Industrial & Engineering Chemistry Research, Vol.41, No.10, 2371-2378, 2002
Methane nonoxidative aromatization over Ru-Mo/HZSM-5 in a membrane catalytic reactor
Low-temperature oxygen-free methane aromatization was carried out over Ru-Mo/HZSM-5 in a catalytic membrane reactor. The 0.5% Ru-3% Mo/HZSM-5 catalyst, prepared by incipient wetness coimpregnation, was highly selective toward benzene production. Methane aromatization was evaluated under two sets of conditions: (i) without hydrogen permeation in a fixed-bed conventional catalytic reactor (CR) and (ii) with hydrogen permeation in a catalytic membrane reactor (CMR). In CR mode, the catalyst exhibited remarkable stability with no significant deactivation for 24 h on stream. Switching to CMR mode gave rise to a significant increase in conversion, which reached levels well beyond the thermodynamic conversion. The continuous withdrawal of coproduced H-2 promoted the formation of carbonaceous species with a low H/C ratio and led to a decrease in benzene production. At a methane space velocity of 270 mL (STP)(.)h(-1.)g(-1) and a temperature of 873 K, the CR mode yielded a maximum conversion of methane to benzene equal to 3.8%, i.e., 73% of the thermodynamic equilibrium conversion (5.2%). Under similar conditions, the maximum conversion to benzene attained in CMR mode was 9%. Alternating CR and CMR sequences under moderate feed flow rates proved to be a viable strategy for maintaining high catalyst activity toward benzene production for more than 100 h on stream. The CR step, through an increased hydrogen concentration, helped regenerate the active sites by hydrogenating the carbonaceous species, while the CMR step contributed in the overshoot of benzene conversion due to the equilibrium shift brought about by hydrogen withdrawal. A two-active-site model was proposed to rationalize the experimental observations. Further tests dealing with hydrogen addition to the methane feed flow clearly demonstrated the beneficial influence of hydrogen on the catalyst activity.