Forging furnace with thermochemical waste-heat recuperation by natural gas reforming: Fuel saving and heat balance

This paper considers thermochemical recuperation (TCR) of waste-heat using natural gas reforming by steam and combustion products. Combustion products contain steam (H₂O), carbon dioxide (CO₂), and ballast nitrogen (N₂). Because endothermic chemical reactions take place, methane steam-dry reforming creates new synthetic fuel that contains valuable combustion components: hydrogen (H₂), carbon monoxide (CO), and unreformed methane (CH₄). There are several advantages to performing TCR in the industrial furnaces: high energy efficiency, high regeneration rate (rate of waste-heat recovery), and low emission of greenhouse gases (CO₂, NO_x). As will be shown, the use of TCR is significantly increasing the efficiency of industrial furnaces – it has been observed that TCR is capable of reducing fuel consumption by nearly 25%. Additionally, increased energy efficiency has a beneficial effect on the environment as it leads to a reduction in greenhouse gas emissions.     

Overview of the applications of thermodynamic databases to steelmaking processes

Computerized thermodynamic databases for solid and liquid steel, slags and solid oxide solutions, for large numbers of components, have been developed over the last three decades by critical evaluation/optimization of all available phase equilibrium and thermodynamic data. The databases contain model parameters specifically developed for molten slags, liquid and solid steel and solid oxide solutions. With user-friendly software, which accesses these databases, complex chemical reactions and phase equilibria occurring throughout the steelmaking process can be calculated over wide ranges of temperature, oxygen potential and pressure. In the present article, the thermodynamic models and databases for molten slag and liquid steel included in well-known thermochemical packages and their applications to complex steelmaking processes involving molten slag, steel, inclusions, refractories and gases are reviewed.     

Comparison of experimental and simulation results on catalytic HI decomposition in a silica-based ceramic membrane reactor

In this study, the catalytic decomposition of hydrogen iodide was theoretically and experimentally investigated in a silica-based ceramic membrane reactor to assess the reactor's suitability for thermochemical hydrogen production. The silica membranes were fabricated by depositing a thin silica layer onto the surface of porous alumina ceramic support tubes via counter-diffusion chemical vapor deposition of hexyltrimethoxysilane. The performance of the silica-based ceramic membrane reactor was evaluated by exploring important operating parameters such as the flow rates of the hydrogen iodide feed and the nitrogen sweep gas. The influence of the flow rates on the hydrogen iodide decomposition conversion was investigated in the lower range of the investigated feed flow rates and in the higher range of the sweep-gas flow rates. The experimental data agreed with the simulation results reasonably well, and both highlighted the possibility of achieving a conversion greater than 0.70 at decomposition temperature of 400 °C. Therefore, the developed silica-based ceramic membrane reactor could enhance the total thermal efficiency of the thermochemical process.     

Harmonised life-cycle indicators of nuclear-based hydrogen

When comparing the life-cycle environmental performance of hydrogen energy systems, significant concerns arise due to potential methodological inconsistencies between case studies. In this regard, protocols for harmonised life cycle assessment (LCA) of hydrogen energy systems are currently available to mitigate these concerns. These protocols have already been applied to conventional hydrogen from steam methane reforming as well as to a large number of both fossil and renewable hydrogen options, allowing robust comparisons between them. However, harmonised life-cycle indicators of nuclear-based hydrogen options are not yet available in the literature. This study fills this gap by using the recently developed software GreenH₂armony® to calculate the harmonised carbon, energy and acidification footprints of nuclear-based hydrogen produced through different pathways (viz., low-temperature electrolysis, high-temperature electrolysis, and thermochemical cycles). Overall, the harmonised case studies of nuclear-based hydrogen show a generally good performance in terms of carbon footprint and acidification, but an unfavourable performance in terms of non-renewable energy footprint.     

Numerical modelling for the solar driven bi-reforming of methane for the production of syngas in a solar thermochemical micro-packed bed reactor

High temperature heat transfer and thermochemical storage performances of the solar driven bi-reforming of methane (SDSCB-RM) in a solar thermochemical micro-packed bed (ST-μPB) reactor are numerically investigated under different operating conditions along ST-μPB reactor length. A pseudo-homogeneous mathematical model is developed to simulate the heat and mass transfer processes coupled with thermochemical reaction kinetics in ST-μPB reactor with radiative heat loss. The effect of several parameters including the gas flow rate (Q_g), effective thermal conductivity (λ_s,eff), operating time (t_i) and operating temperature (T_op.) were investigated. The simulated results shown that the pressure drop increases with the increase of Q_g. When the Q_g is increased, the temperature profiles at the surface of the solid phase as well as the temperature profiles of the gas phase are remarkably decreasing. The consumption of reactants (CH₄, H₂O and CO₂) is increased when the λ_s,eff is gradually increased. On the other hand, the production of products (H₂, and CO) is remarkably increasing with the increase of the λ_s,eff. According to simulated results, the overall conversions of reactants (CH₄ and CO₂) and the dimensionless flow rate (DFR) of H₂ reach the maximum values of 98.18%, 75.61% and 1.6278 at the operating time of 2.50 h. The thermochemical energy storage efficiency (η_Chem) remarkably increases with the operating temperature and the maximum value of the η_Chem can be as high as 74.21% at 1123 K. The overall conversions of reactants (CH₄ and CO₂), DFR of H₂ and the energy stored as chemical enthalpy (Q_Chem) were also evaluated in relation to the operating temperature and their maximum values of 99.43%, 89.03%, 1.6383 and 1.3745 kJ/s are obtained at 1225 K.     

Research and development on membrane IS process for hydrogen production using solar heat

Thermochemical hydrogen production has attracted considerable interest as a clean energy solution to address the challenges of climate change and environmental sustainability. The thermochemical water-splitting iodine-sulfur (IS) process uses heat from nuclear or solar power and thus is a promising next-generation thermochemical hydrogen production method that is independent of fossil fuels and can provide energy security. This paper presents the current state of research and development (R&D) of the IS process based on membrane techniques using solar energy at a medium temperature of 600 °C. Membrane design strategies have the most potential for making the IS process using solar energy highly efficient and economical and are illustrated here in detail. Three aspects of membrane design proposed herein for the IS process have led to a considerable improvement of the total thermal efficiency of the process: membrane reactors, membranes, and reaction catalysts. Experimental studies in the applications of these membrane design techniques to the Bunsen reaction, sulfuric acid decomposition, and hydrogen iodide decomposition are discussed.     

Catalytic properties of dispersed iron oxides Fe2O3/MO2 (M = Zr,Ce, Ti and Si) for sulfuric acid decomposition reaction: Role of support

Supported iron oxides have been established as an important class of catalyst for high temperature sulfuric acid decomposition. With an objective to elucidate the role of support in modifying the overall catalytic properties of dispersed iron oxide catalysts, a series of supported iron oxide based catalysts, Fe₂O₃ (15 wt%)/MO₂ (M = Zr, Ce, Ti and Si), synthesized by adsorption-equilibrium method, is investigated for sulfuric acid decomposition reaction. The structure of dispersed iron oxide phases largely depended on the nature of the support oxide as revealed by the XRD and Mössbauer studies. α-Fe₂O₃ is found to be present as a major phase on ZrO₂ and CeO₂ support while ε-Fe₂O₃ was the major phase on silica supported iron oxide. On the other hand, presence of mixed oxide Fe₂TiO₅ was revealed over TiO₂ support. Strong dispersed metal oxide-support interactions inhibited the total reduction of the dispersed phase on SiO₂ and TiO₂ as compared to complete reduction of dispersed iron oxide on CeO₂ and ZrO₂ supports during temperature programmed reduction upto 1000 °C. The order of catalytic activity at a temperature of ～750 °C is observed as Fe₂O₃/SiO₂ > Fe₂TiO₅/TiO₂ > Fe₂O₃/ZrO₂ > Fe₂O₃/CeO₂, while at higher temperatures of ～900 °C the SO₂ yield is found to be comparable for all catalysts. A relationship between the rate of sulfate decomposition and catalytic activity is established through detailed TG-DTA investigations of sulfated catalyst and support. Considerable influence of the support oxide on the composition, structure, redox properties, morphology and catalytic activities of the active iron oxide dispersed phase has been observed. Thus, the support oxides operate as a critical component in the complex supported metal oxide catalysts and these findings might influence the design and development of future high temperature sulfuric acid decomposition catalysts.     

Thermochemical cycles over redox structured reactors

Structured bodies from redox materials are a key element for the implementation of thermochemical cycles on suitable reactors for the solar H₂O splitting. In the current work different configurations of nickel ferrite were investigated with respect to their performance in H₂O splitting: i) powder, ii) disk, iii) honeycomb flow-through monoliths. The structured bodies were prepared via pressing and extrusion techniques. The performance of the different structures was affected significantly by differences in the structural characteristics. Alternative approaches involving casting techniques for the structuring of nickel ferrite porous bodies were also investigated. This work constitutes a preliminary attempt towards tuning such characteristics to achieve enhanced and cycle-to-cycle stable production yields.