Photoinduced reactivity of titanium dioxide

Advances in the development of novel cobalt Fischer-Tropsch catalysts for synthesis of long-chain hydrocarbons and clean fuels.

The influence of cobalt particle size in the range of 2.6-27 nm on the performance in Fischer-Tropsch synthesis has been investigated for the first time using well-defined catalysts based on an inert carbon nanofibers support material. X-ray absorption spectroscopy revealed that cobalt was metallic, even for small particle sizes, after the in situ reduction treatment, which is a prerequisite for catalytic operation and is difficult to achieve using traditional oxidic supports. The turnover frequency (TOF) for CO hydrogenation was independent of cobalt particle size for catalysts with sizes larger than 6 nm (1 bar) or 8 nm (35 bar), while both the selectivity and the activity changed for catalysts with smaller particles. At 35 bar, the TOF decreased from 23 x 10(-3) to 1.4 x 10(-3) s(-1), while the C5+ selectivity decreased from 85 to 51 wt % when the cobalt particle size was reduced from 16 to 2.6 nm. This demonstrates that the minimal required cobalt particle size for Fischer-Tropsch catalysis is larger (6-8 nm) than can be explained by classical structure sensitivity. Other explanations raised in the literature, such as formation of CoO or Co carbide species on small particles during catalytic testing, were not substantiated by experimental evidence from X-ray absorption spectroscopy. Interestingly, we found with EXAFS a decrease of the cobalt coordination number under reaction conditions, which points to reconstruction of the cobalt particles. It is argued that the cobalt particle size effects can be attributed to nonclassical structure sensitivity in combination with CO-induced surface reconstruction. The profound influences of particle size may be important for the design of new Fischer-Tropsch catalysts.

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Cobalt particle size effects in the fischer- : Tropsch reaction studied with carbon nanofiber supported catalysts

Deactivation of heterogeneous catalysts is a ubiquitous problem that causes loss of catalytic rate with time. This review on deactivation and regeneration of heterogeneous catalysts classifies deactivation by type (chemical, thermal, and mechanical) and by mechanism (poisoning, fouling, thermal degradation, vapor formation, vapor-solid and solid-solid reactions, and attrition/crushing). The key features and considerations for each of these deactivation types is reviewed in detail with reference to the latest literature reports in these areas. Two case studies on the deactivation mechanisms of catalysts used for cobalt Fischer-Tropsch and selective catalytic reduction are considered to provide additional depth in the topics of sintering, coking, poisoning, and fouling. Regeneration considerations and options are also briefly discussed for each deactivation mechanism.

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Heterogeneous Catalyst Deactivation and Regeneration: A Review

National Natural Science Foundation of China [20625310, 20923004]; National Basic Research Program of China [2005CB221408, 2010CB732303]; Research Fund for the Doctoral Program of Higher Education [20090121110007]; Key Scientific Project of Fujian Province [2009HZ0002-1]

Development of Novel Catalysts for Fischer–Tropsch Synthesis: Tuning the Product Selectivity

Temperature programmed reduction (TPR) and hydrogen chemisorption combined with reoxidation measurements were used to define the reducibility of supported cobalt catalysts. Different supports (e.g. Al2O3, TiO2, SiO2, and ZrO2 modified SiO2 or Al2O3) and a variety of promoters, including noble metals and metal cations, were examined. Significant support interactions on the reduction of cobalt oxide species were observed in the order Al2O3>TiO2>SiO2. Addition of Ru and Pt exhibited a similar catalytic effect by decreasing the reduction temperature of cobalt oxide species, and for Co species where a significant surface interaction with the support was present, while Re impacted mainly the reduction of Co species interacting with the support. For catalysts reduced at the same temperature, a slight decrease in cluster size was observed in H2 chemisorption/pulse reoxidation with noble metal promotion, indicating that the promoter aided in reducing smaller Co species that interacted with the support. On the other hand, addition of non-reducible metal oxides such as B, La, Zr, and K was found to cause the reduction temperature of Co species to shift to higher temperatures, resulting in a decrease in the percentage reduction. For both Al2O3 and SiO2, modifying the support with Zr was found to enhance the dispersion. Increasing the cobalt loading, and therefore the average Co cluster size, resulted in improvements to the percentage reduction. Finally, a slurry phase impregnation method led to improvements in the reduction profile of Co/Al2O3.

Fischer–Tropsch synthesis: support, loading, and promoter effects on the reducibility of cobalt catalysts

Fresh and used, unpromoted and noble metal-promoted 15% Co/Al 2 O 3 catalysts were analyzed by XANES and EXAFS to provide insight into catalyst deactivation. XANES analysis of the catalysts gave evidence of oxidation of a fraction of the cobalt clusters by water produced during the reaction. Comparison of XANES derivative spectra to those of reference materials, as well as linear combination fitting with the reference data, suggest that some form of cobalt aluminate species was formed. Because bulk oxidation of cobalt by water is not permitted thermodynamically under normal Fischer–Tropsch synthesis (FTS) conditions, it is concluded that the smaller clusters interacting with the support deviate from bulk-like cobalt metal behavior and these may undergo oxidation in the presence of water. However, in addition to the evidence for reoxidation, EXAFS indicated that significant cobalt cluster growth took place during the initial deactivation period. Promotion with Ru or Pt allowed for the reduction of cobalt species interacting with the support, yielding a greater number of active sites and, therefore, a higher initial catalyst activity on a per gram catalyst basis. However, these additional smaller cobalt clusters that were reduced in the presence of the noble metal promoter, deviated more from bulk-like cobalt, and were therefore, more unstable and susceptible to both sintering and reoxidation processes. The latter process was likely in part due to the higher water partial pressures produced from the enhanced activity. The rate of deactivation was therefore faster for these promoted catalysts.

Fischer-tropsch synthesis: deactivation of noble metal promoted co/al2o3 catalysts

Fischer-tropsch synthesis: characterization and catalytic properties of rhenium promoted cobalt alumina catalysts

Abstract The unpromoted and promoted Fischer–Tropsch synthesis (FTS) catalysts were characterized using techniques such as X-ray diffraction (XRD), temperature programmed reduction (TPR), X-ray absorption spectroscopy (XAS), Brunauer–Emmett–Teller surface area (BET SA), hydrogen chemisorption and catalytic activity using a continuously stirred tank reactor (CSTR). The addition of small amounts of rhenium to a 15% Co/Al2O3 catalyst decreased the reduction temperature of cobalt oxide but the percent dispersion and cluster size, based on the amount of reduced cobalt, did not change significantly. Samples of the catalyst were withdrawn at increasing time-on-stream from the reactor along with the wax and cooled to become embedded in the solid wax for XAS investigation. Extended X-ray absorption fine structure (EXAFS) data indicate significant cluster growth with time-on-stream suggesting a sintering process as a major source of the deactivation. Addition of rhenium increased the synthesis gas conversion, based on catalyst weight, but turnover frequencies calculated using sites from hydrogen adsorption and initial activity were similar. A wide range of synthesis gas conversion has been obtained by varying the space velocities over the catalysts.

The impact of water on the deactivation of a 0.5% Pt-promoted 15% Co/Al 2 O 3 catalyst was studied by XAFS. Catalyst samples were withdrawn from the reactor during synthesis at different partial pressures of added water and cooled in the wax product under an inert gas blanket. Synthesis operating conditions were maintained constant while differing amounts of argon were replaced by added water. Below 25% added water (H 2 O/CO=1.2; H 2 O/H 2 =0.6), the slight negative effect on activity was reversible, and no changes were observed in the EXAFS or XANES spectra. This indicates that the effect of water in this range is most likely kinetic. However, XAFS results strongly suggest that, above 25% water addition, the sudden irreversible loss in activity is due to reaction of the cobalt clusters with the support, forming cobalt aluminate-like species. The XAFS and previously reported activity data indicate that there are two regions for the water effect: at lower H 2 O/CO ratios water influences CO conversion by reversible kinetic effects while at higher H 2 O/CO ratios irreversible oxidation of cobalt occurs.

Jinlin Li

Papers

Fischer–Tropsch synthesis: support, loading, and promoter effects on the reducibility of cobalt catalysts

Fischer-tropsch synthesis: deactivation of noble metal promoted co/al2o3 catalysts

Fischer-tropsch synthesis: characterization and catalytic properties of rhenium promoted cobalt alumina catalysts

Fischer-tropsch synthesis: characterization and catalytic properties of rhenium promoted cobalt alumina catalysts

Fischer–Tropsch synthesis XAFS: XAFS studies of the effect of water on a Pt-promoted Co/Al2O3 catalyst