Enhanced steam electrolysis with exsolved iron nanoparticles in perovskite cathode

The sustainable supply of clean energy may depend on the hydrogen, which usually derives from steam electrolysis for SOEC. However, the current steam electrolysis using SOEC still faces many challenges, such as low catalytic efficiency, poor structural stability. We synthesize a series of La_0.6Sr_0.4Fe_xO_3-δ (LSF_x, x = 0.8–1.2) materials, utilizing in situ exsolved metal (Fe) nanoparticles to construct a metal-oxide interface to enhance the performance of steam electrolysis and coking resistance. The active metal-oxide interface can effectively improve the performance of steam electrolysis. The H₂ production reaches 4.52 mL min^?1 cm^?2 with the current efficiency of 97.81% at 1.6 V and 850 °C for the cell with LSF_1.1-Ce_0.8Sm_0.2O_3-δ cathode and anode. It shows excellent long-term stability and redox cycling capability after dozens of hours of operation. This research is of great significance for efficient hydrogen production.     

A thermodynamic equilibrium analysis of hydrogen and synthesis gas production from steam reforming of acetic acid and acetone blends as bio-oil model compounds

Thermodynamic analysis of steam reforming of blends of two model oxygenates, acetic acid and acetone, representing carboxylic acids and ketones in bio-oil is performed to investigate the effects of their potential interactions on hydrogen yield, synthesis gas composition and progress of reaction network. The results show that both acetic acid and acetone reach complete conversion at all operating conditions. Higher S/C molar ratio results in higher H₂ and CO₂ yields for both acetic acid and acetone. With the increase in pressure, H₂ and CO yields are diminished whereas CH₄ and CO₂ yields are enhanced. H₂ and CO₂ yields increase with the decrease in acetone concentration in the feed blend. CO and CH₄ production are affected adversely for acetic acid rich blends. The maximum H₂ yield values are 75.54%, 78.34%, 80.09%, 81.78% and 84.17% at 700 °C for acetic acid/acetone blends of 0.0/1.0, 0.3/0.7, 0.5/0.5, 0.7/0.3 and 1.0/0.0, respectively.     

Hydrogen production with an auto-thermal MSW steam gasification and direct melting system: A process modeling

Municipal solid waste steam gasification and direct melting system is proposed in this study for H₂ production and ash melting simultaneously. Part of the H₂ generated in gasification is extracted for combustion with pure oxygen in the melting zone to provide the energy necessary for auto-thermal operation. A simulation model is developed with Aspen Plus to investigate the performance and optimum conditions of the system. For the feedstock with a lower heating value of 18.91 MJ/kg used in this study, 39.8% of the generated H₂ needs to be extracted to maintain the heat balance of the system at the gasification temperature of 900 °C, melting temperature of 1400 °C, and S/M of 1. The net H₂ yield is ～77.3 kg/t-MSW with a net cold gas efficiency of 49.1% under the same operating condition. An optimum operation condition for T (850–1000 °C) and S/M (0.6–1.0) is determined considering the balance between H₂ production ability and the auto-thermal energy balance.     

Effect of catalytic washcoat shape and properties on mass transfer characteristics of microstructured steam-methanol reformers for hydrogen production

Many attempts have been made to improve mass transfer by reducing the size of reactors. However, such reduction will fairly quickly reach practical limitations and numerous difficulties still remain. Catalytic washcoat shape and properties may be critical design factors, but the mechanisms for their effects on mass transfer characteristics are still not fully understood. To effectively eliminate problems associated with mass transport phenomena in microstructured steam-methanol reformers, the effects of washcoat shape and properties were investigated in various situations by performing computational fluid dynamics simulations. The dependence of the solution on mass transfer characteristics was reduced to a small number of dimensionless parameters. A dimensionless mass transfer analysis was carried out in terms of the Sherwood, Schmidt, and pore Reynolds numbers. The results indicated that the rate of mass transfer is predominantly controlled by washcoat properties, and porosity and effective thermal conductivity are fundamentally important. The rate of the reforming reaction is typically controlled by kinetics at a temperature of 480 K and limited by mass transfer at a temperature of 580 K. The shape of washcoats affects the overall mass transfer characteristics, depending on the structural and thermal properties of washcoats. The shape effect is limited by heat transfer. A three-fold increase in effectiveness factor can be achieved by increasing the effective thermal conductivity of the washcoat. Design recommendations were finally made to improve transport characteristics for the systems.     

Efficient utilization of waste heat from molten carbonate fuel cell in parabolic trough power plant for electricity and hydrogen coproduction

Direct steam generating parabolic trough power plant is an important technology to match future electric energy demand. One of the problems related to its emergence is energy storage. Solar-to-hydrogen is a promising technology for solar energy storage. Electrolysis is among the most processes of hydrogen production recently investigated. High temperature steam electrolysis is a clean process to efficiently produce hydrogen. In this paper, steam electrolysis process using solar energy is used to produce hydrogen. A heat recovery steam generator generates high temperature steam thanks to the molten carbonate fuel cell's waste heat. The analytical study investigates the energy efficiency of solar power plant, molten carbonate fuel cell and electrolyser. The impact of waste heat utilization on electricity and hydrogen generation is analysed. The results of calculations done with MATLAB software show that fuel cell produces 7.73 MWth of thermal energy at design conditions. 73.37 tonnes of hydrogen and 14.26 GWh of electricity are yearly produced. The annual energy efficiency of electrolyser is 70% while the annual mean electric efficiency of solar power plant is 18.30%.The proposed configuration based on the yearly electricity production and hydrogen generation has presented a good performance.     

Structure-dependent activity and stability of Al2O3 supported Rh catalysts for the steam reforming of n-dodecane

Steam reforming of liquid hydrocarbon fuels is an appealing way for the production of hydrogen. In this work, the Rh/Al₂O₃ catalysts with nanorod (NR), nanofiber (NF) and sponge-shaped (SP) alumina supports were successfully designed for the steam reforming of n-dodecane as a surrogate compound for diesel/jet fuels. The catalysts before and after reaction were well characterized by using ICP, XRD, N₂ adsorption, TEM, HAADF-STEM, H₂-TPR, CO chemisorption, NH₃-TPD, CO₂-TPD, XPS, Al²⁷ NMR and TG. The results confirmed that the dispersion and surface structure of Rh species is quite dependent on the enclosed various morphologies. Rh/Al₂O₃-NR possesses highly dispersed, uniform and accessible Rh particles with the highest percentage of surface electron deficient Rh⁰ active species, which due to the unique properties of Al₂O₃ nanorod including high crystallinity, relatively large alumina particle size, thermal stability, and large pore volume and size. As a consequent, Rh/Al₂O₃-NR catalyst exhibited superior catalytic activity towards steam reforming reactions and hydrogen production rate over other two catalysts. Especially, Rh/Al₂O₃-NR catalyst showed the highest hydrogen production rate of 87,600 mmol g_fuel^?1 g_Rh^?1min^?1 among any Rh-based catalysts and other noble metal-based catalysts to date. After long-term reaction, a significant deactivation occurred on Rh/Al₂O₃–NF and Rh/Al₂O₃-SP catalysts, due to aggregation and sintering of Rh metal particles, coke deposition and poor hydrothermal stability of nanofibrous structure. In contrast, the Rh/Al₂O₃-NR catalyst shows excellent reforming stability with negligible coke formation. No significantly sintering and aggregation of the Rh particles is observed after long-term reaction. Such great catalyst stability can be explained by the role of hydrothermal stable nanorod alumina support, which not only provides a unique environment for the stabilization of uniform and small-size Rh particles but also affords strong surface basic sites.     

Economic competitiveness of compact steam methane reforming technology for on-site hydrogen supply: A Foshan case study

On-site hydrogen production through steam-methane reforming (SMR) from city gas or natural gas is believed to be a cost-effective way for hydrogen-based infrastructure due to high cost of hydrogen transportation. In recent years, there have been a lot of on-site hydrogen fueling stations under design or construction in China. This study introduces current developments and technology prospects of skid-mounted SMR hydrogen generator. Also, technical solutions and economic analysis are discussed based on China's first on-site hydrogen fueling station project in Foshan. The cost of hydrogen product from skid-mounted SMR hydrogen generator is about 23 CNY/kg with 3.24 CNY/Nm³ natural gas. If hydrogen price is 60 CNY/kg, IRR of on-site hydrogen fueling station project reaches to 10.8%. While natural gas price fall to 2.3 CNY/Nm³, the hydrogen cost can be reduced to 18 CNY/kg, and IRR can be raised to 13.1%. The conclusion is that skid-mounted SMR technology has matured and is developing towards more compact and intelligent design, and will be a promising way for hydrogen fueling infrastructures in near future.     

Techno-economical evaluations of decarbonized hydrogen production based on direct biogas conversion using thermo-chemical looping cycles

Hydrogen production by biogas conversion represent a promising solution for reduction of fossil CO₂ emissions. In this work, a detailed techno-economic analysis was performed for decarbonized hydrogen production based on biogas conversion using calcium and chemical looping cycles. All evaluated concepts generate 100,000 Nm³/h high purity hydrogen. As reference cases, the biogas steam reforming design without decarbonization and with CO₂ capture by gas-liquid chemical absorption were also considered. The results show that iron-based chemical looping design has higher energy efficiency compared with the gas-liquid absorption case by 2.3 net percentage points as well as a superior carbon capture rate (99% vs. 65%). The calcium looping case shows a lower efficiency than chemical scrubbing, with about 2.5 net percentage points, but the carbon capture rate is higher (95% vs. 65%). The hydrogen production cost increases with decarbonization, the calcium looping shows the most favourable situation (37.14 €/MWh) compared to the non-capture steam reforming case (33 €/MWh) and MDEA and iron looping cases (about 42 €/MWh). The calcium looping case has the lowest CO₂ avoidance cost (10 €/t) followed by iron looping (20 €/t) and MDEA (31 €/t) cases.     

Operation of Rh/Ce0.75Zr0.25O2-δ-ƞ-Al2O3/FeCrAl wire mesh honeycomb catalytic modules in diesel steam and autothermal reforming

The Rh/Ce_0·75Zr_0·25O_2–δ-ƞ-Al₂O₃/FeCrAl structured catalytic blocks of length 10, 20, and 60 mm were prepared and tested in the reactions of steam and autothermal reforming of n-hexadecane. It was found in a series of experiments on hexadecane steam reforming with the catalyst heating solely through the reactor wall that the complete conversion of hexadecane at a furnace temperature below 750 °C was not achieved even at GHSV = 10,000 h⁻¹. Under these conditions, the formation of carbon on the catalyst surface was observed. At the reactor wall temperature of 800 °C, the complete conversion of hexadecane was achieved even in the 10 mm long catalytic block (GHSV = 60,000 h⁻¹), accompanied by the formation of various intermediate light hydrocarbons. To achieve complete conversion of these intermediate compounds (mainly 1-alkenes), it is necessary to carry out the steam reforming reaction at GHSV = 10,000 h⁻¹. At hexadecane autothermal reforming, heat is supplied to the reaction zone by exothermic oxidation reaction, which makes this process more efficient. In experiments with the use of additional external heat supply through the reactor wall, complete conversion of hexadecane occurred at GHSV = 120,000 h⁻¹. To convert all by-products (mainly 1-alkenes) and achieve a nearly thermodynamic equilibrium distribution of the main reaction products (H₂, CO, CO₂), the reaction should be carried out at GHSV = 20,000 h⁻¹. Without external heat supply, hexadecane conversion decreased, while the content of light hydrocarbons in the reaction products increased. An increase in the inlet amount of oxygen helps to compensate the heat losses in the reactor and to increase the efficiency of hexadecane autothermal reforming. The performed experiments allow better understanding of the processes which occur during the steam and autothermal reforming of diesel.     

Hydrogen-rich syngas production and carbon dioxide formation using aqueous urea solution in biogas steam reforming by thermodynamic analysis

Biogas is a renewable biofuel that contains a lot of CH₄ and CO₂. Biogas can be used to produce heat and electric power while reducing CH₄, one of greenhouse gas emissions. As a result, it has been getting increasing academic attention. There are some application ways of biogas; biogas can produce hydrogen to feed a fuel cell by reforming process. Urea is also a hydrogen carrier and could produce hydrogen by steam reforming. This study then employes steam reforming of biogas and compares hydrogen-rich syngas production and carbon dioxide with various methane concentrations using steam and aqueous urea solution (AUS) by Thermodynamic analysis. The results show that the utilization of AUS as a replacement for steam enriches the production of H₂ and CO and has a slight CO₂ rise compared with pure biogas steam reforming at a temperature higher than 800 °C. However, CO₂ formation is less than the initial CO₂ in biogas. At the reaction temperature of 700 °C, carbon formation does not occur in the reforming process for steam/biogas ratios higher than 2. These conditions led to the highest H₂, CO production, and reforming efficiency (about 125%). The results can be used as operation data for systems that combine biogas reforming and applied to solid oxide fuel cell (SOFC), which usually operates between 700 °C to 900 °C to generate electric power in the future.