Metal supported iron-ruthenium catalysts

The reactions are catalyzed by transition metals (cobalt, iron, and ruthenium) on high-surface-area silica, alumina, or zeolite supports. However, the exact chemical identity of the catalysts is unknown, and their characterization presents challenges as these transformations are carried out under very harsh reaction conditions. Typically, the Fischer-Tropsch process is operated in the temperature range of 150°C-300°C and in the pressure range of one to several tens of atmospheres [66], Thus, the entire process is costly and inefficient and even produces waste [67]. Hence, development of more economical and sustainable strategies for the gas-to-liquid conversion of methane is highly desirable. 

Rare earth oxides are useful for partial oxidation of natural gas to ethane and ethylene. Samarium oxide doped with alkali metal halides is the most effective catalyst for producing predominantly ethylene. In syngas chemistry, addition of rare earths has proven to be useful to catalyst activity and selectivity. Formerly thorium oxide was used in the Fisher-Tropsch process. Recently ruthenium supported on rare earth oxides was found selective for lower olefin production. Also praseodymium-iron/alumina catalysts produce hydrocarbons in the middle distillate range. Further unusual catalytic properties have been found for lanthanide intermetallics like CeCo2, CeNi2, ThNis- Rare earth compounds (Ce, La) are effective promoters in alcohol synthesis, steam reforming of hydrocarbons, alcohol carbonylation and selective oxidation of olefins. 

We are investigating bifunctional catalysts in which one component of the catalyst adsorbs or oxidizes CO and the other component dissociates water. Our present research is focusing on metal-support combinations to promote this bifunctional mechanism. The metallic component is chosen to adsorb CO at intermediate adsorption strengths (platinum [Pt], Ru, palladium [Pd], PtRu, PtCu, cobalt [Co], ruthenium [Ru], silver [Ag], iron [Fe], copper [Cu], and molybdenum [Mo]). The support is chosen to adsorb and dissociate water, typically a mixed-valence oxide with redox properties or oxygen... 

The early development of catalysts for ammonia synthesis was based on iron catalysts prepared by fusion of magnetite with small amounts of promoters. However, Ozaki et al. [52] showed several years ago that carbon-supported alkali metal-promoted ruthenium catalysts exhibited a 10-fold increase in catalytic activity over conventional iron catalysts under the same conditions. In this way, great effort has been devoted during recent years to the development of a commercially suitable ruthenium-based catalyst, for which carbon support seems to be most promising. The characteristics of the carbon surface, the type of carbon material, and the presence of promoters are the variables that have been studied most extensively. 

Studying non-classical preparation procedures, it has been already shown that ultrasound play a relevant role in preparing high dispersed pure amorphous iron [3]. Moreover, it has been recently proposed that ultrasound can improve the metal dispersion in alumina supported ruthenium catalyst 14, 51. 

The inhibition effect of promoters on the methanation. R is commonly believed that for fused iron catalyst, AI2O3 increases iron surface area (structural effect), while K2O donates electrons to iron atom, and increases electron density and enhances the activity of ammonia synthesis reaction (electronic effect). For the supported ruthenium catalysts, the effect of promoters on performances becomes more complex due to the existence of support. ARhough there are a lot of studies on the role of promoter for ammonia synthesis reaction, the chemical state, the distribution and the mechanism are still unclear. The role of promoters include covering chemisorption s site, donating electron to active metal, direct interacting with the adsorption intermediate and electrostatic field and so For supported... 

The elTiciency of cobalt and ruthenium catalysis is not very sensitive to the presence of promoters )21]. With cobalt, the addition of thorium and alkali promoters increases wax production and supports were incorporated to increase the active metal surface area. On the other hand, promoters and supports are essentia) for iron catalysts. 

The metal catalysts active for steam reforming of methane are the group VIII metals, usually nickel. Although other group VIII metals are active, they have drawbacks for example, iron rapidly oxidizes, cobalt cannot withstand the partial pressures of steam, and the precious metals (rhodium, ruthenium, platinum, and palladium) are too expensive for commercial operation. Rhodium and ruthenium are ten times more active than nickel, platinum, and palladium. However, the selectivity of platinum and palladium are better than rhodium [1]. The supports for most industrial catalysts are based on ceramic oxides or oxides stabilized by hydraulic cement. The commonly-used ceramic supports include a-alumina, magnesia, calcium-aluminate, or magnesium-alu-minate [4,8]. Supports used for low temperature reforming (< 770 K) are... 

A key question is whether the diatomic molecule in its interaction with metal surfaces remains molecular or dissociates into carbon and oxygen. Broden et al. (3) predicted, by the perturbation of molecular orbitals for CO adsorbed, that only iron could dissociate CO. However, other metals in Group VIII such as nickel (A) ruthenium (5) and rhodium (6) can dissociate CO. Recently Ichikawa et al.(7) observed that disproportionation of CO to CO2 and carbon occurs on small particles of silica-supported palladium. These results show that carbon deposition phenomena may occur via either dissociation of CO on the metals used or disproportionation of CO to CO and carbon on small platinum particles. Cant and Angove (8) studied the apparent deactivation of Pt/Si02 catalyst for the oxidation of carbon monoxide and they suggested that adsorbed CO forms patches and that oxygen atoms are gradually consumed. 

This new single-step synthesis unites the simplicity of preparation and lower production costs, with the outstanding properties of the final catalysts. By the single-step procedure proposed here, deposition of dispersed nanoparticles of noble metals on ceramic supports with customised textural properties and shape was achieved. Noble metals including platinum, palladium, rhodium, ruthenium, iridium, etc. and metal oxides including copper, iron, nickel, chromimn, cerium oxides, etc on sepiolite or its mixtures with alumina, titania, zirconia or other refractory oxides have been also studied. 

Iron and its compounds (carbide, nitride), as well as ruthenium, cobalt, rhodium, and molybdenum compounds (sulfide, carbide), are used most frequently to produce high-molecular-weight hydrocarbons. Iron can be prepared as a high-surface-area catalyst (==300 m /g) even without using a microporous oxide support. 7-AI2O3, Ti02, and silica are frequently used as supports of the dispersed transition-metal particles. Recently zeolites, as well as thorium oxide and lanthanum oxide, have... 

When titania is used as a support for cobalt iron or ruthenium, veiy active catalysts are prepared, indicating the importance of certain oxide-metal interfaces as active sites for CO hydrogenation. 

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