(532e) Highly Active and Stable Silica-Doped, Alumina-Supported Fe Fischer-Tropsch Catalyst
AIChE Annual Meeting
2013
2013 AIChE Annual Meeting
Catalysis and Reaction Engineering Division
CO Hydrogenation
Wednesday, November 6, 2013 - 4:35pm to 4:55pm
Typical commercial iron Fischer-Tropsch
(FT) catalysts are unsupported and consist of precipitated iron promoted with
copper, potassium, and SiO2. However,
most precipitated iron catalysts are structurally too weak to be used in
slurry-bubble column reactors (SBCR), the most thermally efficient and
economical reactors for FTS [1]. The use of a carrier or support has the
potential to greatly increase the strength and longevity of these catalysts;
however, previous research on silica- and alumina-supported Fe has not been
promising as it has shown activity and productivity values ½ and ¼,
respectively, of those for unsupported iron [2].
To overcome the low activity and attrition
resistant problems, in this study we explored using 4 different alumina
supports, including an original silica-doped g-alumina (AlSi). We
found that AlSi after thermal treatment at 1100°C still maintained excellent pore properties (200 m2/g, 1.06 cm3/g, 24 nm) which allowed higher iron
loadings (40%) without pore blocking or iron aggregation. The 4 catalysts were
prepared by co-impregnation with non-aqueous solution, were tested in a fixed bed reactor, and were
compared to unsupported Fe catalysts from the literature. A
St. Gobain alumina-based catalyst and the AlSi-based catalyst showed the best
activity. Both were nearly three-fold more active than the
silica-supported catalyst reported by Bukur [2], and 6-fold more active than
his alumina-supported catalyst. More importantly, the activity of our catalysts
at 260°C was nearly 20% higher than Bukur's most active unsupported
catalyst. In addition the AlSi based catalyst was tested for 700 h and showed
excellent stability. In fact its activity after 700 h is about 15% higher than its initial activity.
The
results of the present work indicate that the preparation protocol used here produces
supported iron catalysts of high extent of reduction, high dispersion, very
high FTS activity, moderate hydrocarbon selectivity, and excellent stability.
In addition it was shown that our high pore volume SiO2 doped
alumina (AlSi) support served as a superior support for supported Fe FT
catalysts.
References:
1. Bukur, D.B. and X. Lang, Highly Active and Stable Iron Fischer-Tropsch Catalyst for Synthesis Gas Conversion to Liquid Fuels. Ind. Eng. Chem. Res., 1999. 38(9): p. 3270?3275.
2. Bukur, D.B. and C. Sivaraj, Supported iron catalysts for
slurry phase Fischer?Tropsch
synthesis. Applied Catalysis A: General,
2002. 231(1-2): p. 201-214.