Search Results (23)

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

Several Cu and Ni-based catalysts were synthetized over Ce-based supports, either pure or mixed with different amounts of alumina (1:2 and 1:3 mol/mol). Different metal loadings (10–40 wt%) and preparation methods (wet impregnation, co-precipitation, and flame-spray pyrolysis—FSP) were compared for the oxidative steam reforming of methanol. Characterization of the catalysts has been performed, e.g., through XRD, BET, XPS, TPR, SEM, and EDX analyses. All the catalysts have been tested in a bench-scale continuous setup. The hydrogen yield and methanol conversion obtained have been correlated with the operating conditions, metal content, crystallinity of the catalyst particles, total surface area, and with the interaction of the metal with the support. A Cu loading of 20% wt/wt was optimal, while the presence of alumina was not beneficial, decreasing catalyst activity at low temperatures compared with catalysts supported on pure CeO₂. Ni-based catalysts were a possible alternative, but the activity towards the methanation reaction at relatively high temperatures decreased inevitably the hydrogen yield. Durability and deactivation tests showed that the best-performing catalyst, 20% wt. Cu/CeO₂ prepared through coprecipitation was stable for a long period of time. Full methanol conversion was achieved at 280 °C, and the highest yield of H₂ was ca. 80% at 340 °C, higher than the literature data. Full article

Fe-modified Cu catalysts with CeO₂ support, prepared by the impregnation method, were subjected to physicochemical analysis and catalytic tests in the steam reforming of methanol (SRM). Physicochemical studies of the catalysts were carried out using the XRF, TEM, STEM-EDS, XRD, TPR and nitrogen adsorption/desorption methods. XRD, TEM studies and catalytic tests of the catalysts were carried out at two reduction temperatures, 260 °C and 400 °C, to determine the relationship between the form and oxidation state of the active phase of the catalysts and the catalytic properties of these systems in the SRM. Additionally, the catalysts after the reaction were analysed for the changes in the structure and morphology using TEM methods. The presented results show that the composition of the catalysts, morphology, structure, form and oxidation state of the Cu and Fe active metals in the catalysts and the reaction temperature significantly impact their activity, selectivity and stability in the SRM process. The gradual deactivation of the studied catalysts under SRM conditions could result from the forming of carbon deposits and/or the gradual oxidation of the copper and iron phases under the reaction conditions. Full article

Biogas has emerged as a valid feedstock for biomethanol production from steam reforming. This study investigates an alternative layout based on an auto-thermal electrified reforming assuming a 1 MW equivalent anaerobic digestion plant as a source for methanol synthesis. The process considers an oxy-steam combustion of biogas and direct carbon sequestration with the presence of a reverse water–gas shift reactor to convert CO₂ and H₂ produced by a solid oxide electrolyzer cell to syngas. Thermal auto-sufficiency is ensured for the reverse water–gas shift reaction through the biogas oxy-combustion, and steam production is met with the integration of heat network recovery, with an overall process total electrical demand. This work compares the proposed process of electrification with standard biogas reforming and data available from the literature. To compare the results, some key performance indicators have been introduced, showing a carbon impact of only 0.04 kgCO₂/kgMeOH for the electrified process compared to 1.38 kgCO₂/kgMeOH in the case of biogas reforming technology. The auto-thermal electrified design allows for the recovery of 66.32% of the carbon available in the biogas, while a similar electrified process for syngas production reported in literature reaches only 15.34%. The overall energy impact of the simulated scenarios shows 94% of the total energy demand for the auto-thermal scenario associated with the electrolyzer. Finally, the introduction of the new layout is taken into consideration based on the country’s carbon intensity, proving carbon neutrality for values lower than 75 gCO₂/kWh and demonstrating the role of renewable energies in the industrial application of the process. Full article

The conversion of hydrogen to power via combined external reforming of liquid alcohol and solid oxide fuel cell (SOFC) technology is an effective approach to address future energy challenges. In this study, an La_0.8Ba_0.1Mn_0.8Ni_0.1Cu_0.1O₃ (LBMNCu) perovskite nanofiber with high porosity was synthesized with a modified electrostatic spinning method, which acted as an efficient catalyst for steam reforming of liquid alcohols (methanol and ethanol). After reduction, fine metallic Ni-Cu was uniformly distributed throughout the perovskite nanofiber surface. The obtained composite displayed a methanol conversion above 99.9% at 450 °C and an ethanol conversion above 99% at 600 °C, which was highly superior to the common Ni-Cu/Al₂O₃ catalyst. The catalytic performance of our assembled catalysts also remained stable in methanol and ethanol atmospheres for 50 h and no coking was detected. Furthermore, when the reformed gas was fed into a Y_0.08Zr_0.92O₂ (YSZ)-based SOFC system, the open circuit voltage remained around 1.1 V at 700 °C for 50 h accordingly, without coking, and the voltage remained virtually unchanged at 0.7 V for 50 h at 700 °C and 400 mA cm⁻² during galvanostatic discharge mode, indicating that using LBMNCu nanofiber as a catalyst for hydrogen production and utilization is an efficient strategy. The interaction of the in situ exsolved metallic nanoparticles and nanofibrous perovskite could also be a promising approach for designing a highly active catalyst for H₂ generation. Full article

Copper manganese oxide spinels and related (multiphase) materials with the formula Cu_xMn_3−xO₄ are the active catalysts in a wide variety of industrially important processes due to their great diversity in their phase relations, metal ion valence/site distribution, and chemical properties. In this review, we summarize the preparation methods and their effects on the composition, properties, and catalytic properties of various Cu_xMn_3−xO₄ catalysts with various Cu/Mn ratios. The main summarized catalytic reactions are the oxidation of carbon monoxide, nitrogen oxide, and hydrogen sulfide and the oxidative removal of organic solvents such as benzene, toluene, and xylene from the air. Some industrially important reactions (steam reforming of methanol or synthesis gas) and the manufacture of organic chemicals (methyl formate, propylene oxide, and benzyl alcohol) catalyzed by Cu_xMn_3−xO₄ spinels are also reviewed. Full article

Hydrogen can be employed as an alternative renewable energy source in response to climate change, global warming, and the energy problem. Methanol gas steam reforming (SRM) is the major method used in industry to produce hydrogen. In the SRM process, the catalyst nature offers benefits such as low cost, simplicity, and quickness. In this work, delafossite copper yttrium oxide (CuYO₂) nanofibers were successfully prepared by electrospinning. The prepared CuYO₂ nanofibers have different physical and chemical properties including thermoelectric behavior. The electrospinning method was used to produce as-spun fibers and annealed in an air atmosphere to form Cu₂Y₂O₅ fibers; then, Cu₂Y₂O₅ fibers were annealed in a nitrogen atmosphere to form CuYO₂ nanofibers. X-ray diffraction studies and thermogravimetric and transmission electron microscope analysis confirmed the formation of CuYO₂ nanofibers. The CuYO₂ nanofibers were applied to methanol steam reforming for hydrogen production to confirm their catalytic ability. The CuYO₂ nanofibers exhibited high catalytic activity and the best hydrogen production rate of 1967.89 mL min⁻¹ g-cat⁻¹ at 500 °C. The highly specific surface area of CuYO₂ nanofibers used in steam reforming reactions could have significant economic and industrial implications. The performance of these CuYO₂ nanofibers in hydrogen generation could be very important in industries with a global economic impact. Furthermore, the H₂ production performance increases at higher reaction temperatures. Full article

To elucidate the thermofluid reacting environment and thermal stress inside a solid oxide fuel cell (SOFC), a three-dimensional SOFC model is implemented by using the finite element method in the commercial software COMSOL Multiphysics^®, which contains both a geometric model of the full-cell structure and a mathematical model. The mathematical model describes heat and mass transfer, electrochemical reactions, internal reforming reactions, and mechanical behaviors that occur within the cell. A parameter study is performed focusing on the inlet fuel composition, where humidified hydrogen and methane syngas (the steam-to-carbon ratio is 3) as well as the local distribution of temperature, velocity, gas concentrations, and thermal stress are predicted and presented. The simulated results show that the fuel inlet composition has a significant effect on the temperature and gas concentration distributions. The high-temperature zone of the hydrogen-fueled SOFC is located at the central part of units 5, 6, and 7, and the maximum value is about 44 K higher than that of methane syngas-fueled SOFC. The methane-reforming and electrochemical reactions in the anode active layer result in a significant concentration gradient between the anode support layer and the active layer of the methane syngas-fueled SOFC. It is also found that the thermal stress distributions of different fuel inlet compositions are rather different. The maximum stress variation gradient between electrode layers of hydrogen SOFC is larger (44.2 MPa) than that of methanol syngas SOFC (14.1 MPa), but the remaining components have a more uniform stress distribution. In addition, the electrode layer of each fuel SOFC produces a significant stress gradient in the y-axis direction, and stress extremes appear in the corner regions where adjacent assembly components are in contact. Full article

This paper reviews the progress in applying the plasma-driven solution electrolysis (PDSE), which is also referred to as the contact glow-discharge electrolysis (CGDE) or plasma electrolysis, for hydrogen production. The physicochemical processes responsible for the formation of PDSE and effects occurring at the discharge electrode in the cathodic and anodic regimes of the PDSE operation are described. The influence of the PDSE process parameters, especially the discharge polarity, magnitude of the applied voltage, type and concentration of the typical electrolytic solutions (K₂CO₃, Na₂CO₃, KOH, NaOH, H₂SO₄), presence of organic additives (CH₃OH, C₂H₅OH, CH₃COOH), temperature of the electrolytic solution, the active length and immersion depth of the discharge electrode into the electrolytic solution, on the energy efficiency (%), energy yield (g(H₂)/kWh), and hydrogen production rate (g(H₂)/h) is presented and discussed. This analysis showed that in the cathodic regime of PDSE, the hydrogen production rate is 33.3 times higher than that in the anodic regime of PDSE, whereas the Faradaic and energy efficiencies are 11 and 12.5 times greater, respectively, than that in the anodic one. It also revealed the energy yield of hydrogen production in the cathodic regime of PDSE in the methanol–water mixture, as the electrolytic solution is 3.9 times greater compared to that of the alkaline electrolysis, 4.1 times greater compared to the polymer electrolyte membrane electrolysis, 2.8 times greater compared to the solid oxide electrolysis, 1.75 times greater than that obtained in the microwave (2.45 GHz) plasma, and 5.8% greater compared to natural gas steam reforming. Full article

Methanol steam reforming (MSR) is considered an effective method for hydrogen storage and to generate high-quality hydrogen for fuel cells. In this work, a comprehensive investigation of the methanol steam reforming process using a bimetallic Pt–Rh and Cu–Ni based on different oxide supports is presented. Highly dispersed titania and zirconia doped with indium and niobium ions were synthesized by sol–gel method. The effect of the nature and quantity of the dopant cation (In, Nb) on the catalytic performance of titania supported metal catalysts was investigated. The conclusions obtained show a significant effect of both the metal alloy and the oxide support nature on the activity and selectivity of the methanol steam reforming process. Pt–Rh alloy catalyst shows higher hydrogen yield, but its selectivity in the MSR process is lower than for the catalysts containing the Cu_0.8-Ni_0.2 alloy. Heterovalent indium doping of titania leads to the catalytic activity increase. It was suggested that this is due to the defects formation in the oxygen TiO₂ sublattice. On the contrary, the use of niobium oxide as a dopant decreases the catalyst activity in the methanol steam reforming process but leads to the selectivity increase in the studied process. Full article

Magnetic inducement was applied during metal loading to enhance Cu-Zn catalysts for methanol steam reforming in the temperature range of 200–300 °C. The supports used in this study were the γ-Al₂O₃ support and CeO₂-Al₂O₃ supports prepared under different magnetic environments. Cu-Zn loading between the north and south poles (N-S) on the CeO₂-Al₂O₃ support, prepared between two north poles (N-N), led to the highest H₂ production at 300 °C (2796 ± 76 µmol/min), which is triple that of Cu-Zn/CeO₂-Al₂O₃ prepared without magnetic inducement and ~11-fold the activity of the Cu-Zn/Al₂O₃ reference catalyst. The N-S magnetic environment during metal loading leads to lower reduction temperatures and larger Cu(1+):Cu(2+) ratio. These results showed that the pole arrangement of magnets during metal loading could affect the catalytic activity of the Cu-Zn catalyst owing to its influence on the reducibility and the oxidation state of Cu active metal. Full article

Due to the oxygen shortage at high altitudes, the use of diesel engines in small aircraft is limited to a low ceiling level. Here, we propose to significantly extend the ceiling level by introducing an in-cylinder steam reforming system. In this arrangement, the fuel direct-injection assembly comprises of a two-stage process. In the first stage, a blend of methanol and water is injected into the hot previously compressed cylinder charge onto an in-cylinder catalyst. Residual heat is absorbed due to the blend evaporation and the steam-reforming process to produce hydrogen. In the second stage, diesel fuel with a lower ignition temperature than the hydrogen fuel is injected to initiate combustion, while the absorbed heat (from the first stage) is released through the hydrogen oxidation. Essentially, the absorbed heat is exploited to produce extra hydrogen fuel, which increases the cycle efficiency. In this arrangement, the in-cylinder oxygen content is significantly increased due to the additional oxygen atoms that are included in the methanol and in particular in the water molecules. These are released when the methanol and water are decomposed during the steam-reforming process. We show that owing to the addition of the oxygen content in the cylinder, the flight ceiling level can be extended from 5000 to 9000 ft, and that the indicated efficiency can be increase up to 6%. Full article

The glycerol hydrogenolysis to produce 1,2-propanediol without using externally supplied hydrogen was investigated using methanol present in crude glycerol to provide in situ hydrogen via its steam reforming reaction. This paper focuses on the promoting effect of Pd on the reactivity of a Cu/Zn/Al₂O₃ catalyst. Adding 2 wt% Pd onto a Cu/ZnO/Al₂O₃ catalyst significantly improved the selectivity to 1,2-propanediol from 63.0% to 82.4% and the glycerol conversion from 70.2% to 99.4%. This enhancement on the catalytic activity by Pd is mainly due to the improved hydrogenation of acetol, which is the intermediate formed during the glycerol dehydration. The rapid hydrogenation of acetol can shift the reaction equilibrium of glycerol dehydration forward resulting in a higher glycerol conversion. The improved reducibility of the catalyst by Pd allows the catalyst to be reduced in situ during the reaction preventing any loss of catalyst activity due to any potential oxidation of the catalyst. The catalyst was slightly deactivated when it was firstly recycled resulting in a 5.4% loss of glycerol conversion due to the aggregation of Cu and the deactivation became less noticeable upon further recycling. Full article

In this work, the electronic properties of the metal sites in cubic and monoclinic ZrO₂ supported Pd and PdCu catalysts have been investigated using CO as probe molecule in in-situ IR studies, and the surface composition of the outermost layers has been studied by APXPS (Ambient Pressure X-ray Photoemission Spectroscopy). The reaction products were followed by mass spectrometry, making it possible to relate the chemical properties of the catalysts under reaction conditions with their selectivity. Combining these techniques, it has been shown that the structure of the support (monoclinic or cubic ZrO₂) affects the metal dispersion, mobility, and reorganization of metal sites under methanol steam reforming (MSR) conditions, influencing the oxidation state of surface metal species, with important consequences in the catalytic activity. Correlating the mass spectra of the reaction products with these spectroscopic studies, it was possible to conclude that electropositive metal species play an imperative role for high CO₂ and H₂ selectivity in the MSR reaction (less CO formation). Full article