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Platinum-rhodium gauzes are frequently used to catalyse the high temperature ammonia oxidation step for production of synthetic nitrogen-based fertilisers. The gauzes suffer from Pt loss in the form of platinum dioxide (PtO2), due to the highly exothermic nature of the oxidation reaction. Industrially this is mitigated by installing one or more palladium-nickel catchment gauzes directly downstream of the combustion gauzes, to capture the lost Pt. The Pd-Ni catchment gauzes undergo severe structural modification during operation. In this study, we undertake a systematic study in a laboratory-scale furnace system to determine the role of each of the constituent gases O2, H2O and PtO2 on the structural changes of the Pd-Ni gauzes. In addition, some samples are exposed to real industrial conditions in an ammonia combustion pilot plant reactor. Fresh and spent catchment gauzes are analysed by means of scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA) and inductively coupled plasma mass spectroscopy/optical emission spectroscopy (ICP-MS/OES). By combining analysis of samples from furnace and pilot scale experiments, the main findings are that Pd-Ni gauzes undergo internal oxidation to nickel(II) oxide (NiO); which in the presence of steam results in Ni depletion and that PtO2 vapour causes severe grain reconstruction. Furthermore, in laboratory-scale experiments no significant Pd loss is observed, which is in contrast to observations from the pilot plant where the samples are exposed to real post-ammonia oxidation conditions. Pd loss is likely attributed to some gas species contained in the real post-ammonia oxidation gas stream.
Discovery of the Six Members of the Platinum Group and Their Mineralogical Characterisation[67, (2), 138 ]
The native platinum group elements (PGE), namely, the light PGE (ruthenium, rhodium and palladium) and the heavy PGE (osmium, iridium and platinum), are important historically, scientifically and industrially. Some of the scientists who discovered and refined these metals in the 18th and early 19th centuries, besides being chemists, were also physicians, but all were also knowledgeable of mineralogy. We cannot but be impressed by their achievements because of the complexity of the minerals they studied. The PGE alloys occurred as a fraction of the heavy minerals concentrated from alluvial deposits. Today we can understand why some details of their discovery and mineralogy have not been well understood because of a lack of modern mineralogical studies and misunderstandings of some of the early literature, especially for native palladium and platinum. Though reported widely, highlights of the historical discoveries are here assembled in a single paper and discussed with respect to the mineralogy of the samples studied.