Activation of Cobalt Foil Catalysts for CO Hydrogenation

CO hydrogenation has been studied on cobalt foils as model catalysts for Fischer–Tropsch (FT) synthesis. The effect of pretreatment (number of calcinations and different reduction times) for cobalt foil catalysts at 220 °C, 1 bar, and H2/CO = 3 has been studied in a microreactor. The foils were examined by scanning electron microscopy (SEM). It was found that the catalytic activity of the cobalt foil increases with the number of pretreatments. The mechanism is likely an increase in the available cobalt surface area from progressively deeper oxidation of the foil, supported by surface roughness detected by SEM. The highest FT activity was obtained using a reduction time of only 5 min (compared to 1 and 30 min). Prolonged reduction caused the sintering of cobalt crystallites, while too short of a reduction time led to incomplete reduction and small crystallites susceptible to low turn-over frequency from structure sensitivity. Larger crystals from longer reduction times gave increased selectivity to heavier components. The paraffin/olefin ratio increased with the increasing number of pretreatments due to olefin hydrogenation favored by enhanced cobalt site density. From the results, it is suggested that olefin hydrogenation is not structure sensitive, and that mass transfer limitations may occur depending on the pretreatment procedure. Produced water did not influence the results for the low conversions experienced in the present study (<6%).

The Mitigation of CO Present in the Water–Gas Shift Reformate Gas Over IR-TiO2 and IR-ZrO2 Catalysts

CO hydrogenation and oxidation were conducted over Ir supported on TiO2 and ZrO2 catalysts using a feed mimicking the water–gas shift reformate stream. The influence of the support interaction with Ir and the catalysts’ redox and CO chemisorption properties on activity and selectivity were evaluated. Both catalysts oxidised CO to CO2 in the absence of H2, and a conversion of 70% was obtained at 200 °C. For the CO oxidation in the presence of H2 over these catalysts, the oxidation of H2 was favoured over CO due to H2 spillover occurring at the active metal and support interface, resulting in the formation of interstitials catalysed by Ir. However, both catalysts showed promising activity for CO hydrogenation. Ir-ZrO2 was more active, giving 99.9% CO conversions from 350 to 370 °C, with high selectivity towards CH4 using minimal H2 from the feed. Furthermore, results for the Ir-ZrO2 catalyst showed that the superior activity compared to the Ir-TiO2 catalyst was mainly due to the reducibility of the support and its interaction with the active metal. Controlling the isoelectric point during the synthesis allowed for a stronger interaction between Ir and the ZrO2 support, which resulted in higher catalytic activity due to better metal dispersions, and higher CO chemisorption capacities than obtained for the Ir-TiO2 catalyst.