Iron-alumina catalysts sintering

Further, a stabilization of the total surface of the main catalyst by added substances may explain some promoter effects, but this explanation holds only for a few multicomponent catalysts. For the iron-alumina catalyst, a beneficial stabilizing effect of the promoter alumina on the fine structure of the iron has to be accepted as a partial explanation. The fact that highly dispersed pure iron sinters at temperatures above 300°C. to a considerable extent, and that sintering practically does not occur with iron of the same high dispersion which contains 1 to 2% of alumina, is a strong qualitative support for this concept. In a quantitative way, the work of P. H. Emmett (47) and his associates has proved this point beyond any doubt it gives similarly valuable... 

It should be noted that the results for the formic acid decomposition donor reaction have no bearing for ammonia synthesis. On the contrary, if that synthesis is indeed governed by nitrogen chemisorption forming a nitride anion, it should behave like an acceptor reaction. Consistent with this view, the apparent activation energy is increased from 10 kcal/mole for the simply promoted catalyst (iron on alumina) to 13-15 kcal/mole by addition of K20. Despite the fact that it retards the reaction, potassium is added to stabilize industrial synthesis catalysts. It has been shown that potassium addition stabilizes the disorder equilibrium of alumina and thus retards its self-diffusion. This, in turn, increases the resistance of the iron/alumina catalyst system to sintering and loss of active surface during use. 

A large number of phenomena such as sintering, wetting, shape changes, splitting, etc., occur during heating of iron-on-alumina catalysts in H2 or 02 environments. Some of these phenomena are discussed below ... 

Iron-based catalysts are used in both LTFT and HTFT process mode. Precipitated iron catalysts, used in fixed-bed or slurry reactors for the production of waxes, are prepared by precipitation and have a high surface area. A sihca support is commonly used with added alumina to prevent sintering. HTFT catalysts for fluidized bed apphcations must be more resistant to attrition. Fused iron catalysts, prepared by fusion, satisfy this requirement (Olah and Molnar, 2003). For both types of iron-based catalysts, the basicity of the surface is of vital importance. The probability of chain growth increases with alkali promotion in the order Li, Na, K, and Rb (Dry, 2002), as alkalis tend to increase the strength of CO chemisorption and enhance its decomposition to C and O atoms. Due to the high price o Rb, K is used in practice as a promoter for iron catalysts. Copper is also typically added to enhance the reduction of iron oxide to metallic iron during the catalyst pretreatment step (Adesina, 1996). Under steady state FT conditions, the Fe catalyst consists of a mixture of iron carbides and reoxidized Fe304 phase, active for the WGS reaction (Adesina, 1996 Davis, 2003). 

The industrial catalysts for ammonia synthesis consist of far more than the catalyticaHy active iron (74). There are textural promoters, alumina and calcium oxide, that minimise sintering of the iron and a chemical promoter, potassium (about 1 wt % of the catalyst), and possibly present as K2O the potassium is beheved to be present on the iron surface and to donate electrons to the iron, increasing its activity for the dissociative adsorption of N2. The primary iron particles are about 30 nm in size, and the surface area is about 15 m /g. These catalysts last for years. 

Catalyst composition also depends on the type of reactor used. Fixed-bed iron catalysts are prepared by precipitation and have a high surface area. A silica support is commonly used with added alumina to prevent sintering. Catalysts for fluidized-bed application must be more attrition-resistant. Iron catalysts produced by fusion best satisfy this requirement. The resulting catalyst has a low specific surface area, requiring higher operating temperature. Copper, another additive used in the preparation of precipitated iron catalysts, does not affect product selectivity, but enhances the reducibility of iron. Lower reduction temperature is beneficial in that it causes less sintering. 

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). 

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],... 

The main functions of a carrier or support are usually to lend mechanical strength, increase stability to sintering and provide a larger active surface area than would otherwise be available. There is evidence that, in many instances, compound or complex formation takes place between the catalyst and the support, with a consequent effect on the catalytic properties. The most commonly used support materials are silica, alumina, silica-alumina, titania, silicon carbide, diatomaceous earths, magnesia, zinc oxide, iron oxide and activated carbon. 

The scope of the present paper is to emphasize the role of wetting and spreading in the aging by sintering, and in the redispersion of supported metal catalysts. In the next section, some experimental results regarding the behavior of iron supported on alumina are presented to demonstrate that surface phenomena do play a major role. This is followed by stability considerations which are employed to explain the coexistence of multilayer surface films with crystallites in an oxygen atmosphere and the rupture of thin films into crystallites in a hydrogen atmosphere. 

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. 

The specific surface area of the activated catalyst was found to increase with alumina content up to about 20 m /g at around 2% AI2O3 and then to remain constant (10), demonstrating the role of this additive as structural promoter that (together with other nonreducible phases such as hercynite and calcium ferrite) prevents sintering of the metallic iron particles into low surface area material. These values are compatible with the mean particle sizes of around 30 nm, as determined by mercury porosimetry and seen directly in the scanning electron microscope (Fig. 2) (11). This agreement further shows that the texture of the catalyst permits the N2 molecules of the BET analysis to reach essentially the whole internal surface. 

Structural promotion can take two main forms, although both are concerned with maintaining the effective surface area of the catalyst active component. The use of alumina to generate the pore structure of iron catalysts has been investigated extensively and is discussed fully in an earlier chapter. In the absence of alumina, iron sinters on reduction, giving low surface areas. In the presence of the optimum level of alumina (approximately 2%) surface areas as high as 25 m g" can be obtained although, in the presence of potassium, this is reduced to 10-15 g ... 

Promoters are often used for supported catalysts. These can be grouped into physical and chemical promoters. A physical promoter is an inert substance that inhibits the sintering of crystallites of the catalyst by being present in the form of very fine particles. An example is the incorporation of a small amount of alumina in the conventional iron catalyst used for the synthesis of ammonia, To be effective, the physical promoter must generally be of considerably smaller particle size than that of the active, catalytic species, it must be well dispersed, and it must not... 

---