Journal
JOURNAL OF CATALYSIS
Volume 284, Issue 1, Pages 9-22Publisher
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jcat.2011.08.008
Keywords
Fischer-Tropsch synthesis; Modified alumina; Water; Co; Zn; Mg; Ni; Re
Categories
Funding
- The Norwegian Academy of Science and Letters (VISTA)
- Statoil
- Department of Chemical Engineering at the Norwegian University of Science and Technology
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The effect of different modifications (Zn, Mg, Ni, Re) has been studied for alumina-supported 12 wt% Co-catalysts in the Fischer-Tropsch synthesis (FTS) using a fixed-bed reactor at 483 K, 20 bar, and H-2/CO = 2. Different parameters including calcination temperature, loading, impregnation sequence, and water partial pressure during FTS have been studied. When compared to low surface area alpha-Al2O3, mechanical strength was substantially improved for Ni- and Mg-modified aluminas calcined at very high temperatures (>1400 K), thus making them more suitable for slurry or fluidized-bed operation. However, Mg was found to have a loading-dependent negative effect on both activity and selectivity. The wt% effect was stronger when co-impregnated with Co-Re and calcined at 773 K, than when impregnated on the support and calcined at a high temperature (1173 K) prior to impregnation with Co-Re. Co-impregnating Co-Re with Zn also had a strong loading-dependent negative effect on activity and selectivity, while impregnating Zn on the support and calcining at a high temperature (1173 K) prior to impregnation with Co-Re had no negative effect on the overall C5+ yield. The negative effects of Mg and Zn could not be explained by dispersion or particle size effects and were likely related to a chemical/site effect similar to that of alkalies reported on in the literature. The effect of water for the Ni-modified support was in accordance with the literature, improving reaction rates and C5+, selectivity, while inhibiting olefin hydrogenation, as demonstrated by the propene/propane ratio. The catalysts were characterized with H-2 chemisorption, N-2 sorption, mercury intrusion, X-ray diffraction, temperature-programmed reduction, and O-2 titration. (C) 2011 Elsevier Inc. All rights reserved.
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