Johnson Matthey Technology Review - Volume 63, Issue 4, 2019

Recent advances in energy technology are driven by the need to mitigate climate change and find sustainable, non-polluting ways to power our communities. However, a large proportion of the impact arises from the materials used to make energy devices (1) and it is therefore important to generate and use materials effectively, while finding ways to minimise waste, energy use and harmful chemicals during device fabrication. This editorial describes the materials science toolbox for making the most of our resources.

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.

Interfaces are a type of extended defect which govern the properties of materials. As the nanostructuring of materials becomes more prevalent the impact of interfaces such as grain boundaries (GBs) becomes more important. Computational modelling of GBs is vital to the improvement of our understanding of these defects as it allows us to isolate specific structures and understand resulting properties. The first step to accurately modelling GBs is to generate accurate descriptions of the structures. In this paper, we present low angle mirror tilt GB structures for fluorite structured materials (calcium fluoride and ceria). We compare specific GB structures which are generated computationally to experimentally known structures, wherein we see excellent agreement. The high accuracy of the method which we present for predicting these structures can be used in the future to predict interfaces which have not already been experimentally identified and can also be applied to heterointerfaces.

Microemulsions were used to develop a catalyst with high selectivity towards ethylene and ethane while maintaining considerable methane (CH4) conversion. The use of this technique to produce lanthanum nanoparticles was studied under different conditions. Temperature was shown to have the most significant effect on the final material properties providing a minimum crystallite size at 25°C. The morphology observed for all the samples was flake or needle like materials containing nanocrystallites. To obtain the catalytically active materials a thermal treatment was needed and this was studied using in situ X-ray diffraction (XRD). This analysis demonstrated that the materials exhibited significant changes in phase and crystallite size when submitted to thermal treatment and these were shown to be difficult to control, meaning that the microemulsion synthesis method is a challenging route to produce La nanoparticles in a reproducible manner. The materials were tested for oxidative coupling of methane (OCM) and no correlation could be observed between the ‘as synthesised’ crystallite size and activity. However, the presence of La carbonates in the materials produced was deemed to be crucial to ensure an adequate OCM activity.

Solvent extraction is a key separation process in several industries. Mixer-settlers and agitated or pulsed columns are mainly used as liquid-liquid contactors. However, these units require large solvent inventories and long residence times, while flow fields are often not uniform and mixing is poor. These drawbacks can be overcome with process intensification approaches where small channel extractors are used instead. The reduced volumes of small units in association with the increased efficiencies facilitate the use of novel, often expensive, but more efficient and environmentally friendly solvents, such as ionic liquids. The small throughputs of intensified contactors, however, can limit their full usage in industrial applications, thus robust scale-up strategies need to be developed. This paper reviews promising intensified technologies for liquid-liquid extractions based on small channels. In particular, extractions in single channels and in confined impinging jets are considered. The increase in throughput via scale-out approaches with appropriate manifolds is discussed, based on the use of many channels in parallel. The combination of small channels and centrifugal forces is exploited in counter-current chromatography (CCC) systems where many mixing and settling steps are combined within the contactors. Scale up is possible via centrifugal partition chromatography (CPC) configurations.