Nitrogen is an essential element to plants, animals, human beings and all the other living things on earth. Nitrogen fixation, which converts inert atmospheric nitrogen into ammonia or other valuable substances, is a very important part of the nitrogen cycle. The Haber-Bosch process plays the dominant role in the chemical nitrogen fixation as it produces a large amount of ammonia to meet the demand from the agriculture and chemical industries. However, due to the high energy consumption and related environmental concerns, increasing attention is being given to alternative (greener) nitrogen fixation processes. Among different approaches, plasma-assisted nitrogen fixation is one of the most promising methods since it has many advantages over others. These include operating at mild operation conditions, a green environmental profile and suitability for decentralized production. This review covers the research progress in the field of plasma-assisted nitrogen fixation achieved in the past five years. Both the production of NO_x and the synthesis of ammonia are included, and discussion on plasma reactors, operation parameters and plasma-catalysts are given. In addition, outlooks and suggestions for future research are also given.

Oxidative coupling of methane (OCM) is a process to directly convert methane into ethylene. However, its ethylene yield is limited in conventional reactors by the nature of the reaction system. In this work, the integration of different membranes to increase the overall performance of the large-scale oxidative coupling of methane process has been investigated from a techno-economic point of view. A 1D membrane reactor model has been developed, and the results show that the OCM reactor yield is significantly improved when integrating either porous or dense membranes in packed bed reactors. These higher yields have a positive impact on the economics and performance of the downstream separation, resulting in a cost of ethylene production of 595–625 €/ton_C2H4 depending on the type of membranes employed, 25–30% lower than the benchmark technology based on oil as feedstock (naphtha steam cracking). Despite the use of a cryogenic separation unit, the porous membranes configuration shows generally better results than dense ones because of the much larger membrane area required in the dense membranes case. In addition, the CO₂ emissions of the OCM studied processes are also much lower than the benchmark technology (total CO₂ emissions are reduced by 96% in the dense membranes case and by 88% in the porous membranes case, with respect to naphtha steam cracking), where the high direct CO₂ emissions have a major impact on the process. However, the scalability and the issues associated with it seem to be the main constraints to the industrial application of the process, since experimental studies of these membrane reactor technologies have been carried out just on a very small scale.

This paper reports the findings of a FP7 project (DEMCAMER) that developed materials (catalysts and membranes) and new processes for four industrially relevant reaction processes. In this project, active, stable, and selective catalysts were developed for the reaction systems of interest and their production scaled up to kg scale (TRL5 (TRL: Technology Readiness Level)). Simultaneously, new membranes for gas separation were developed; in particular, dense supported thin palladium-based membranes for hydrogen separation from reactive mixtures. These membranes were successfully scaled up to TRL4 and used in various lab-scale reactors for water gas shift (WGS), using both packed bed and fluidized bed reactors, and Fischer-Tropsch (FTS) using packed bed reactors and in prototype reactors for WGS and FTS. Mixed ionic-electronic conducting membranes in capillary form were also developed for high temperature oxygen separation from air. These membranes can be used for both Autothermal Reforming (ATR) and Oxidative Coupling of Methane (OCM) reaction systems to increase the efficiency and the yield of the processes. The production of these membranes was scaled up to TRL3–4. The project also developed adequate sealing techniques to be able to integrate the different membranes in lab-scale and prototype reactors.

Carbon molecular sieve membranes (CMSMs) are emerging as promising solution to overcome the drawbacks of Pd-based membranes for H₂ separation since (i) they are relatively easy to manufacture; (ii) they have low production and raw material costs; (iii) and they can work at conditions where polymeric and palladium membranes are not stable. In this work CMSMs have been investigated in pure gas and gas mixture tests for a proper understanding of the permeation mechanism, selectivity and purity towards hydrogen. No mass transfer limitations have been observed with these membranes, which represents an important advantage compared to Pd-Ag membranes, which suffer from concentration polarization especially at high pressure and low hydrogen concentrations. H₂, CH₄, CO₂ and N₂ permeation at high pressures and different temperatures in presence of dry and humidified stream (from ambient and water vapour) have been carried out to investigate the effect of the presence of water in the feed stream. Diffusion is the main mechanism observed for hydrogen, while methane, nitrogen and especially carbon dioxide permeate through adsorption-diffusion at low temperatures and high pressures. Finally, H₂ permeation from H₂-CH₄ mixtures in presence of water has been compared at different temperatures and pressure, which demonstrates that water adsorption is an essential parameter to improve the performance of carbon molecular sieve membranes, especially when working at high temperature. Indeed, a hydrogen purity of 98.95% from 10% H₂—90% CH₄ was achieved. The main aim of this work is to understand the permeation mechanisms of CMSMs in different operating conditions and find the best conditions to optimize the separation of hydrogen.

For a better understanding and description of the mass transport phenomena in dense multiphase gas-solids systems such as fluidized bed reactors, detailed and quantitative experimental data on the concentration profiles is required, which demands advanced non-invasive concentration monitoring techniques with a high spatial and temporal resolution. A novel technique based on the selective detection of a gas component in a gas mixture using infra-red properties has been further developed. The first stage development was carried out using a very small sapphire reactor and CO₂ as tracer gas. Although the measuring principle was demonstrated, the real application was hindered by the small reactor dimensions related to the high costs and difficult handling of large sapphire plates. In this study, a new system has been developed, that allows working at much larger scales and yet with higher resolution. In the new system, propane is used as tracer gas and quartz as reactor material. In this study, a thorough optimization and calibration of the technique is presented which is subsequently applied for whole-field measurements with high temporal resolution. The developed technique allows the use of a relatively inexpensive configuration for the measurement of detailed concentration fields and can be applied to a large variety of important chemical engineering topics.

The concept of liquid metal membranes for hydrogen separation, based on gallium or indium, was recently introduced as an alternative to conventional palladium-based membranes. The potential of this class of gas separation materials was mainly attributed to the promise of higher hydrogen diffusivity. The postulated improvements are only beneficial to the flux if diffusion through the membrane is the rate-determining step in the permeation sequence. Whilst this is a valid assumption for hydrogen transport through palladium-based membranes, the relatively low adsorption energy of hydrogen on both liquid metals suggests that other phenomena may be relevant. In the current study, a microkinetic modeling approach is used to enable simulations based on a five-step permeation mechanism. The calculation results show that for the liquid metal membranes, the flux is limited by the dissociative adsorption over a large temperature range, and that the membrane flux is expected to be orders of magnitude lower compared to the membrane flux through pure palladium membranes. Even when accounting for the lower cost of the liquid metals compared to palladium, the latter still outperforms both gallium and indium in all realistic scenarios, in part due to the practical difficulties associated with making liquid metal thin films.