Effect of Cu and Sn promotion on the catalytic deoxygenation of model and algal lipids to fuel-like hydrocarbons over supported Ni catalysts

The ability of Cu and Sn to promote the performance of a 20% Ni/Al2O3 catalyst in the deoxygenation of lipids to fuel-like hydrocarbons was investigated using model triglyceride and fatty acid feeds, as well as algal lipids. In the semi-batch deoxygenation of tristearin at 260 °C a pronounced promotional effect was observed, a 20% Ni-5% Cu/Al2O3 catalyst affording both higher conversion (97%) and selectivity to C10-C17 alkanes (99%) in comparison with unpromoted 20% Ni/Al2O3 (27% conversion and 87% selectivity to C10-C17). In the same reaction at 350 °C, a 20% Ni-1% Sn/Al2O3 catalyst afforded the best results, giving yields of C10-C17 and C17 of 97% and 55%, respectively, which contrasts with the corresponding values of 87 and 21% obtained over 20% Ni/Al2O3. Equally encouraging results were obtained in the semi-batch deoxygenation of stearic acid at 300 °C, in which the 20% Ni-5% Cu/Al2O3 catalyst afforded the highest yields of C10-C17 and C17. Experiments were also conducted at 260 °C in a fixed bed reactor using triolein − a model unsaturated triglyceride − as the feed. While both 20% Ni/Al2O3 and 20% Ni-5% Cu/Al2O3 achieved quantitative yields of diesel-like hydrocarbons at all reaction times sampled, the Cu-promoted catalyst exhibited higher selectivity to longer chain hydrocarbons, a phenomenon which was also observed in experiments involving algal lipids as the feed. Characterization of fresh and spent catalysts indicates that Cu enhances the reducibility of Ni and suppresses both cracking reactions and coke-induced deactivation

Infrared Studies on Bimetallic Copper/Nickel Catalysts Supported on Zirconia and Ceria/Zirconia

Infrared spectroscopy has been employed for a detailed characterization of ZrO2 and CeO2/ZrO2 supported nickel and copper/nickel catalysts to be utilized for methane decomposition. Adsorption of CO at 303 K was performed in order to determine the surface composition and accessible adsorption sites. Alloy formation occurred during reduction, as indicated by a red-shift of the vibrational band of CO on Ni: by 27 cm−1 on nickel-rich CuNi alloy, by 34 cm−1 on 1:1 Cu:Ni and by 36 cm−1 on copper-rich CuNi alloy. CuNi alloy formation was confirmed by X-ray absorption spectroscopy during reduction revealing a considerably lower reduction temperature of NiO in the bimetallic catalyst compared to the monometallic one. However, hydrogen chemisorption indicated that after reduction at 673 K copper was enriched at the surface of the all bimetallic catalysts, in agreement with IR spectra of adsorbed CO. In situ IR studies of methane decomposition at 773 K demonstrated that the addition of Cu to Ni strongly reduced coking occurring preferentially on nickel, while maintaining methane activation. Modification of the zirconia by ceria did not have much effect on the adsorption and reaction properties. Ceria-zirconia and zirconia supported samples exhibited very similar properties and surface chemistry. The main difference was an additional IR band of CO adsorbed on metallic copper pointing to an interaction of part of the Cu with the ceria.ISSN:1011-372XISSN:1572-879