期刊
ACS CATALYSIS
卷 12, 期 15, 页码 -出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.2c01955
关键词
preferential oxidation; selective hydrogen combustion; SHC; PROX; H-2 removal; Ni-based catalysts; microkinetic modeling
资金
- European Union [768919]
- Flemish Research Foundation (FWO) under the CATCO2RE project [S004118N]
- Flemish Government and Flanders Innovation & Entrepreneurship (VLAIO) through the Moonshot project D2M [HBC.2019.0107]
- Research Foundation -Flanders (FWO)
- Flemish Government
- Nadadur Veeraraghavan Srinath (Ghent University)
The study investigates the selective oxidation of hydrogen in CO-rich streams resembling steel mill gases and finds that high water selectivity can be achieved under certain conditions, reducing the industry's carbon footprint.
The shift toward unconventional CO/CO2 sources for chemicals production is accompanied by several challenges, e.g., those associated with their composition. The use of CO/CO2-rich steel mill gases as an alternative feedstock promotes carbon circularity, contributing to reducing the industry's carbon footprint. The upgrading of steel mill gases as a carbon source in some cases requires efficient and selective H-2 removal. This study investigates the preferential oxidation of H-2 in CO-rich streams, resembling blast furnace steel mill gas, over a 15 wt % Ni/gamma-Al2O3 catalyst combining experimental and modeling techniques. A reaction temperature of 310 degrees C was selected to prevent carbonyl-induced sintering for CO partial pressures of 26 kPa and higher. Despite the excess CO, an O-2-to-H2O selectivity of 65% was achieved at full O-2 conversion for an optimum H-2/O-2 inlet ratio of 3.3. By investigating the effects of the CO and H-2 inlet partial pressures, a relation between the CO/H-2 inlet ratio and the water selectivity was established. Catalyst stability was confirmed over a 24 h oxidation test. In situ TPO showed negligible amounts of deposited carbon, and subsequent XRD analysis showed only a minor change in diffraction patterns. First-principles microkinetic modeling attributes the high water selectivity over O*-saturated Ni(111) to a 33 kJ mol(-1) difference in barrier between H* and CO* oxidation, which compensates the low H*/CO* coverage ratios. The model further highlights the relation between the CO/H-2 inlet ratio and the water selectivity with changes in the CO*/H* coverage ratio. The microkinetic model predicts a water selectivity of 91% at 310 degrees C, significantly higher than the experimental data. Combining several experimental tests with characterization techniques, we attribute the somewhat lower experimental selectivity to WGS activity, possible formation of surface NiO species that are highly active for CO-PROX, and undercoordinated Ni sites that are active for CO dissociation.
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