Iron nitride catalysts reduction

The reasoning which led the author to make this first shot in the dark regarding the usefulness of combinations of solid compounds as ammonia catalysts was as follows If we assume that a labile iron nitride is an interminate in the catalytic ammonia synthesis, every addition to the iron which favors the formation of the iron nitride ought to be of advantage. In other words, the hypothesis was used that surface catalysis acts via the formation of intermediate compounds between the catalyst and one or more of the reactants. An experimental support for this theory was the fact that a stepwise synthesis via the formation and successive hydrogen reduction of nitrides had been carried out with calcium nitrides (Haber), and cerium nitrides (Lipski). Later, the author found molybdenum nitride as being the best intermediate for such a stepwise synthesis. 

It is established that reduction of the iron oxide pre-catalyst gives a resulting ot-iron phase. However, it is also well known that iron nitrides (Fe Nj,) can be formed from the reaction between iron and ammonia. ... 

Since the binding site for N2 in the enzyme seems to be a rectangular array of four Fe atoms in the waist region of FeMo-co, perhaps the most relevant model system is Holland s four-iron complex. On reduction with the powerful reductant, KCg, N2 can be split into two coordinated nitrides as shown in Eq. 16.20. In the Haber process, N2 is believed to be split into two coordinated nitrides bound to the surface of the Fe catalyst, so there may be a mechanistic similarity with N2ase. 

Thus, ammonia does not reduce magnetite at an appreciable rate at temperatures below 450°C., and it appeal s that at 450°C. and above, the reduction may be accomplished by decomposition products of ammonia rather than by ammonia itself. This contention is based on the fact that the reduction of fused catalysts with ammonia at 450°C. and 550°C. appeared to be an autocatalytic process that is, the rate of reduction increased with time in the initial part of the experiment. Reduction with hydrogen does not appear to be autocatalytic. It may be postulated that a-iron and nitride formed in the reduction are better catalysts for the ammonia decomposition than iron oxide. 

The reduction of nitrides of iron in pure hydrogen was very rapid, and at 200°C. nitrogen was virtually completely removed from fused iron catalysts in three hours. The hydrogenation of carbonitrides was considerably slower than that of nitrides, and the rate varied inversely with the carbon content of the carbonitride (Table III and reference 19). In... 

Anderson et al. (1964) studied fused iron catalysts which had either been reduced or reduced and nitrided prior to use in fixed-bed reactors, determining reaction kinetics and the effects of the extent of reduction and particle size on catalyst activity. Particle sizes ranged from 42—60 mesh to 4—6 mesh. The catalyst activity increased with smaller particle size until the diameter reached about 0.3 mm for the most active catalysts tested. Catalyst particles were modeled as an active layer of catalyst surrounding an inert core, with the depth of the active layer governed by the reduction temperature. Their calculations allowed them to estimate the effective reactant dif-fusivity, and they were also able to quantify the depth of the active layer of catalyst. Variations in catalyst activity were attributed to the diffusion of reactant through a wax-filled pore and the depth of the active layer. 

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