Search Results (51)

Refractory metals are being studied as alternatives to Pd and its alloys for the separation of hydrogen in high-temperature processes. The development of a membrane reactor for the production of hydrogen via water splitting has required studying hydrogen permeability through Ta at temperatures above 1273 K, for which no data is available in the literature. A dedicated experimental setup has been realized for testing Ta tubes in the temperature range 673–1573 K. Despite the use of controlled atmospheres and ultra-pure gases (with oxygen content below a few ppm), the tests over 1473 K have involved the formation of oxide layers over the metal surfaces, as verified by SEM-EDS analyses. The presence of oxide layers significantly increases the energy barrier to permeation: in agreement with a modest surface oxidation, at lower temperatures (673–1273 K) the activation energy of 2679.8 K has been measured against the value of 30,691 K measured in the high-temperature tests (1473–1573 K). Full article

The biogas dry reforming reaction offers a promising route for syngas production while simultaneously mitigating greenhouse gas emissions. Membrane reactors have proven to be an excellent option for hydrogen production and separation in a single unit, where conversion and yield can be enhanced over conventional processes. In this study, a Pd/YSZ membrane integrated with a Ru/CeO₂ catalyst was evaluated for biogas reaction under varying operating conditions. The selective removal of hydrogen through the palladium membrane improved reactant conversion and suppressed side reactions such as methanation and the reverse water–gas shift. Experiments were performed at temperatures ranging from 500 to 600 °C, pressures of 1–6 bar, and a gas hourly space velocity (GHSV) of 800 h⁻¹. Maximum conversions of CH₄ (43%) and CO₂ (46.7%) were achieved at 600 °C and 2 bar, while the maximum hydrogen recovery of 78% was reached at 6 bar. The membrane reactor outperformed a conventional reactor, offering up to 10% higher CH₄ conversion and improved hydrogen production and yield. Also, a comparative analysis between Ru/CeO₂ and Ni/Al₂O₃ catalysts revealed that while the Ni-based catalyst provided higher CH₄ conversion, it also promoted methane decomposition reaction and coke formation. In contrast, the Ru/CeO₂ catalyst exhibited excellent resistance to coke formation, attributable to ceria’s redox properties and oxygen storage capacity. The combined system of Ru/CeO₂ catalyst and Pd/YSZ membrane offers an effective and sustainable approach for hydrogen-rich syngas production from biogas, with improved performance and long-term stability. Full article

The efficiency of membrane reactors for steam reforming of hydrocarbons depends critically on the performance and selectivity of hydrogen-permeable membranes. In this work, a strategy for controlling the catalytic and gas-transport characteristics of Pd-Ag-Ru membranes by modifying the surface and controlling the morphology of nanostructured coatings was developed. It was found that as the process temperatures approached ~200 °C and the membrane thickness decreased, a transition to limitation of the hydrogen transfer process by surface stages was observed. Surface modification with pyramidal nanoparticles resulted in a significant increase in the hydrogen flux by up to 1.5 times compared to membranes with spiked nanoparticles and up to 2 times compared to membranes with spherical nanoparticles. The maximum difference in fluxes of up to 12 times was achieved compared to uncoated membranes. The achieved result is due to a significant increase in the active surface area associated with a systematic change in the morphology of the coatings. This aspect was a key factor in improving the catalytic activity of the material, reducing the energy barrier of sorption and accelerating the stages of hydrogen transfer through the developed membranes. Thus, modification with shape-controlled nanoparticle coatings presents an effective strategy for overcoming the limitations of the permeability of palladium-based membranes under conditions of small thickness and low temperatures. The use of the developed membranes in steam reforming reactors of alcohols can provide increased energy efficiency, conversion and purity of hydrogen. Full article

The electrocatalytic hydrogenation (ECH) of biomass-derived phenolic compounds is a promising approach to the production of value-added chemicals and biofuels in a sustainable way under moderate reaction conditions. This study provides a comprehensive comparison of electrochemical and thermochemical hydrogenation processes, highlighting their relative advantages in terms of energy efficiency, product selectivity, and environmental impact. Several electrocatalysts (Pt, Pd, Rh, Ru), membranes (Nafion, Fumasep, GO-based PEMs), and reactor configurations are tested for the selective conversion of model compounds such as phenol, guaiacol, furfural, and levulinic acid. The contributions made by the electrode material, electrolyte composition, membrane nature, and reaction conditions are critically evaluated in relation to Faradaic efficiency, conversion rates, and product selectivity. The enhancement in the performance achieved by a new catalyst architecture is emphasized, such as MOF-based systems and bimetallic/trimetallic catalysts. In addition, a demonstration of graphite-based membranes and membrane-separated slurry reactors (SSERs) is provided, for enhanced ion transport and reaction control. The results illustrate the potential of using ECH as a low-carbon, scalable, and tunable method for the upgrading of biomass. This study offers valuable insights and guidelines for the rational design of next-generation electrocatalytic systems toward green chemical synthesis and emphasizes promising perspectives for the strategic development of electrochemical technologies in the pathway of a sustainable energy economy. Full article

Ammonia (NH₃) represents a promising zero-emission fuel in hydrogen fuel cells. Membrane reactors for NH₃ decomposition based on Pd-alloys have demonstrated high NH₃ conversion, high hydrogen diffusivity, and high hydrogen selectivity, which allows for the production of high-purity H₂ without the need for gas separation or purification. However, it is observed that Pd-alloy membranes are to a various degree prone to H₂ flux inhibition in the presence of NH₃. Hence, finding proper means to tailor the surface adsorption properties through, e.g., alloying is imperative to further improve the technology. In the current work, hydrogen and ammonia co-adsorption phenomena on M(1 1 1) and Pd₃M(1 1 1) (M = Pd, Ru, Ag, Au, Cu) surfaces are studied using density functional theory calculations. It is shown that the surface adsorption properties are strongly dependent on the surface composition, which can be linked to the corresponding electronic structure at the membrane surface. Full article

The purpose of this study is to reveal the characteristics of a Pd/Cu membrane and Ni/Cr catalyst adopted in a biogas dry reforming (BDR) membrane reactor by the numerical simulation procedure. The commercial software COMSOL Multiphysics ver. 6.2 was adopted in the numerical simulation. COMSOL is one type of commercial software that can solve multiphysics phenomena, i.e., chemical reaction, fluid dynamics, heat transfer, etc. The impact of the initial reaction temperature and the thickness of the Pd/Cu membrane on the performance of the BDR membrane reactor using an Ni/Cr catalyst is also investigated. The initial reaction temperatures adopted were 400 °C, 500 °C, and 600 °C, and the thicknesses of the Pd/Cu membrane were varied at 20 μm, 40 μm, and 60 μm. It was discovered that when the initial reaction temperature was raised, the molar concentration of H₂ increased while the molar concentrations of CH₄ and CO₂ decreased. Because the penetration resistance of the Pd/Cu membrane decreased with the decrease in the thickness of the Pd/Cu membrane, the molar concentrations of H₂ remaining in the Pd/Cu membrane and sweep chamber rose with the decrease in the thickness of the Pd/Cu membrane. Full article

The aim of the present study was to clarify the influence of the thickness of the Pd/Cu membrane on the characteristics of biogas dry reforming (BDR) with aNi/Cr/Ru catalyst. We also clarified the impact of the reaction temperature, the molar ratio of CH₄:CO₂, the differential pressure between the reaction and sweep chambers, and the introduction of a sweep gas on the characteristics of a BDR reactor with a Pd/Cu membrane and a Ni/Cr/Ru catalyst. Through this study’s results, we clarify that the concentration of H₂ in the reaction chamber and the sweep chamber increases with the increase in the reaction temperature. In addition, this study clarifies that the highest concentration of H₂ in the reaction chamber and the sweep chamber can be obtained with a molar ratio of CH₄:CO₂ = 1.5:1. This study also clarifies that the highest concentration of H₂ can be obtained with a thickness of 40 μm, a molar ratio of CH₄:CO₂ = 1.5:1, and a differential pressure between the reaction chamber and the sweep chamber of 0 MPa without a sweep gas, which was 4890 ppmV in the reaction chamber and 38 ppmV in the sweep chamber. Under these conditions, CH₄ conversion, H₂ yield, and thermal efficiency were 75.0%, 0.214%, and 2.92%, respectively. Full article

A multiparametric study was conducted on a hydrogen (H₂) production rig designed to process 0.25 Nm³·h⁻¹ of syngas. The rig consists of two Pd-Ag membrane permeator units and two Pd-Ag membrane reactor units for the water–gas shift (WGS) reaction, enabling a detailed and comprehensive analysis of its performance. The aim was to find the optimal conditions to maximize hydrogen production by WGS and its separation in a pure stream by varying the temperature, pressure, and steam-to-CO ratio (S/CO). Two syngas mixtures obtained from an updraft gasifier using different gasification agents (air–steam and oxy–steam) were used to investigate the effect of gas composition. The performance of the rig was investigated under nine combinations of temperature, pressure, and S/CO in the respective ranges of 300–350 °C, 2–8 bar, and 1.1–2 mol·mol⁻¹, as planned with the help of design of experiment (DOE) software. The three parameters positively affected performance, both in terms of capacity to separate a pure stream of H₂, reported as moles permeated per unit of surface area and time, and in producing new H₂ from WGS, reported as moles of H₂ produced per volume of catalyst unit and time. The highest yields were obtained using syngas from oxy–steam gasification, which had the highest H₂ concentration and was free of N₂. Full article

In a previous study, we developed an integrated reaction system combining NH₃ decomposition and CO₂ methanation within a membrane reactor, significantly enhancing reactor performance through efficient H₂ separation. Ru/Ba/γ-Al₂O₃ and Ru/ZrO₂ were employed as catalysts for each reaction. To ensure the accuracy and reliability of our results, they were validated through 1D models using FlexPDE Professional Version 7.21/W64 software. Key parameters such as reactor arrangement, catalyst bed positioning, overall heat transfer coefficient, rate constants, and H₂ permeance were investigated to optimize system efficiency. The study revealed that positioning the NH₃ decomposition on the shell side and CO₂ methanation on the tube side resulted in a better performance. Additionally, shifting the methanation catalyst bed downward by approximately one-eighth (10 mm from 80 mm) achieves the highest CO₂ conversion. A sensitivity analysis identified the rate constant of the NH₃ decomposition catalyst and the H₂ permeance of the membrane as the most influential factors in enhancing CO₂ conversion. This highlights the priority of improving membrane H₂ permeance and catalytic activity for NH₃ decomposition to maximize system efficiency. Full article

Background: The issue of renewable energy (RE) source intermittency, such as wind and solar, along with the geographically uneven distribution of the global RE potential, makes it imperative to establish an energy transport medium to balance the energy demand and supply areas. A promising energy vector to address this situation is hydrogen, which is considered a clean energy carrier for various mobile and portable applications. Unfortunately, at standard pressure and temperature, its energy content per volume is very low (0.01 kJ/L). This necessitates alternative storage technologies to achieve reasonable capacities and enable economically viable long-distance transportation. Among the hydrogen storage technologies using chemical methods, liquid organic hydrogen carrier (LOHC) systems are considered a promising solution. They can be easily managed under ambient conditions, the H₂ storage/release processes are carbon-free, and the carrier liquid is reusable. However, the evolution of the proposals from the carrier liquid type and catalyst elemental composition point of view is scarcely studied, considering that both are critical in the performance of the system (operational parameters, kinetic of the reactions, gravimetric hydrogen content, and others) and impact in the final cost of the technology deployed. The latter is due to the use of the Pt group elements (PGEs) in the catalyst that, for example, have a high demand in the hydrogen production sector, particularly for polymer electrolyte membrane (PEM) water electrolysis. With that in mind, our objective was to examine the evolution and the focus of the research in recent years related to proposals of LOHCs and catalysts for hydrogenation and dehydrogenation reactions in LOHC systems which can be useful in defining routes/strategies for new participants interested in becoming involved in the development of this technology. Data sources: For this systematic review, we searched the SCOPUS database and forward and backward citations for studies published in the database between January 2011 and December 2022. Eligibility criteria: The criteria include articles which assessed or studied the effect of the type of catalyst, type of organic liquid, reactor design(s)/configuration(s), and modification of the reactor operational parameters, among others, over the performance of the LOHC system (de/hydrogenation reaction(s)). Data extraction and analysis: The relevant data from each reviewed study were collected and organized into a pre-designed table on an Excel spreadsheet, categorized by reference, year, carrier organic liquid, reaction (hydrogenation and/or dehydrogenation), investigated catalyst, and primary catalyst element. For processing the data obtained from the selected scientific publications, the data analysis software Orbit Intellixir was employed. Results: For the study, 233 studies were included. For the liquid carrier side, benzyltoluene and carbazole dominate the research strategies. Meanwhile, platinum (Pt) and palladium (Pd) are the most employed catalysts for dehydrogenation reactions, while ruthenium (Ru) is preferred for hydrogenation reactions. Conclusions: From the investigated liquid carrier, those based on benzyltoluene and carbazole together account for over 50% of the total scientific publications. Proposals based on indole, biphenyl, cyclohexane, and cyclohexyl could be considered to be emerging within the time considered in this review, and, therefore, should be monitored for their evolution. A great activity was detected in the development of catalysts oriented toward the dehydrogenation reaction, because this reaction requires high temperatures and presents slow H₂ release kinetics, conditioning the success of the implementation of the technology. Finally, from the perspective of the catalyst composition (monometallic and/or bimetallic), it was identified that, for the dehydrogenation reaction, the most used elements are platinum (Pt) and palladium (Pd), while, for the hydrogenation reaction, ruthenium (Ru) widely leads its use in the different catalyst designs. Therefore, the near-term initiatives driving progress in this field are expected to focus on the development of new or improved catalysts for the dehydrogenation reaction of organic liquids based on benzyltoluene and carbazole. Full article

The present study pays attention to biogas dry reforming for the purpose of producing H₂. It is known that biogas contains approximately 40 vol% CO₂, causing a decrease in the efficiency of power generation due to its lower heating value compared to natural gas, i.e., CH₄. We suggest a hybrid system composed of a biogas dry reforming membrane reactor and a high-temperature fuel cell, i.e., a solid oxide fuel cell (SOFC). Since biogas dry reforming is an endothermic reaction, we adopt a membrane reactor, controlled by providing a non-equilibrium state via H₂ separation from the reaction site. The purpose of the present study is to understand the effect of the thickness of the Pd/Cu membrane on the performance of the biogas dry reforming membrane reactor with a Pd/Cu membrane as well as a Ni/Cr catalyst. The impact of the reaction temperature, the molar ratio of CH₄:CO₂ and the differential pressure between the reaction chamber and the sweep chamber on the performance of the biogas dry reforming membrane reactor with the Pd/Cu membrane as well as the Ni/Cr catalyst was investigated by changing the thickness of the Pd/Cu membrane. It was revealed that we can obtain the highest concentration of H₂, of 122,711 ppmV, for CH₄:CO₂ = 1:1 at a reaction temperature of 600 °C and a differential pressure of 0 MPa and using a Pd/Cu membrane with a thickness of 40 μm. Under these conditions, it can be concluded that the differential pressure of 0 MPa provides benefits for practical applications, especially since no power for H₂ separation is necessary. Therefore, the thermal efficiency is improved, and additional equipment, e.g., a pump, is not necessary for practical applications. Full article

This study proposes a combination system consisting of a biogas dry reforming reactor and a solid oxide fuel cell (SOFC). Since biogas dry reforming is an endothermic reaction, this study adopted a membrane reactor operated due to the non-equilibrium state with H₂ separation from the reaction space. This study aimed to clarify the performance of the Ni/Cr/Ru catalyst using a biogas dry reforming membrane reactor. Additionally, this study also undertook a comparison of the performance of the Ni/Cr/Ru catalyst with that of the Ni/Cr catalyst. The impact of operation temperature, the molar ratio of CH₄:CO₂, the differential pressure between the reaction chamber and the sweep chamber, and the introduction of a sweep gas on the performance of the biogas dry reforming membrane reactor using a Pd/Cu membrane and a Ni/Cr/Ru catalyst was examined. The concentration of H₂ using the Ni/Cr/Ru catalyst was greater than that using the Ni/Cr catalyst by 2871 ppmV for the molar ratio of CH₄:CO₂ = 1.5:1 at the reaction temperature of 600 °C and the differential pressure of 0 MPa without a sweep gas in particular. Under this condition, CH₄ conversion, H₂ yield, and thermal efficiency were 67.4%, 1.77 × 10⁻²%, and 0.241%, respectively. Full article

The utilization of ammonia for hydrogen storage relies on the implementation of efficient decomposition techniques, and the membrane reactor, which allows simultaneous ammonia decomposition and hydrogen recovery, can be regarded as a promising technology. While Pd-based membranes show the highest performance for hydrogen separation, their applicability for NH₃-sensitive applications, such as proton exchange membrane (PEM) fuel cells, demands relatively thick, and therefore expensive, membranes to meet the purity targets for hydrogen. To address this challenge, this study proposes a solution involving the utilization of a downstream hydrogen purification unit to remove residual ammonia, thereby enabling the use of less selective, therefore more cost-effective, membranes. Specifically, a carbon molecular sieve membrane was prepared on a tubular porous alumina support and tested for ammonia decomposition in a membrane reaction setup. Operating at 5 bar and temperatures ranging from 450 to 500 °C, NH₃ conversion rates exceeding 90% were achieved, with conversion approaching thermodynamic equilibrium at temperatures above 475 °C. Simultaneously, the carbon membrane facilitated the recovery of hydrogen from ammonia, yielding recoveries of 8.2–9.8%. While the hydrogen produced at the permeate side of the reactor failed to meet the purity requirements for PEM fuel cell applications, the implementation of a downstream hydrogen purification unit comprising a fixed bed of zeolite 13X enabled the production of fuel cell-grade hydrogen. Despite performance far from being comparable with the ones achieved in the literature with Pd-based membranes, this study underscores the viability of carbon membranes for fuel cell-grade hydrogen production, showcasing their competitiveness in the field. Full article

Hydrogen permeation sparked a renewed interest in the second half of the 20th century due to the favorable features of this element as an energy factor. Furthermore, niche applications such as nuclear fusion gained attention for the highest selectivity ensured by self-supported dense metallic membranes, especially those consisting of Pd-based alloys. In this framework, the ENEA Frascati laboratories have decades of experience in the manufacturing, integration, and operation of Pd-Ag permeators. Most of the experimental investigations were performed on single-tube membranes, proving their performance under relevant operational conditions. Nowadays, once the applicability of this technology has been demonstrated, the scalability of the single-tube experience over medium- and large-scale units must be verified. To do this, ENEA Frascati laboratories have designed and constructed a multi-tube permeator, namely the Medium-Scaled Membrane Reactor (MeSMeR), focused on scalability assessment. In this work, the results obtained with the MeSMeR facility have been compared with previous experimental campaigns conducted on single-tube units, and the scalability of the permeation results has been proven. Moreover, post-test simulations have been performed based on single-tube finite element modeling, proving the scalability of the numerical outcomes and the possibility of using this tool for scale-up design procedures. Full article

H₂ production via membrane-assisted steam methane reforming (MA-SMR) can ensure higher energy efficiency and lower emissions compared to conventional reforming processes (SMR). Ceramic-supported Pd–Ag membranes have been extensively investigated for membrane-assisted steam methane reforming applications, with outstanding performance. However, costs, sealings for integration in the reactor structure, and resistance to solicitations remain challenging issues. In this work, the surface quality of a low-cost, porous Hastelloy-X filter is improved by asymmetric filling with α-Al₂O₃ of decreasing size and deposition of γ-Al₂O₃ as an interdiffusion barrier. On the modified support, a thin Pd–Ag layer was deposited via electroless plating (ELP), resulting in a membrane with H₂/N₂ selectivity >10,000. The permeation characteristics of the membrane were studied, followed by testing for membrane-assisted methane steam reforming. The results showed the ability of the membrane reactor to overcome thermodynamic conversion of the conventional process for all explored operating conditions, as well as ensuring 99.3% H₂ purity in the permeate stream at 500 °C and 4 bar. Full article