Iron-ammonia catalyst promoters

Figure 7.21. Fraction of unoccupied sites, and of sites occupied by atomic nitrogen and NH, as a function of reactor length on a potassium-promoted iron ammonia catalyst at 673 K,...

However, the hydrogenation catalysts can be promoted also by compounds which are ineffective for the iron ammonia catalysts, e.g., by silica and silicates, silicofluorides, borates, and phosphates. An interesting type of hydrogenation catalysts was found in the form of zeolites which by ion exchange were impregnated with heavy metal salts. 

From a study of the mechanism of the poisoning action of water vapors mill oxygen on iron ammonia catalysts 21 and by making certain assumptions, Almquistsu has been able to calculate that in pure iron catalysts about one atom in two thousand is active toward ammonia synthesis, whereas in iron catalysts promoted by alumina about one atom in two hundred is active. This shows the remarkable added activity obtainable by the use of promoters. That the effect is complicated beyond any simple explanation is evidenced further by some of the results of Almquist and Black, These workers have shown that whereas an iron-alumina catalyst shows greater activity toward ammonia synthesis at atmospheric pressure than an iron catalyst containing both alumina and potassium oxide, the hitter catalyst is 50 per cent more active when the pressure is raised to 1(X) atmospheres. 

Chemisorption of Nitrogen and Hydrogen It is generally agreed that at least one of the reactants of every catalytic reaction must be chemisorbed on to the catalyst surface. Such data were, therefore, taken on typical iron ammonia catalysts. Results show that three different types of chemisorption of hydrogen exist on a singly promoted iron catalyst type C ( ) in the temperature range -195 C to... 

Recent commercialization efforts have focused on improved activity synthesis catalysts, which allow ammonia synthesis to be conducted at significantly lower pressures and temperatures. Catalyst manufacturers have focused on enhancing the activity of the iron-based catalyst through the use of promoters (23). 

Research in catalysts for ammonia manufacture is stiU going on, and though the use of supported metals such as mthenium may be two to three times as active as promoted iron oxide, catalysts 50—100 times more active than promoted iron oxide are required to affect process economics significantly. 

The effect of alkali additives on N2 chemisorption has important implications for ammonia synthesis on iron, where alkali promoters (in the form of K or K20) are used in order to increase the activity of the iron catalyst. 

N2 and CO, respectively [31,32], Empirical knowledge about the promoting effect of many elements has been available since the development of the iron ammonia synthesis catalyst, for which some 8000 different catalyst formulations were tested. Recent research in surface science and theoretical chemistry has led to a fairly complete understanding of how a promoter works [33,34],... 

The main emphasis was laid, in this initial work, on Haber s catalysts, e.g., osmium and uranium compounds, as well as on a series of iron catalysts. Some other metals and their compounds which we tested are, as we know today, less accessibble to an activation by added substances than iron. Therefore, they showed no improvement or only small positive effects if used in the form of multicomponent catalysts. Finally, the substances which we added to the metal catalysts in this early stage of our work were mostly of the same type as those which had proved to favor the nitride formation, e.g., the flux promoting chlorides, sulfates, and fluorides of the alkali and alkaline earth metals. Again, we know today that just these compounds do not promote, but rather impair the activity of ammonia catalysts. 

Molybdenum In its pure form, without additions, it is the most efficient catalyst of all the easily obtainable and reducible substances, and it is less easily poisoned than iron. It catalyzes in another way than iron, insofar as it forms analytically easily detectable amounts of metal nitrides (about 9% nitrogen content) during its catalytic action, whereas iron does not form, under synthesis conditions, analytically detectable quantities of a nitride. In this respect, molybdenum resembles tungsten, manganese and uranium which all form nitrides during their operation, as ammonia catalysts. Molybdenum is clearly promoted by nickel, cobalt and iron, but not by oxides such as alumina. Alkali metals can act favorably on molybdenum, but oxides of the alkali metals are harmful. Efficiency, as pure molybdenum, 1.5%, promoted up to 4% ammonia. 

One of the simplest examples for such effects is the oxidation of ammonia with iron oxide-bismuth oxide as a catalyst. Here, the addition of bismuth oxide results in the formation of nitrous oxides as the main product whereas an iron oxide catalyst without bismuth oxide yields nitrogen almost exlcusively. Selectively guiding catalysts become increasingly important in the synthesis of organic compounds, e.g., in the hydrogenation of carbon monoxide where the type of obtainable product can be varied, within wide limits, by the kinds of catalysts and promoters which are employed. 

Recently, independent publications by Kojima and Aika and workers from Topsoe have reported on the high activity and stability of Cs/ C03M03N based catalysts for ammonia synthesis. The activity has been found to be significantly higher than for the commercial iron based catalyst. Table 3 gives a comparison of the ammonia synthesis rates of Cs and K promoted catalysts at various promoter loadings (2, 5, 10 and 30 mol%) for low conversion at 400°C and atmospheric pressure. ... 

From these results, it is concluded that, in a fully reduced catalyst, FeAl204 is not present furthermore, the aluminum inside the iron particle is present as a phase that does not contain iron (e.g., A1203), and this phase must be clustered as inclusions 3 nm in size. These inclusions may well account for the strain observed by Hosemann et al. From the Mossbauer effect investigation then, the process schematically shown in Fig. 17 was suggested for the reduction of a singly promoted iron synthetic ammonia catalyst. Finally, these inclusions and their associated strain fields provide another mechanism for textural promoting (131). 

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. 

In the Haber-Bosch process, ammonia is formed from the reaction between N2 and H2, using a Fe304 (magnetite) catalyst promoted with A1203, CaO, K20 and a moderately small amount of iron and other elements [25], In this mixture, the catalytically active... 

A number of substances show considerable activity as ammonia catalysts. Fe, Os, and Re and nitrides of Mo, W, and U are the best known. Iron in the form of promoted iron catalysts is by far the most important, maybe the only type in industrial use, and except for a few comparisons, iron catalysts will be the only type dealt with in this paper. Furthermore, the discussion will be limited to the type of catalysts made by fusing iron oxides together with the promoter components and subsequently reducing the catalysts. This limitation is not too important, since this type of catalyst is the one most widely used and also the type on which most fundamental work has been done. 

The theory of Kobozev is open to criticism of the character recently stated by Kummer and Emmett (184), who observed that there was a very rapid exchange between the isotopes of nitrogen in the presence of singly and doubly promoted iron synthetic ammonia catalyst. Kobozev (167) had concluded earlier that iron synthetic ammonia catalysts consisted of an ensemble of iron atoms to which were attached the promoter molecules. Each ensemble was capable of adsorbing only one nitrogen molecule further, in accordance with his theory, these ensembles, separated from one another by geometrical barriers, would make the... 

From the early days of ammonia production to the present, the only catalysts that have been used have been iron catalysts promoted with nonreducible oxides. Recently, a ruthenium-based catalyst promoted with rubidium has found industrial application. The basic composition of iron catalysts is still very similar to that of the first catalyst developed by BASF. 

The ammonia synthesis catalyst problem could be considered solved when the catalytic effectiveness of iron in conversion and its onstream life were successfully and substantially improved by adding reduction-resistant metal oxides [232] (Table 15). The iron catalysts promoted with aluminum and potassium oxides proved to be most serviceable [238]. Later, calcium was added as the third activator. Development work in the United States from 1922 can be found in [239]. 

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],... 

With regard to the sulfur bound on the catalyst surface, differences exist between the various types of ammonia catalysts, especially between those that contain alkali and alkaline earth metals and those that are free of them. Nonpromoted iron and catalysts activated only with alumina chemisorb S2N2 and thiophene. When treated with concentrations that lie below the equilibrium for the FeS bond, a maximum of 0.5 mg of sulfur per m2 of inner surface or free iron surface is found this corresponds to monomolecular coverage [382], [383], The monolayer is also preserved on reduction with hydrogen at 620 °C, whereas FeS formed by treatment above 300 °C with high H2S concentrations is reducible as far as the monolayer. For total poisoning, 0.16-0.25 mg S/m2 is sufficient. Like oxygen, sulfur promotes recrystallization of the primary iron particle. 

It is useful, however, to recall an example which does not conform to this condition, the decomposition of ammonia on doubly-promoted iron synthetic ammonia catalysts as studied by Love and EmmettT They found a kinetic equation,... 

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