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At least 505 records · Page 28

Porosity in Sr 1-x Ca x FeO 3-δ oxygen carriers: The role of surface area and pretreatment on storage activity

Perovskite oxides have generated interest as robust, low-temperature oxygen carrier materials for a variety of clean energy applications, including chemical looping gasification and air separations. Methods to improve O 2 desorption kinetics are vital to allow these carriers to compete economically with traditional metal oxide carriers or cryogenic separations. In this report we investigated the cumulative roles that surface area, pretreatment, and elemental composition have on the oxygen storage properties of a state-of-the-art carrier system, Sr 1-x Ca x FeO 3-δ (x = 0.20, 0.25, 0.30) synthesized using multiple methods. Porous materials synthesized by the Pechini, or citrate, method had their surface area controlled using the synthesis temperature. The high surface area of the Sr 0.7 Ca 0.3 FeO 3-δ materials is most beneficial at low operating temperatures, such as 350 and 400 °C, as their reduction rates are twice as fast as those obtained with their bulk counterparts. These effects are observed at higher operating temperatures and within a single composition, but temperature tunability using variable Ca 2+ substitution in the Sr 1-x Ca x FeO 3-δ overshadows the improvements gained from higher surface areas. Additionally, we establish that pretreatment in N2 at an elevated temperature is necessary to enhance kinetics further. For maximum efficiency, pretreatment at the synthesis temperature is suggested for the Pechini method-synthesized systems, whereas 800 °C is adequate for bulk materials.

36 MATERIALS SCIENCE↗

Permeability and porosity of hydrate-bearing sediments in the northern Gulf of Mexico

Hydrate-bearing sands are being actively explored because they contain the highest concentrations of hydrate and are the most economically recoverable hydrate resource. However, relatively little is known about the mechanisms or timescales of hydrate formation, which are related to methane supply, fluid flux, and host sediment properties such as permeability. We used logging-while-drilling data from locations in the northern Gulf of Mexico to develop an effective medium theory-based model for predicting permeability based on clay-sized sediment fraction. The model considers permeability varying between sand and clay endpoint permeabilities that are defined from laboratory data. We verified the model using permeability measurements on core samples from three boreholes, and then used the model to predict permeability in two wells drilled in Walker Ridge Block 313 during the Gulf of Mexico Gas Hydrate Joint Industry Project Leg II expedition in 2009. We found that the cleanest sands (clay-sized fraction <0.05) had intrinsic (hydrate-free) permeability contrasts of 5-6 orders of magnitude with the surrounding clays, which is sufficient to provide focused hydrate formation due to advection of methane from a deep source or diffusion of microbial methane from nearby clay layers. In sands where the clay-sized fraction exceeds 0.05, the permeability reduces significantly and focused flow is less pronounced. In these cases, diffusion of dissolved microbial methane is most likely the preferred mode of methane supply for hydrate formation. In conclusion, our results provide important constraints on methane supply mechanisms in the Walker Ridge area and have global implications for evaluating rates of methane migration and hydrate formation in hydrate-bearing sands.

58 GEOSCIENCES↗