Rhodium ammonia oxidation

The most important use of ammonia is in the production of nitric acid (HNO3). Ammonia burns in oxygen, releasing hydrogen to form water and free nitrogen. With the catalysts platinum and rhodium, ammonia is oxidized and reacted with water to form nitric acid. Nitric acid treated... 

By far the most important use of the platinum metals is for catalysis. The largest single use is in automobile catalytic converters. Platinum is the principal catalyst, but catalytic converters also contain rhodium and palladium. These elements also catalyze a wide variety of reactions in the chemical and petroleum industry. For example, platinum metal is the catalyst for ammonia oxidation in the production of nitric acid, as described in Pt gauze, 1200 K... 

Currently, nitric acid is manufactured exclusively by catalytic oxidation of ammonia. Platinum or platinum-rhodium is an effective catalyst of this oxidation (Ostwald process). Three basic steps in such ammonia oxidation process are (1) oxidation of ammonia to form nitric oxide ... 

Other workers (165) used X-ray photoelectron spectroscopy (XPS) to examine the influence of ammonia oxidation on the surface composition of alloy gauzes. After several months on stream, the surface was covered by the same types of highly faceted structures noted by others. As illustrated in Fig. 14, XPS analysis provides evidence that the top microns, and in particular the top 100 A of the surface, were enriched in rhodium. This enrichment was attributed to the preferential volatilization of platinum oxide. The rhodium in the surface layers was present in the oxide form. Other probes confirm the enrichment of the surface in rhodium after ammonia oxidation (166). Rhodium enrichment has been noted by others (164, 167), and it has been postulated that in some cases it leads to catalyst deactivation (168). 

Fig. 14. Rhodium enrichment of a Pt/Rh gauze (10% Rh) after ammonia oxidation, (a) Photoelectron spectra (Rh 3d and Pt 4d) of a moderately oxidized gauze, (b) In-depth analysis of a used gauze. One minute of sputtering is roughly equivalent to 20 A (165).

F. Sperner and W. Hohmann, Rhodium-Platinum Gauzes for Ammonia Oxidation, Platinum Metals Review. Volume 20, Number 1, DD. 2-20 (1976). 

Figure 9.1. Effect of rhodium content on catalyst efficiency in ammonia oxidation.

At present, the main industrial catalyst of ammonia oxidation is platinum and its alloys with aluminium and rhodium. Taking into account the deficit and high cost of platinum metals, the dcCTcasing of the consumption and losses of platinum metals is an urgent problem. Therefore, several compositions of complex oxide catalysts have been developed with iron (111), cobalt and chromium oxides as an active component. Complex oxides with perovskite structure are used as new catalysts they provide selective oxidation of ammonia with an yield not less than 90 %. The authors of [33] proposed to use perovskite powders LaMeOj, where Me=Fe, Co, Ni, Cr, Mn, and La,.,Sr,Me03, where Me=Co, Mn and x=0.25-0.75. To prepare these compounds, they used the precipitation by tetraethyl ammonia from diluted nitrate solutions taken at necessary ratios. The powders as prepared are poorly molded as in the form of honeycomb stractures as well as in the form of simple granules. 

Figure 4 Schematic differences between woven gauzes and the new, knitted gauzes. The lower photograph is a micrograph of the surface developed on a knitted platinum/rhodium gauze after use in an ammonia oxidation plant.

A development in catalyst support systems in which half of the 5-10% rhodium-platinum alloy gauzes were replaced by nonnoble metal supports or by ordinary metal catalysts gave cost economies without adversely affecting operating efficiency [47]. More recently, ammonia oxidation in a two-bed system (Pt gauzes followed by monolithic oxide layers) gave nearly the same ammonia conversion while reducing platinum losses by 50% [48]. 

The cobalt oxide catalyst for oxidation of ammonia, worked out in our laboratory, has the form of granules of high mechanical strength, owing to which it may be applied both in stationary and in fluidized beds. The yields of ammonia oxidation to NO measured during laboratory and large laboratory studies of that catalyst exceeded 95%. Optimum temperature of ammonia oxidation process carried out on our catalyst (760-780 ) is lower than that needed for platinum-rhodium wire gauze currently appli in industrial reactors. 

A major step in the production of nitric acid [7697-37-2] (qv) is the catalytic oxidation of ammonia to nitric acid and water. Very short contact times on a platinum—rhodium catalyst at temperatures above 650°C are required. 

Ammonia vapor is mixed with air and converted into nitrogen oxide at an elevated temperature in the presence of a catalyst, which generally contains noble metals such as platinum and rhodium. The optimal gauge temperature is maintained by controlled ammonia and combustion air preheating. The reaction is highly exothermic ... 

Similarity with cobalt is also apparent in the affinity of Rh and iH for ammonia and amines. The kinetic inertness of the ammines of Rh has led to the use of several of them in studies of the trans effect (p. 1163) in octahedral complexes, while the ammines of Ir are so stable as to withstand boiling in aqueous alkali. Stable complexes such as [M(C204)3], [M(acac)3] and [M(CN)5] are formed by all three metals. Force constants obtained from the infrared spectra of the hexacyano complexes indicate that the M--C bond strength increases in the order Co < Rh < [r. Like cobalt, rhodium too forms bridged superoxides such as the blue, paramagnetic, fCl(py)4Rh-02-Rh(py)4Cll produced by aerial oxidation of aqueous ethanolic solutions of RhCL and pyridine.In fact it seems likely that many of the species produced by oxidation of aqueous solutions of Rh and presumed to contain the metal in higher oxidation states, are actually superoxides of Rh . ... 

Nitric acid is commercially produced hy oxidizing ammonia with air over a platinum-rhodium wire gauze. The following sequence represents the reactions occurring over the heterogeneous catalyst ... 

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