Molybdenum substitution by copper or zinc in H-ZSM-5 zeolite for catalyzing the direct conversion of natural gas to petrochemicals under non-oxidative conditions

This work aims to investigate the influence of substituting half the Mo content in a standard 6%Mo/H-ZSM-5 catalyst with either Cu or Zn in H-ZSM-5 support, on the direct conversion of methane in a flow-type fixed-bed reactor atmospherically at 700 °C at a gas hourly space velocity 1500 cm3 h−1 g−1 and times-on stream (TOS) up to 240 min. The most active was 6%Mo/H-ZSM-5 catalyst while Mo–Zn/H-ZSM-5 was more active than Mo–Cu/H-ZSM-5. The XRD data showed that the crystallite (particle) sizes were found compatible with the catalytic activities. At the initial TOS (5 min), methane splitting selectivity to C and H2 approached 100%. Higher carbon deposition on Mo–Cu catalyst caused more inhibition of ethylene further conversion to larger hydrocarbons thus leading to ethylene accumulation. TPR showed an almost complete reduction of Cu oxides at relatively lower temperatures such that the Mo–Cu catalyst acquired the highest dehydrogenation activity that enhanced markedly ethylene formation. An outstanding accomplishment is obtaining the highest benzene yield and selectivity using Mo–Zn/H-ZSM-5 catalyst, which is a prosperous challenge against the standard monometallic one. The large size of naphthalene molecule caused significant diffusion restriction on its formation in catalytic pores. The exceptional enhancement of naphthalene yield and selectivity at longer TOS using the Mo–Cu/H-ZSM-5 catalyst can be indicative that naphthalene was mostly formed on external zeolitic surface.

► The work is focused to conversion of natural gas to petrochemicals under non-oxidative conditions in a flow reactor at 700 oC.
► Comparing the catalytic activities and selectivities of 6%Mo, 3%Mo–3%Zn or 3%Mo+3%Cu/H-ZSM-5 catalysts for methane aromatization reactions.
► From XRD, the crystallite sizes were compatible with the catalytic activities.
► TPR showed much faster and complete reduction of Cu oxides to Cu relative to Zn or Mo oxides, which enhances ethylene production.
► Zn combination with Mo results in producing the highest benzene yield and selectivity.