Bifunctional catalysis of Mo/HZSM-5 in the dehydroaromatization of methane with CO/CO2 to benzene and naphthalene

The catalytic dehydrocondensation of methane to aromatics such as benzene and naphthalene was studied on the Mo carbide catalysts supported on micro- and mesoporous materials such as HZSM-5 (0.6 nm) and FSM-16 (2.7 nm). The Mo catalysts supported on H-ZSM-5 having appropriate micropores (0.6 nm size) and Si/Al ratios (20-70) exhibit higher yields (90-150 nmol/g-cat/s) and selectivities (higher than 74% on the carbon basis) in methane conversion to aromatic products such as benzene and naphthalene at 973 K and 1 atm, although they are drastically deactivated because of substantial coke formation. It was demonstrated that the CO/CO2 addition to methane effectively improves the catalyst performance by keeping a higher methane conversion and selectivities of benzene formation in the prolonged time-on-stream. The oxygen derived from CO and CO2 dissociation suppresses polycondensation of aromatic products and coke formation in the course of methane conversion. XAFS and TG/DTA/mass-spectrometric studies reveal that the zeolite-supported Mo oxide is endothermally converted under the action of methane around 955 K to nanosized particles of molybdenum carbide (Mo2C) (Mo-C, coordination number = 1, R = 2.09 Angstrom; Mo-Mo, coordination number = 2.3-3.5; R = 2.98 Angstrom) The SEM pictures showed that the nanostructured Mo carbide particles are highly dispersed on and inside the HZSM-5 crystals. On the other hand, it was demonstrated by IR measurements of pyridine adsorption that the Mo/HZSM-5 catalysts having the optimum SiO2/Al2O3 ratios around 40 show the maximum Bronsted acidity among the catalysts with the SiO2/Al2O3 ratios of 20-1900. There is a close correlation between the activity of benzene formation in the methane aromatization and the Bronsted acidity of HZSM-5 due to the bifunctional catalysis.