Platinum ammonia oxidation

In the presence of catalyst, usually platinum, ammonia is oxidised by oxygen (and air) to nitrogen oxide. NO. This reaction, used to obtain nitric acid from ammonia (p. 238), can be demonstrated in the laboratory using the apparatus shown in Figure 9.4 the oxygen rate should be slow. 

Dual-Pressure Process. Dual-pressure processes have a medium pressure (ca 0.3—0.6 MPa) front end for ammonia oxidation and a high pressure (1.1—1.5 MPa) tail end for absorption. Some older plants still use atmospheric pressure for ammonia conversion. Compared to high monopressure plants, the lower oxidation pressure improves ammonia yield and catalyst performance. Platinum losses are significantiy lower and production mns are extended by a longer catalyst life. Reduced pressure also results in weaker nitric acid condensate from the cooler condenser, which helps to improve absorber performance. Due to the spHt in operating conditions, the dual-pressure process requires a specialized stainless steel NO compressor. 

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... 

Rebrov, E. V., Duinkerke, S.A., de Croon, M. H. J. M., Schouten, J. C., Optimization of heat transfer characteristics, flow distribution, and reaction processing for a microstructured reactor/ heat-exchanger for optimal peformance in platinum catalyzed ammonia oxidation, Chem. Eng. 93 (2003) 201-216. 

Figure 3.30 Ignition/extinction loops for ammonia oxidation over platinum performed in micro reactors with different membranes [19],...

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 ... 

The situation is different in the case of ammonia oxidation. Both on platinum (156) and nonplatinum (157) catalysts under the conditions of a commercial process, the reaction occurs in the external diffusion region. Diffusion of ammonia rather than of oxygen is determining the rate since the reaction is conducted with oxygen in excess with respect to stoichiometry, as given by (397). Concentration of ammonia at the surface of the catalyst is so small as compared to its concentration in the gas flow that the difference of concentrations that determines the rate of diffusion virtually coincides with the ammonia content in the flow. 

For ammonia oxidation on platinum gauzes under atmospheric pressure, using the analogy between diffusion and heat transfer, an equation was obtained (156) equivalent to the following ... 

To observe ammonia oxidation on platinum in the kinetic region, the reaction must be carried out at low pressures since the decrease in pressure increases the diffusion coefficient and slows down the reaction, both factors favoring the transition to the kinetic region. 

The need to reduce metal losses during ammonia oxidation led to the development of a number of specialized technologies. The first was the substitution of alloy gauzes for pure platinum gauzes. Handforth and Tilley (143) demonstrated that platinum gauzes containing 10-20% Rh lost far less metal than pure platinum screens and were actually somewhat more active than pure... 

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). 

One caveat pertains to the platinum oxide transport model It does not appear to be able to explain the differences in metal weight loss during ammonia oxidation and hydrogen cyanide synthesis by the Andrussow process. In the Andrussow process a mixture of methane, ammonia, and air is used to maintain a high temperature (1200°C) while generating hydrogen cyanide. Alternative processes require energy input, because HCN synthesis is an endothermic reaction. Thus, in both ammonia oxidation and HCN synthesis, platinum or alloy... 

Researchers returned to the oxidation of ammonia in air, (recorded as early as 1798) in an effort to improve production economics. In 1901 Wilhelm Ostwald had first achieved the catalytic oxidation of ammonia over a platinum catalyst. The gaseous nitrogen oxides produced could be easily cooled and dissolved in water to produce a solution of nitric acid. This achievement began the search for an economic process route. By 1908 the first commercial facility for production of nitric acid, using this new catalytic oxidation process, was commissioned near Bochum in Germany. The Haber-Bosch ammonia synthesis process came into operation in 1913, leading to the continued development and assured future of the ammonia oxidation process for the production of nitric acid. 

Recent developments in the ammonia oxidation process have included efforts to reduce catalyst losses in the process. Platinum recovery filters have been installed at various stages in the process. Gold/palladium gauze filter pads have been added on the exit side of the catalyst bed, inside the reactor/converter units. These filters have reportedly ensured a platinum recovery of 80% (Ref. PT4). Another trend has been for the use of additional filters in the downstream units. These filters are of alumino-silicate construction. 

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

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