo/ZSM-5, Molecular Catalysis, 437: 114-120 (2017).
[42] Hedlund J., Noack M., Kolxch P., Creaser D., Caro J., Sterte J., ZSM-5 Membranes Synthesized without Organic Template Using a Seeding Technique, Journal of Membrane Science, 159: 263-237 (1999).
[43] Armaroli T., Simon L.J., Digne M., Montanari T., Bevilacqua M., Valtchev V., Patarin J., Busca G., Effects of Crystal Size and Si/Al Ratio on the Surface Properties of H-ZSM-5 Zeolites, Applied Catalysis A: General, 306: 78-84 (2006).
[44] Li B., Li S., Li N., Chen H., Zhang W., Bao X., Lin B., Structure and Acidity of Mo/ZSM-5 Synthesized by Solid State Reaction for Methane Dehydrogenation and Aromatization, Microporous and Mesoporous Materials, 88: 244-253 (2006).
[45] Tempelman C.H.L., Zhu X., Hensen E.J.M., Activation of Mo/HZSM-5 for Methane Aromatization, Chinese Journal of Catalysis, 36: 829-837 (2015).
[46] Fila V., Bernauer M., Bernauer B., Sobalik Z., Effect of Addition of a Second Metal in Mo/ZSM-5 Catalyst for Methane Aromatization Reaction under Elevated Pressures, Catalysis Today, 256: 269-275 (2015).
[47] Ma D., Wang D., Su L., Shu Y., Xu Y., Bao X., Carbonaceous Deposition on Mo/HMCM-22 Catalysts for Methane Aromatization: A Technique Investigation, Journal of Catalysis, 208: 260-269 (2002).