Mar 11, 2016
Brauer Hall, Room 12
Presenter: Peter Smirniotis
Panagiotis (Peter) Smirniotis, PhD, received his BS in Chemical Engineering from the University of Patras, Greece in 1989 and his PhD in Chemical Engineering from The University at Buffalo in 1994, working with Dr. Eli Ruckenstein. Peter joined the Chemical Engineering Department at the University of Cincinnati (UC) in 1994 as Assistant Professor and he was promoted to Associate Professor in 1999 and to Professor in 2002.
Nowadays hydrogen is considered to be the most important candidate for a clean energy carrier. As it can be produced from renewable energy sources, it represents one possibility to reduce the negative impact of civilization on the environment such as the greenhouse effect and air pollution. Most of the processes require high purity hydrogen. Production of H2 using membrane reactors via high temperature water gas shift reaction has received much importance in recent years because hydrogen can be selectively permeate through a membrane, and produce high purity hydrogen. The WGS reaction in a membrane reactor (MR) is potentially capable of completing the CO conversion and achieving simultaneous H2/CO2 separation in a single stage operation. A membrane for this reaction typically operates at 400 oC to 550 oC temperatures and pressures ranging from 1-20 bars. Development of catalysts for membrane reactors operating at these high pressures and temperatures have to meet stringent requirements. The present study is aimed at developing various modified ferrite catalysts for high temperature WGS membrane reactor applications. The idea was to stimulate the ferrite formation via doping with certain foreign cations and to stabilize the Fe3+ <=> Fe2+ redox couple. For this purpose, various doped modified ferrite catalysts were prepared using industrially economical and environmental friendly ammonia assisted coprecipitation method. The WGS reaction carried out in the temperature region 400-550 oC and at a stream to CO ratio 3.5 and 1.5 which the conditions used in our membrane reactor. The WGS activity observed was found to be determined by the nature and amount of dopant used in a given case. Temperature programmed reduction measurements (TPR) inferred that Cu selectively promotes the reduction of Hematite (Fe2O3) to Magnetite (Fe3O4) in all modified ferrite catalysts. However, Cu does not promote the reduction of Magnetite to Wustite or reduction of other-metal oxide present in the ferrite. Mössbauer effect studies show distortions in the Fe local environments when Cu is codoped in Magnetite. These distortions are reflected in the internal magnetic field at octahedral sites with characteristic isomer shift ‘d’. Mössbauer effect results also show that Cu enters at M- modified octahedral sites in Magnetite upon activation of the catalysts to replace Fe2+ ions at octahedral sites, and in general, promotes the WGS activity. The Mössbauer spectra and XPS measurements show that Cu plays different role on Fe3+/Fe2+ redox chemistry in the bulk and surface. During the activation some of the Cu enters at the Oh sites of the Magnetite and replaces Fe2+ ions and remaining Cu forms metallic Cu species except for the Fe/Ce. This dual promotional role is responsible for the observed high temperature WGS activity in Cu co-doped M-modified ferrites. These results will be presented.
Organizer / Host: Kim Coleman, (314) 935-5548