Advances and Perspectives of H2 Production from NH3 Decomposition in Membrane Reactors

Hydrogen is often regarded as an ideal energy carrier. Its use in energy conversion devices does in fact not produce any pollutants. However, due to challenges related to its transportation and storage, liquid hydrogen carriers are being investigated. Among the liquid hydrogen carriers, ammonia is considered very promising because it is easy to store and transport, and its conversion to hydrogen has only nitrogen as a byproduct. This work focuses on a review of the latest results of studies dealing with ammonia decomposition for hydrogen production. After a general introduction to the topic, this review specifically focuses on works presenting results of membrane reactors for ammonia decomposition, particularly describing the different reactor configurations and operating conditions, membrane properties, catalysts, and purification steps that are required to achieve pure hydrogen for fuel cell applications

Long-Term Stability of Thin-Film Pd-Based Supported Membranes

Membrane reactors have demonstrated a large potential for the production of hydrogen via reforming of different feedstocks in comparison with other reactor types. However, the long-term performance and stability of the applied membranes are extremely important for the possible industrial exploitation of these reactors. This study investigates the long-term stability of thin-film Pd-Ag membranes supported on porous Al2O3 supports. The stability of five similarly prepared membranes have been investigated for 2650 h, up to 600 °C and in fluidized bed conditions. Results show the importance and the contribution of the sealing of the membranes at temperatures up to 500 °C. At higher temperatures the membranes surface deformation results in pinhole formation and a consequent decrease in selectivity. Stable operation of the membranes in a fluidized bed is observed up to 450 °C, however, at higher temperatures the scouring action of the particles under fluidization causes significant deformation of the palladium surface resulting in a decreased selectivity.The presented work is funded within BIONICO. This project has received funding from the Fuel Cells and Hydrogen 2 Joint Undertaking under grant agreement No 671459. This Joint Undertaking receives support from the European Union’s Horizon 2020 Research and Innovation Programme, Hydrogen Europe and N.ERGHY

Mixed Ionic-Electronic Conducting Membranes (MIEC) for Their Application in Membrane Reactors: A Review

Mixed ionic-electronic conducting membranes have seen significant progress over the last 25 years as efficient ways to obtain oxygen separation from air and for their integration in chemical production systems where pure oxygen in small amounts is needed. Perovskite materials are the most employed materials for membrane preparation. However, they have poor phase stability and are prone to poisoning when subjected to CO2 and SO2, which limits their industrial application. To solve this, the so-called dual-phase membranes are attracting greater attention. In this review, recent advances on self-supported and supported oxygen membranes and factors that affect the oxygen permeation and membrane stability are presented. Possible ways for further improvements that can be pursued to increase the oxygen permeation rate are also indicated. Lastly, an overview of the most relevant examples of membrane reactors in which oxygen membranes have been integrated are provided.This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 679933. The present publication reflects only the author’s views and the European Union is not liable for any use that may be made of the information contained therein

Membrane reactors for green hydrogen production from biogas and biomethane:A techno-economic assessment

This work investigates the performance of a fluidized-bed membrane reactor for pure hydrogen production. A techno-economic assessment of a plant with the production capacity of 100 kgH2/day was carried out, evaluating the optimum design of the system in terms of reactor size (diameter and number of membranes) and operating pressures. Starting from a biomass source, hydrogen production through autothermal reforming of two different feedstock, biogas and biomethane, is compared. Results in terms of efficiency indicates that biomethane outperforms biogas as feedstock for the system, both from the reactor (97.4% vs 97.0%) and the overall system efficiency (63.7% vs 62.7%) point of views. Nevertheless, looking at the final LCOH, the additional cost of biomethane leads to a higher cost of the hydrogen produced (4.62 €/kgH2@20 bar vs 4.39 €/kgH2@20 bar), indicating that at the current price biogas is the more convenient choice.</p

Measurement of solids circulation rates with optical techniques in circulating beds and comparison to pressure drop methods

The number of applications employing circulating fluidized beds has increased considerably over the last years following the important development of chemical looping technologies for power generation (combustion) or fuel conversion (reforming) with inherent CO2 capture. The performance of these reactors is strongly determined by the amount of solids transferred from one reactor to the other, commonly referred to as the Solids Circulation Rate (SCR). The solids inventory, particle characteristics and gas velocities strongly influence the SCR. The determination of the SCR has been carried out using invasive and non-invasive measurement techniques. The direct measurement through solids collection in the loop seal is the most applied technique, but this technique requires opening of the loop seals and thus may be expensive, whereas other methods suffer from large inaccuracies. There is yet no optimal technique available that combines good accuracy with reasonable costs, as recently also discussed by Alghamdi et al. (1). In this work, a pseudo 2D internally circulating fluidized bed (Figure 1) has been built to explore the potential of optical techniques like Particle Image Velocimetry (PIV) combined with Digital Image Analysis (DIA) for non-invasive, whole-field measurements. Moreover, the setup allows for the measurement of the pressure drop (fluctuations) along the riser and the collection of particles circulating from one reactor to the other, so that the three different measurement techniques can be compared. Please click Additional Files below to see the full abstract

Characterization of wake properties in freely bubbling fluidized beds using Particle Image Velocimetry

The performance of fluidized beds in many physical or chemical operations is predominantly determined by the hydrodynamics and mass transfer characteristics. However, a proper description of a fluidized bed using phenomenological models requires correlations based on many different assumptions for the bubble and emulsion phases, where most of these assumptions have not been validated thoroughly at different operating conditions. One of the most typical assumptions is the fact that the wake of a bubble rises with exactly the same velocity as the bubble and occupies a specific and constant fraction in the bed, commonly around 15% of the bubble volume (1). The wake fraction has been studied using optical techniques and the geometry of the single bubbles injected has been analysed at different experimental conditions (2). However, these results are mainly based on geometric observations, and are not based on specific properties of fluidized beds. In this study, two new methods for the characterization of wake properties in fluidized beds are developed and studied based on the dynamics of the solids phase. Particle Image Velocimetry (PIV) allows to determine the solids phase velocity profiles in detail, which is used for the investigation of the wake properties. PIV combined with Digital Image Analysis (DIA) can provide the average solids mass fluxes throughout the fluidized bed, along with the bubble properties. When relating all positive solids fluxes to the solids carried along by the bubbles in their wakes, the average wake fraction can be obtained directly, as presented in the Figure 1. This method provides information on average results and therefore accounts for all bubbles observed during the experimental evaluation. Please click Additional Files below to see the full abstract

Gliding Arc Reactor under AC Pulsed Mode Operation:Spatial Performance Profile for NO_x Synthesis

A two-dimensional gliding arc reactor for NOx synthesis was investigated in this study using AC pulsed mode operation. Tests with a duty cycle of 40 or 60% achieved the lowest energy consumption of 6.95 MJ/mol, which is an improvement of 15% from the case of continuous operation. Based on the results achieved, a new method for analyzing the spatial profile of the reactor was presented. The reactor was divided into five zones along the arc propagation, and results indicated that the first zone and last zone of the gliding arc reactor had higher energy consumption (9.59 and 8.63 MJ/mol, respectively), while lower consumption was observed in the middle parts of the reactor with a minimum of 5.00 MJ/mol. Spatial-resolved optical emission spectra, the deduced electron density, and temperature indicated the nonuniformity in plasma properties, which corresponds to the NOx production performance across the reactor. This research provides information and discussion that can be used for understanding and optimization of gliding arc reactors toward efficient nitrogen fixation.</p

Techno-economic assessment of the one-step CO₂conversion to dimethyl ether in a membrane-assisted process

This study investigates the impact of the membrane reactor (MR) technology with in-situ removal of water to boost the performance of the one-step DME synthesis via CO2 hydrogenation at process scale. Given the higher efficiency in converting the feedstock, the membrane reactor allows for a remarkable decrease in the main cost drivers of the process, i.e., the catalyst mass and the H2 feed flow, by ca. 39% and 64%, respectively. Furthermore, the MR-assisted process requires 46% less utilities than the conventional process, especially in terms of cooling water and refrigerant, with a corresponding decrease in environmental impact (i.e., 25% less CO2 emissions). Both the conventional and MR-assisted plants were found effective for the mitigation of the CO2 emissions, avoiding ca. 1.4-1.6 tonCO2/tonDME. However, given the higher reactor and process efficiency, the membrane technology contributes to a significant reduction (i.e., 25%) in the operating costs, which is a remarkable improvement in this OPEX intensive process. Nevertheless, the calculated minimum DME selling price (i.e., 1739 €/ton and 1960 €/ton for the MR-assisted and the conventional process, respectively) is over 3 times greater than the current DME market price. Yet, with the predicted decrease of renewable H2 price and a zero-to-negative cost for the CO2 feedstock, the MR-assisted system could become competitive with the benchmark between 2025 and 2050.</p