Rare Earth-doped Ceria Catalysts for ODHE Reaction in a Catalytic Modified MIEC Membrane Reactor

Abstract

[EN] An intensification process for the selective oxidation of hydrocarbons integrates a catalytic reactor and an oxygen separation membrane. This work presents the study of oxidative dehydrogenation of ethane at 1123 K in a catalytic membrane reactor based on mixed ionic-electronic conducting (MIEC) membranes. The surface of a membrane made of Ba0.5Sr0.5Co0.8Fe0.2O3-d has been activated using different porous catalytic layers based on rare earth-doped cerias (fluorite structure) and the porous catalytic coating was deposited by screen printing (coating around 15 mu m). The different catalyst formulations were developed by partial substitution of Ce and were synthesized by co-precipitation followed by cobalt impregnation when required. Specifically, seven different catalysts based on the system Ce1-xLnxO2-d (x=0.1 or 0.2; Ln=Tb, Pr, Er, Gd, and Tb+Er), including the effect of cobalt addition (2?% molar) in Ce0.8Tb0.2O2-d, were studied. The ceria catalysts were studied by XRD, SEM, DC-conductivity as a function of oxygen partial pressure, and the high-temperature stability in a CO2 environment was assessed using thermogravimetry. Then, the influence of the ceria catalytic coating on the oxygen permeation flux through the MIEC membrane was studied using argon and methane as the sweep gas in the permeate side. Finally, oxidative dehydrogenation of ethane reaction tests were performed at 1123 K, as a function of the ethane concentration in the feed. The use of a disk-shaped membrane in the reactor made it possible to prevent the direct contact of gaseous oxygen and hydrocarbons and thus to increase the ethylene yield. High ethylene yields (up to approximate to 84?%) were obtained using a catalytic coating based on 20?% Tb-doped ceria including macropores produced by the addition of graphite platelets in the screen printing ink. The high yields obtained in this kind of catalytic membrane are attributed to the combination of: the high catalytic activity; the control of the oxygen concentration in the gas phase (reaction chamber); and the appropriate fluid dynamics, enabling the fast ethylene evacuation.