Fischer-Tropsch synthesis in microchannels

Different metallic supports (aluminum foams of 40ppi, honeycomb monolith and micromonolith of 350 and 1180cpsi, respectively) have been loaded with a 20%Co-0.5%Re/γ-Al2O3 catalyst by the washcoating method. Layers of different thicknesses have been deposited onto the metallic supports. The catalytic coatings were characterized measuring their textural properties, adhesion and morphology. These structured catalysts have been tested in the Fischer-Tropsch synthesis (FTS) and compared with a microchannel block presenting perpendicular channels for reaction and cooling. The selectivity depends on the type of support used and mainly on the thickness of the layer deposited. In general, the C5+ selectivity decreased at increasing CO conversion for all of the systems (powder, monoliths, foams and microchannels block). On the other hand, the selectivity to methane increased with the thickness of the catalytic layer due to the higher effective H2/CO ratio over the active sites resulting from the higher diffusivity of H2 compared with CO in the liquid products filling the pores. The C5+ selectivity of the microchannels reactor is higher than that of the structured supports and the powder catalyst.Ministerio de Ciencia e Innovación MAT2006-12386-C05, ENE2009-14522-C0

Preferential oxidation of CO (CO-PROX) over CuOx/CeO2 coated microchannel reactor

The general aspects of the synthesis and characterization results of a CuOx/CeO2 catalyst were presented. In addition the principal steps for manufacturing a microchannel reactor and for the coating of the CuOx/CeO2 catalyst onto the microchannels walls, were also summarized. The catalytic activity of this microchannel reactor during the preferential oxidation of CO (CO-PROX) was evaluated employing a feed-stream that simulates a reformate off-gas after the WGS unit. Two activation atmospheres were studied (H2/N2 and O2/N 2). The reducing pretreatment improved the resistance to deactivation by formation of carbonaceous species over the catalyst surface at high temperatures. The presence of H2O and CO2 in the feed-stream was also analyzed indicating that the adsorption of CO2 inhibited the conversion of CO at lower temperatures because these compounds modified the active sites through the formation of carbonaceous species on the catalyst surface. Finally, the experimental results of the microreactor performance were compared with CFD simulations that were carried out using a kinetic for the CuOx/CeO2 powder catalyst. The experimental results were reasonably well described by the model, thus confirming its validity.Peer Reviewe

Preferential oxidation of CO (CO-PROX) over CuOx/CeO2 coated microchannel reactor

The general aspects of the synthesis and characterization results of a CuOx/CeO2 catalyst were presented. In addition the principal steps for manufacturing a microchannel reactor and for the coating of the CuOx/CeO2 catalyst onto the microchannels walls, were also summarized. The catalytic activity of this microchannel reactor during the preferential oxidation of CO (CO-PROX) was evaluated employing a feed-stream that simulates a reformate off-gas after the WGS unit. Two activation atmospheres were studied (H2/N2 and O2/N 2). The reducing pretreatment improved the resistance to deactivation by formation of carbonaceous species over the catalyst surface at high temperatures. The presence of H2O and CO2 in the feed-stream was also analyzed indicating that the adsorption of CO2 inhibited the conversion of CO at lower temperatures because these compounds modified the active sites through the formation of carbonaceous species on the catalyst surface. Finally, the experimental results of the microreactor performance were compared with CFD simulations that were carried out using a kinetic for the CuOx/CeO2 powder catalyst. The experimental results were reasonably well described by the model, thus confirming its validity.Ministerio de Ciencia e Innovación ENE2009-14522-C05-01, ENE2009-14522-C05-03Junta de Andalucía P09-TEP-545

Gold supported on CuOx/CeO2 catalyst for the purification of hydrogen by the CO preferential oxidation reaction (PROX)

Hydrogen produced from the conversion of hydrocarbons or alcohols contains variable amounts of CO that should be removed for some applications such as feeding low-temperature polymer electrolyte membrane fuel cells (PEMFCs). The CO preferential oxidation reaction (PROX) is particularly well-suited for hydrogen purification for portable and on-board applications. In this work, the synthesis and characterization by XRF, BET, XRD, Raman spectroscopy and H 2-TPR of a gold catalyst supported on a copper-cerium mixed oxide (AuCeCu) for the PROX reaction are presented. The comparison of this catalyst with the copper-cerium mixed oxide (CeCu) revealed that the experimental procedure used for the deposition of gold gave rise to the loss of reducible material by copper lixiviation. However, the AuCeCu solid was more active for CO oxidation at low temperature. A kinetic study has been carried over the AuCeCu catalyst for the PROX reaction and compared with that of the CeCu catalyst. The main difference between the models affected the contribution of the CO adsorption term. This fact may be related to the surface electronic activity produced by the interaction of the cationic species in the AuCeCu solid, able to create more active sites for the CO adsorption and activation in the presence of gold.Peer Reviewe

Iron-modified ceria and Au/ceria catalysts for Total and Preferential Oxidation of CO (TOX and PROX)

Iron-modified ceria supports containing different molar percentages of Fe (0%, 10%, 25%, and 50%) were synthesized by thermal decomposition of the metal propionates. The formation of a Ce-Fe oxide solid solution is evidenced through XRF, XRD, BET and Raman spectroscopy. For iron contents above 25% the formation of ¿-Fe2O3 was detected, pointing out the formation of the isolated oxides. The catalytic activity of the Fe-modified catalysts in the Total Oxidation of CO reaction (TOX) is higher than for the bare CeO 2 material. The synergy between Ce and Fe shows a maximum for 10% Fe content (CeFe10), catalyst that shows the highest CO conversion per atom of Fe incorporated. Gold catalyst was also prepared on CeFe10 and its catalytic activity compared with Au/CeO2 catalyst. The addition of iron to the gold catalyst resulted in an enhancement of the catalytic activity for CO oxidation especially at low temperature. This Au/CeFe10 catalyst was also active and selective with excellent stability in the Preferential Oxidation of CO (PROX) showing a higher CO conversion than the Au/CeO2 catalyst at temperatures below 150 °C being hardly affected by the presence of CO 2 and H2O in the gas stream.Peer Reviewe

Structured and micro-structured catalysts: A fascinating future for a sustainable world – A special issue in tribute to the careers of Professors Mario Montes and Jos´e Antonio Odriozola

Peer reviewe