Co2MnO4/Ce0.8Tb0.2O2-δ Dual-Phase Membrane Material with High CO2 Stability and Enhanced Oxygen Transport for Oxycombustion Processes.

Oxygen transport membranes (OTMs) are a promising oxygen production technology with high energy efficiency due to the potential for thermal integration. However, conventional perovskite materials of OTMs are unstable in CO2 atmospheres, which limits their applicability in oxycombustion processes. On the other hand, some dual-phase membranes are stable in CO2 and SO2 without permanent degradation. However, oxygen permeation is still insufficient; therefore, intensive research focuses on boosting oxygen permeation. Here, we present a novel dual-phase membrane composed of an ion-conducting fluorite phase (Ce0.8Tb0.2O2-δ, CTO) and an electronic-conducting spinel phase (Co2MnO4, CMO). CMO spinel exhibits high electronic conductivity (60 S·cm-1 at 800 °C) compared to other spinels used in dual-phase membranes, i.e., 230 times higher than that of NiFe2O4 (NFO). This higher conductivity ameliorates gas-solid surface exchange and bulk diffusion mechanisms. By activating the bulk membrane with a CMO/CTO porous catalytic layer, it was possible to achieve an oxygen flux of 0.25 mL·min-1·cm-2 for the 40CMO/60CTO (%vol), 680 µm-thick membrane at 850 °C even under CO2-rich environments. This dual-phase membrane shows excellent potential as an oxygen transport membrane or oxygen electrode under high CO2 and oxycombustion operation.

Evaluation of Er Doped CeO2-δ as Oxygen Transport Membrane.

Ceria based materials are robust candidates for a range of applications involving redox reactions and high oxygen activity. The substitution of erbium in the ceria lattice introduces extrinsic oxygen vacancies. Further addition of Co introduces electronic carriers. We have studied the structural and redox behavior of Ce1-xErxO2-δ (x = 0.1 and 0.2) and the influence of adding 2 mol% of Co in the electrochemical properties. A limitation in the solubility of Er cation is found. Diffusion and surface exchange coefficients have been obtained by electrical conductivity relaxation and the DC-conductivity and O2 permeation measurements show the importance of the electronic component in the transport properties, obtaining an oxygen permeation flux of 0.07 mL·min-1·cm-2 at 1000 °C, for a 769 µm thick membrane.

Mixed Ionic-Electronic Conduction in NiFe2 O4 -Ce0.8 Gd0.2 O2-δ Nanocomposite Thin Films for Oxygen Separation.

NiFe2 O4 -Ce0.8 Gd0.2 O2-δ (NFO/CGO) nanocomposite thin films were prepared by simultaneously radio-frequency (RF) magnetron sputtering of both NFO and CGO targets. The aim is the growth of a CO2 -stable composite layer that combines the electronic and ionic conduction of the separate NFO and the CGO phases for oxygen separation. The effect of the deposition temperature on the microstructure of the film was studied to obtain high-quality composite thin films. The ratio of both phases was changed by applying different power to each ceramic target. The amount of each deposited phase as well as the different oxidation states of the nanocomposite constituents were analyzed by means of X-ray photoelectron spectroscopy (XPS). The transport properties were studied by conductivity measurements as a function of temperature and pO2 . These analyses enabled (1) selection of the best deposition temperature (400 °C), (2) correlation of the p-type electronic behavior of the NFO phase with the hole hopping between Ni3+ -Ni2+ , and (3) following the conductivity behavior of the grown composite layer (prevailing ionic or electronic character) attained by varying the amount of each phase. The sputtered layer exhibited high ambipolar conduction and surfaceexchange activity. A 150 nm-thick nanograined thin film was deposited on a 20 µm-thick Ba0.5 Sr0.5 Co0.8 Fe0.2 O3-δ asymmetric membrane, resulting in up to 3.8 mL min-1 cm-2 O2 permeation at 1000 °C under CO2 atmosphere.

Dual-Phase Oxygen Transport Membranes for Stable Operation in Environments Containing Carbon Dioxide and Sulfur Dioxide.

Dual-phase membranes are appealing candidates for oxygen transport membranes owing to their unique combination of ambipolar electron-ion transport and endurance. However, O2 separation in industrial environments demands very high stability and effectiveness in the presence of CO2- and SO2-bearing process gases. Here, the composition of dual-phase membranes based on NiFe2O4-Ce(0.8) Tb(0.2)O(2-δ) (NFO-CTO) was optimized and the effective performance of catalytically-activated membranes was assessed in presence of CO2 and SO2. Further insight into the limiting mechanisms in the permeation was gained through electrical conductivity studies, permeation testing in several conditions and impedance spectroscopy analysis. The dual-phase membranes were prepared by one-pot sol-gel method and their permeability increases with increasing fluorite content. An O2 flux of 0.25 (ml min(-1) cm(-2)) mm at 1000 °C was obtained for a thick self-standing membrane with 40:60 NFO/CTO composition. An in-depth study mimicking typical harsh conditions encountered in oxyfuel flue gases was performed on a 50:50 NFO/CTO membrane. CO2 content as well as SO2 presence in the sweep gas stream were evaluated in terms of O2 permeation. O2 fluxes of 0.13 and 0.09 mL min(-1) cm(-2) at 850 °C were obtained for a 0.59 mm thick membrane under CO2 and 250 ppm SO2 in CO2 sweep conditions, respectively. Extended periods at work under CO2- and SO2-containing atmospheres revealed good permeation stability over time. Additionally, XRD, backscattered electrons detector (BSD)-SEM, and energy-dispersive X-ray spectroscopy (EDS) analysis of the spent membrane confirmed material stability upon prolonged exposure to SO2.

Enhanced oxygen separation through robust freeze-cast bilayered dual-phase membranes.

Dual-phase oxygen-permeable asymmetric membranes with enhanced oxygen permeation were prepared by combining freeze-casting, screen-printing, and constraint-sintering techniques. The membranes were evaluated under oxyfuel operating conditions. The prepared membranes are composed of an original ice-templated La(0.6)Sr(0.4)Co(0.2)Fe(0.8)O(3-δ) support with hierarchically oriented porosity and a top fully densified bilayered coating comprising a 10 µm-thick La(0.6)Sr(0.4)Co(0.2)Fe(0.8)O(3-δ) layer and a top protective 8 µm-thick layer made of an optimized NiFe2O4/Ce(0.8)Tb(0.2)O(2-δ) composite synthesized by the one-pot Pechini method. Preliminary analysis confirmed the thermochemical compatibility of the three involved phases at high temperature without any additional phase detected. This membrane exhibited a promising oxygen permeation value of 4.8 mL min(-1) cm(-2) at 1000 °C upon using Ar and air as the sweep and feed gases, respectively. Mimicking oxyfuel operating conditions by switching argon to pure CO2 as a sweep gas at 1000 °C and air as feed enabled an oxygen flux value of 5.6 mL min(-1) cm(-2) to be reached. Finally, under the same conditions and increasing the oxygen partial pressure to 0.1 MPa in the feed, the oxygen permeation reached 12 mL min(-1) cm(-2). The influence of CO2 content in the sweep gas was studied and its reversible and positive effect over oxygen permeation at temperatures equal to or above 950 °C was revealed. Finally, the membrane stability over a period of 150 h under CO2-rich sweep gas showed a low degradation rate of 2.4×10(-2)  mL min(-1) cm(-2) per day.

Ethylene production by ODHE in catalytically modified Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) membrane reactors.

Process intensification by the integration of membranes and high-temperature reactors offers several advantages with regard to conventional process schemes, that is, energy saving, safe operation, reduced plant/unit size, and higher process performance, for example, higher productivity, catalytic activity, selectivity, or stability. We present the study of oxidative dehydrogenation of ethane at 850 °C on a catalytic membrane reactor based on a mixed ionic-electronic conducting membrane. The surface of the membrane made of Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) has been activated by using different porous catalytic layers based on perovskites. The layer was deposited by screen printing, and the porosity and thickness was studied for the catalyst composition. The different catalyst formulations are based on partial substitution of A- and B-site atoms of doped strontium ferrite/cobaltites (A(0.6)Sr(0.4)Co(0.5)Fe(0.5)O(3-δ) and Ba(0.6)Sr(0.4)BO(3-δ)) and were synthesized by an ethylenediaminetetraacetic acid-citrate complexation route. The use of a disk-shaped membrane in the reactor enabled the direct contact of gaseous oxygen and hydrocarbons to be avoided, and thus, the ethylene content increased. High ethylene yields (up to ≈81 %) were obtained by using a catalytic coating based on Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ), which included macropores produced by the addition of graphite platelets into the screen-printing ink. The promising catalytic results obtained with this catalytically modified membrane reactor are attributed to the combination of 1) the high activity, as a result of the high temperature and oxygen species diffusing through the membrane; 2) the control of oxygen dosing and the low concentration of molecules in the gas phase; and 3) suitable fluid dynamics, which enables appropriate feed contact with the membrane and the rapid removal of products.