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Nanocrystalline dense oxide materials as high mixed conductivity membranes for efficient methane conversion into syngas by the oxygen of air; fundamentals of synthesis by advanced methods and factors determining their performance

Ziel

The proposed project is devoted to the development of new nanocrystalline complex oxides ceramic materials with high mixed conductivity for application to promising ecological process of methane conversion. Main problems encountered in this application are due to insufficient oxygen flux at reasonable operating temperatures (600-800C), surface degradation of solid conductors in reducing atmospheres, its cracking due to mechanical stresses created by difference in the oxygen stoichiometry at boundaries contacting with methane or air, respectively; segregation of reduced transition metals leading to coking due to methane decomposition. A promising approach to enhance the oxygen flux and mechanical stability of ceramic membranes could be a development of dense nanocrystalline/nanocomposite materials with a high density of grain boundaries with increased oxygen mobility. Though this hypothesis appears to be a reasonable one, it still has not been systematically verified. Such materials could be obtained by using new advanced mechanochemical technique, conventional hydrolysis-polycondensation routes, Pechini method and their combination as well.

The main goal of this project is to develop nanocrystalline/nanocomposite material with high mixed conductivity and enhanced other properties relatively known today. For realization this material a list of promising systems and modern procedures is selected. Among these systems there are Sr-Fe-Co-O with end members: perovskite, Sr4Fe6O13, brownmillerite structure; perovskite BaCeO3; pyrochlore/fluorite Sr-Sb-O; sheelite Sr-Mo-O. Fast mechanochemical synthesis of complex oxides with nanocrystalline and composite structure is a new technique, which has not yet been realized for fabrication of superionics. Specific features of powders obtained by mechanochemical route, including high ability to consolidation and sintering, high content of vacancies, possibility of synthesis of new metastable compounds which cannot be prepared by other way, in combination with facilities of wet advanced techniques provide a wide field for tailored preparation of enhanced materials. To suppress the grain growth at sintering, nanocomposites of two structurally different systems (fluorite-perovskite), each having a high mixed conductivity will be studied as well. Procedure of doping by appropriate impurities is planned for regulation crystal structure stability, defect concentration, sintering ability and other properties.

The investigations of crystal structure of products, point and other defects, powder morphology, thermal stability and structure transformations will be done by combination of modern methods, including X-Ray Diffraction, ESR, MAS NMR, FT IR and Raman spectroscopy, SEM and TEM, gas adsorption methods, pycnometer, DSC, Thermal analysis technique. The relation between microstructure of ceramics and their properties will be established by studies of conductivity in different atmosphere in a wide range of T and P with the help of complex impedance method and measurements of oxygen permeability. To check performance of developed materials and their long-term stability, catalytic tube flow reactor will be constructed. Characterization of material properties with developed surface promoter will be done in methane conversion process. Criteria of success is formulated: more than 98 % of methane conversion per pass at contact times in the range of 1 sec with oxygen supplied by flux through membrane walls from air.


Achieving of success in this project will result in the breakthrough in very important field of modern chemical and petrochemical industry, namely, efficient conversion of methane into syngas.

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Foundation of Research & Technology
EU-Beitrag
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Adresse
Stadiou 18, Platani
26500 Patras
Griechenland

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