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Adsorption, methanation and sulfur poisoning on nickel and ruthenium

Thesis/Dissertation ·
OSTI ID:6222523

The adsorption and methanation of CO and CO/sub 2/ in SiO/sub 2/- and Al/sub 2/O/sub 3/- supported Ni and Ru catalysts were studied with temperature-programmed desorption (TDS) and temperature-programmed reaction (TDR). S poisoning of the reactions was also studied with the same techniques. CO/sub 2/ adsorption on Ni/SiO/sub 2/ and Ru/SiO/sub 2/ was found to be very temperature dependent. On both catalysts CO/sub 2/ dissociated to CO and O atoms, and O atoms reacted with H/sub 2/ at room temperature. The CH/sub 4/ peak temperature did not change with initial coverage, indicating methanation is first order in CO coverage. Thus, following adsorption, CO and CO/sub 2/ methanation proceed by the same mechanism. On Ni/Al/sub 2/O/sub 3/, desorption and decomposition of CO and CO/sub 2/ and their hydrogenation to CH/sub 4/ were found to be influenced by metal-support interactions. Only one distinct CO binding state was present in Ni/Al/sub 2/O/sub 3/ and Ru/Al/sub 2/O/sub 3/, while more than one were observed on Ni/SiO/sub 2/ and Ru/SiO/sub 2/. CO disproportionation was slower on Ni/Al/sub 2/O/sub 3/ than Ni/SiO/sub 2/, but a much larger fraction of CO disproportionated on Ni/Al/sub 2/O/sub 3/. Methanation proceeded faster on Ni/Al/sub 2/O/sub 3/ than on Ni/SiO/sub 2/, but two CH/sub 4/ reaction states were observed on Ni/Al/sub 2/O/sub 3/. S poisoning of the CO and CO/sub 2/ reactions studied were examined as a function of surface coverage on Ni/SiO/sub 2/ and Ru/SiO/sub 2/. On Ni/SiO/sub 2/, S preferentially poisoned strongly-bound CO sites, but the specific rates of CO disproportionation and CO methanation remained unchanged on partially S-covered surfaces. Interaction between adsorbed CO and S on partially S-covered Ru/SiO/sub 2/ caused CO desorption, CO/sub 2/ formation, and methanation to occur at a lower specific rate than on clean Ru/SiO/sub 2/. A new method for preparing supported Ni catalysts by precipitation of Ni-dimethylglyoxime onto SiO/sub 2/ yielded catalysts that can be reduced at low temperature (498/sup 0/K) and have both high dispersions and high percentage reduction to elemental Ni is described.

OSTI ID:
6222523
Country of Publication:
United States
Language:
English