Iron-ammonia catalysts structure

Insofar as small crystals of nonreducible oxides dispersed on the internal interfaces of the basic structural units (platelets) will stabilize the active catalyst surface Fe(lll), the paracrystallinity hypothesis will probably hold true. But the assumption that this will happen on a molecular level on each basic structural unit is not true. The unique texture and anisotropy of the ammonia catalyst is a thermodynamically metastable state. Impurity stabilization (structural promotion) kinetically prevents the transformation of platelet iron into isotropic crystals by Ostwald ripening [154]. Thus the primary function of alumina is to prevent sintering by acting as a spacer, and in part it may also contribute to stabilizing the Fe(lll) faces [155], [156], [298],... 

A remarkable new observation is also attributed to the presence of the amorphous structure in connection with the ammonia synthesis (165). In situ X-ray diffractograms showed the presence of a-iron in catalysts prepared from unpromoted Fe304 after treatment with hydrogen at 723 K. In contrast, however, promoted industrial (BASF and ICI) ammonia synthe-... 

Magnetic methods are, like x-ray diffraction, a tool for gaining structural information. These methods have been used to measure the effective dispersion of a paramagnetic oxide such as chromia gel or chromia supported on alumina and to determine oxidation states and bonding types under conditions where other procedures are difficult or inapplicable. Magnetic methods are useful also in the identification and estimation of ferromagnetic components such as iron carbide in Pischer-Tropsch or synthetic ammonia catalysts. 

Ruthenium has long been known to be an effective catalyst for ammonia synthesis. However, compared to the traditional iron-based catalysts, studies on ruthenium-based catalysts are limited. The rate determining step of ammonia synthesis, the dissociative adsorption of dinitrogen, has been shown to extremely structure sensitive on both iron and mthenium catalysts. To study this structure sensitivity on ruthenium, density functional theory calculations were performed on Ru(OOl) and Ru(llO) clusters. End-on, side-on, and dissociated adsorption states were investigated on both surfaces. While the Ru(llO) cluster could stabilize aJl three adsorption modes, a minimum energy structure for the side-on adsorption on Ru(OOl) could not be found. It is likely that this side-on mode can provide a low energy pathway to the dissociated state, thereby resulting in faster dissociative adsorption on Ru(llO). 

We now encounter a semantic problem of considerable size. It has been recognised for a very long time that the activity of metal catalysts can be helped by the presence of quite small amounts of substances that of themselves have no or little activity. This concept first achieved prominence in the development of iron catalysts for ammonia catalysts, and of iron and cobalt catalysts for Fischer-Tropsch synthesis, and the term promoter was applied to these substances. They were of two kinds (i) structural promoters such as alumina, which acted as grain stabilisers and prevented metal particle sintering and (ii) electronic promoters such as potassium that entered the metallic phase and actually enhanced its activity. In these cases the metal is the major component, so that the catalyst is a promoted metal rather than a supported metal. 

Prom recent single crystal studies, DFT calculations, and studies of supported catalysts, it was found that ammonia synthesis reaction over ruthenium is an even more structure-sensitive reaction than over iron-based catalysts. In order to... 

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... 

At first this new assumption seemed confirmed by the enhanced activities of catalysts which were obtained by pressing loose powders of iron oxide into dense tablets. Soon, however, it was found that magnetites of another origin than the Swedish specimen yielded no ammonia, or only negligible amounts, in spite of the dense structure of their reduction products. 

Bridger, G.W. Snowden, C.B. (1970) Ammonia synthesis catalysts. In Catalyst Handbook. Wolfe Scientific Books, 126-147 Brindley, G.W. Bish, D.L. (1976) Green rust a pyroaurite type structure. Nature 263 353 Bromfield, S.M. Williams, E.G. (1963) An examination of the biological reduction method for estimating active iron in soils. J. Soil Sd. 14 346-359... 

The transition metals iron and copper have been known since antiquity and have played an important role in the development of civilization. Iron, the main constituent of steel, is still important as a structural material. Worldwide production of steel amounts to some 800 million tons per year. In newer technologies, other transition elements are useful. For example, the strong, lightweight metal titanium is a major component in modern jet aircraft. Transition metals are also used as heterogeneous catalysts in automobile catalytic converters and in the industrial synthesis of essential chemicals such as sulfuric acid, nitric acid, and ammonia. 

Structural promotion A highly dispersed support can provide and (or) stabilize a high surface area of the catalyst supported by it. A typical example is ammonia synthesis where the thermal sintering of the iron catalyst is inhibited by alumina (although the phase configuration is different). 

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