Comparative study of the activity of nickel ferrites for solar hydrogen production by two-step thermochemical cycles

In this work, we compare the activity of unsupported and monoclinic zirconia – supported nickel ferrites, calcined at two different temperatures, for solar hydrogen production by two-step water-splitting thermochemical cycles at low thermal reduction temperature. Commercial nickel ferrite, both as-received and calcined in the laboratory, as well as laboratory made supported NiFe₂O₄, are employed for this purpose. The samples leading to higher hydrogen yields, averaged over three cycles, are those calcined at 700 °C in each group (supported and unsupported) of materials. The comparison of the two groups shows that higher chemical yields are obtained with the supported ferrites due to better utilisation of the active material. Therefore, the highest activity is obtained with ZrO₂-supported NiFe₂O₄ calcined at 700 °C.     

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.     

Operational strategy of a two-step thermochemical process for solar hydrogen production

A two-step thermochemical cycle process for solar hydrogen production from water has been developed using ferrite-based redox systems at moderate temperatures. The cycle offers promising properties concerning thermodynamics and efficiency and produces pure hydrogen without need for product separation.     

Techno economic feasibility study on hydrogen production using concentrating solar thermal technology in India

The techno-economic analysis of hydrogen (H₂) production using concentrating solar thermal (CST) technologies is performed in this study. Two distinct hydrogen production methods, namely: a) thermochemical water splitting [model 1] and b) solid oxide electrolysers [model 2], are modeled by considering the total heat requirement and supplied from a central tower system located in Jaisalmer, India. The hourly simulated thermal energy obtained from the 10 MW_th central tower system is fed as an input to both these hydrogen production systems for estimating the hourly hydrogen production rate. The results revealed that these models yield hydrogen at a rate of 31.46 kg/h and 25.2 kg/h respectively for model 1 and model 2. Further, the Levelized cost of hydrogen (LCoH) for model 1 and model 2 is estimated as ranging from $ 8.23 and $ 14.25/kg of H₂ and $ 9.04 and $ 19.24/kg, respectively, for different scenarios. Overall, the present work displays a different outlook on real-time hydrogen production possibilities and necessary inclusions to be followed for future hydrogen plants in India. The details of the improvisation and possibilities to improve the LCoH are also discussed in this study.     

Life cycle analysis of a solar thermal system with thermochemical storage process

Solar energy itself is generally considered as environmentally friendly, nevertheless it is still important to take into consideration the environmental impacts caused by production of thousands of solar thermal systems. In this work the standard LCA methodology has been extended to analyse the total environmental impacts of a new more efficient solar thermal system SOLARSTORE during its whole life cycle. This system is being developed by a 5th Framework EC project. The LCA results show that to produce 1 GJ energy with SOLARSTORE system will result in global warming potential of 6.3–10 kg CO₂, acidification potential of 46.6–70 g SO₂, eutrophication of 2.1–3.1 g phosphate and photochemical oxidant of 0.99–1.5 g C₂H₄. The raw material acquisition and components manufacturing processes contribute 99% to the total environmental impacts. In comparison with traditional heating systems, SOLARSTORE system provides a considerably better solution for reduction of negative environmental impacts by using solar energy more efficiently.     

A strategy for optimizing efficiencies of solar thermochemical fuel production based on nonstoichiometric oxides

Thermochemical cycling (TC) is a promising means of harvesting solar energy. Two-step TC with a redox active metal oxide (e.g., ceria, a benchmark material) serving as a reaction intermediate for dissociating steam or carbon dioxide, has attracted much attention recently. However, further improving the energy conversion efficiency of this process remains a major challenge. In this work, we propose an innovative modification to the heat recovery approach as a means of enhancing efficiency. Specifically, a variable amount of oxidant (e.g., steam) is injected to actively assist the cooling of thermally reduced metal oxide, achieving both in-situ heat recovery and potentially faster cooling rates than conventional approaches. Our analysis, based on a thermochemical heat engine model, shows that the solar-to-fuel efficiency using ceria under typical solar TC operating conditions could be significantly improved (the efficiency of the new strategy can reach 24.36% without further gas or solid heat recovery when the reduction temperature is 1600 °C) whilst temperature swing be reduced simultaneously compared with conventional methods. Exergy efficiency is also analyzed for thermochemical splitting of water and CO₂. This new strategy contributes significantly to the simplification of solar reactor design and to potential enhancement in both fuel productivity and energy conversion efficiency on a temporal basis.     

Modeling of a direct solar receiver reactor for decomposition of sulfuric acid in thermochemical hydrogen production cycles

Hydrogen production thermochemical cycles, based on the recirculation of sulfur-based compounds, are among the best suited processes to produce hydrogen using concentrated solar power. The sulfuric acid decomposition section is common to each sulfur-based cycle and represents one of the fundamental steps. A novel direct solar receiver-reactor concept is conceived, conceptually designed and simulated. A detailed transport phenomena model, including mass, energy and momentum balance expressions as well as suitable decomposition kinetics, is described adopting a finite volume approach. A single unit reactor is simulated with an inlet flow rate of 0.28 kg/s (corresponding to a production of approximately 11 kg_H2/h in a Hybrid Sulfur process) and a direct solar irradiation at a constant power of 143 kW/m². Results, obtained for the high temperature catalytic decomposition of SO₃ into SO₂ and O₂, demonstrate the effectiveness of the proposed concept, operating at pressures of 14 bar. A maximum temperature of 879 °C is achieved in the reactor body, with a corresponding average SO₂ mass fraction of 27.8%. The overall pressure drop value is 1.7 bar. The reactor allows the SO₃ decomposition into SO₂ and O₂ to be realized effectively, requiring an external high temperature solar power input of 123.6 kJ/molSO2 (i.e. 123.6 kJ/mol_H2).     

Features of solar thermochemical redox cycles for hydrogen production from water as a function of reactants’ main characteristics

Promising applications of concentrated solar energy are thermochemical cycles based on metal-metal oxide redox reactions for hydrogen production. These cycles usually consist of two steps: metal hydrolysis followed by solar reduction or thermal decomposition of the metal oxide. Thermodynamic analysis sustained by experimental results obtained for different reactants such as boron, zinc, tin and cadmium indicates that the cycle efficiency essentially depends on molar weight, valence, vapor pressure of reduced metals at reaction temperature, and strength of metal-oxygen (Me-O) bonds. Metals with lower molecular weight-to-valence ratio and stronger Me-O bonds demonstrate higher hydrogen productivity, better conversion and larger amount of heat released during the hydrolysis reaction. However, they require higher temperatures or multiple steps for the reduction of their oxides.This paper compares previously published results about these two-step processes complemented by more recent ones and describes the main aspects of selecting solid reactants to enable effective, reliable and safe operation of both the hydrolysis and the reduction steps.     

The use of boron for thermochemical storage and distribution of solar energy

Boron has been proposed as a candidate for hydrogen production. In this study a process is described in which boron is used as a means to store and transport solar energy from a production site to motor vehicles, where it is used to generate hydrogen and heat. The proposed multi-step fuel cycle includes no carbon as a reducing agent and, therefore, no release of CO₂ to the atmosphere. This process is safe, mostly involving harmless materials and well-understood technologies. It eliminates the distribution, storage, and pumping of hydrogen at the refueling station, and diminishes the amount of hydrogen stored on the vehicle to a minimum. It is shown that the boron reaction with water, performed on-board of a vehicle, has high hydrogen storage capacity based on both volume and mass, compared with other candidate technologies. An energy balance of the entire process predicts that the overall efficiency of converting solar energy to work by the vehicle engine can be about 11%.     

Two-step water splitting thermochemical cycle based on iron oxide redox pair for solar hydrogen production

This study deals with solar hydrogen production from the two-step iron oxide thermochemical cycle (Fe₃O₄/FeO). This cycle involves the endothermic solar-driven reduction of the metal oxide (magnetite) at high temperature followed by the exothermic steam hydrolysis of the reduced metal oxide (wustite) for hydrogen generation. Thermodynamic and experimental investigations have been performed to quantify the performances of this cycle for hydrogen production. High-temperature decomposition reaction (metal oxide reduction) was performed in a solar reactor set at the focus of a laboratory-scale solar furnace. The operating conditions for obtaining the complete reduction of magnetite into wustite were defined. An inert atmosphere is required to prevent re-oxidation of Fe(II) oxide during quenching. The water-splitting reaction with iron(II) oxide producing hydrogen was studied to determine the chemical kinetics, and the influence of temperature and particles size on the chemical conversion. A conversion of 83% was obtained for the hydrolysis reaction of non-stoichiometric solar wustite Fe_(1−y)O at 575 °C.     

Experimental assessment of the cyclability of the Mn2O3/MnO thermochemical cycle for solar hydrogen production

The cyclability of Mn₂O₃/MnO thermochemical cycle for solar hydrogen production has been experimentally evaluated. The results of three consecutive cycles show a stable hydrogen production per mass of initial solid that is in agreement with the maximum expected amount according to the stoichiometry of the process. The characterization of the material recovered after each cycle shows a mixture of different manganese oxide phases that are completely converted into MnO in the subsequent thermal reduction, maintaining the productivity of the cycles. Based on that, a modification of the thermochemical cycle scheme is proposed taking into account the differences observed between the first cycle and the following ones. MnO₂/MnO thermochemical cycle appears as a promising alternative, working in the same temperature range but with a theoretical hydrogen production per unit mass of solid manganese oxide almost twice than that obtained with the conventional Mn₂O₃/MnO cycle. Finally, the results of exergy efficiency of the complete cycle give new insights into the commercial possibilities of the cycle for hydrogen production, demonstrating the sustainable cyclability of the process regarding the manganese containing materials at lower temperatures than those theoretically reported in literature and consequently with higher exergy efficiencies that the common values associated to this cycle.     

Two-step thermochemical electrolysis: An approach for green hydrogen production

Electrolysis and thermochemical water splitting are approaches to produce green hydrogen that use either an electrical potential (electrolysis) or a chemical potential (thermochemical water splitting) to split water. Electrolysis is technologically mature when applied at low temperatures, but it requires large quantities of electrical energy. In contrast to electrolysis, thermochemical water splitting uses thermal energy, as thermal energy can typically be supplied at a lower unit cost than electrical energy using concentrating solar power. Thermochemical water splitting, however, typically suffers from high thermal losses at the extremely high process temperatures required, substantially increasing the total energy required. We show how, by combining electrical and chemical potentials, a novel and cost-efficient water splitting process can be envisioned that overcomes some of the challenges faced by conventional electrolysis and thermochemical water splitting. It uses a mixed ionic and electronic conducting perovskite with temperature-dependent oxygen non-stoichiometry as an anode in an electrolyzer. If solar energy is used as the primary source of all energy required in the process, the cost of the energy required to produce hydrogen could be lower than in high-temperature electrolysis by up to 7%.     

Solar hydrogen production by two-step thermochemical cycles: Evaluation of the activity of commercial ferrites

In this work, we report on the evaluation of the activity of commercially available ferrites with different compositions, NiFe₂O₄, Ni_0.5Zn_0.5Fe₂O₄, ZnFe₂O₄, Cu_0.5Zn_0.5Fe₂O₄ and CuFe₂O₄, for hydrogen production by two-step thermochemical cycles, as a preliminary study for solar energy driven water splitting processes. The samples were acquired from Sigma–Aldrich, and are mainly composed of a spinel crystalline phase. The net hydrogen production after the first reduction–oxidation cycle decreases in the order NiFe₂O₄ > Ni_0.5Zn_0.5Fe₂O₄ > ZnFe₂O₄ > Cu_0.5Zn_0.5Fe₂O₄ > CuFe₂O₄, and so does the H₂/O₂ molar ratio, which is regarded as an indicator of potential cyclability. Considering these results, the nickel ferrite has been selected for longer term studies of thermochemical cycles. The results of four cycles with this ferrite show that the H₂/O₂ molar ratio of every two steps increases with the number of cycles, being the total amount stoichiometric regarding the water splitting reaction. The possible use of this nickel ferrite as a standard material for the comparison of results is proposed.     

Analysis of sulfur–iodine thermochemical cycle for solar hydrogen production. Part I: decomposition of sulfuric acid

The sulfur–iodine (S–I) thermochemical water splitting cycle is one of the most studied cycles for hydrogen (H₂) production. S–I cycle consists of four sections: (I) acid production and separation and oxygen purification, (II) sulfuric acid concentration and decomposition, (III) hydroiodic acid (HI) concentration, and (IV) HI decomposition and H₂ purification. Section II of the cycle is an endothermic reaction driven by the heat input from a high temperature source. Analysis of the S–I cycle in the past thirty years have been focused mostly on the utilization of nuclear power as the high temperature heat source for the sulfuric acid decomposition step. Thermodynamic as well as kinetic considerations indicate that both the extent and rate of sulfuric acid decomposition can be improved at very high temperatures (in excess of 1000 °C) available only from solar concentrators. The beneficial effect of high temperature solar heat for decomposition of sulfuric acid in the S–I cycle is described in this paper. We used Aspen Technologies' HYSYS chemical process simulator (CPS) to develop flowsheets for sulfuric acid (H₂SO₄) decomposition that include all mass and heat balances. Based on the HYSYS analyses, two new process flowsheets were developed. These new sulfuric acid decomposition processes are simpler and more stable than previous processes and yield higher conversion efficiencies for the sulfuric acid decomposition and sulfur dioxide and oxygen formation.     

Characterization of a thermochemical reactor for thermal solar energy

The main purpose of this work is to elucidate the thermochemical characteristics of a fluidized bed reactor to be used as a solar reactor in thermal energy storage. Zinc sulfate dissociation was studied over the temperature range from 973 to 1123 K. During the reaction problems such as non isothermisity of the bed and pressure drop changes with the reaction, were detected. It was shown that the fluidity increased with temperature and degree of dissociation, but the pressure drop amplitude increased exponentially with gas velocity and particle size when slugging is present in the bed.     

Interplay of material thermodynamics and surface reaction rate on the kinetics of thermochemical hydrogen production

Production of chemical fuels using solar energy has been a field of intense research recently, and two-step thermochemical cycling of reactive oxides has emerged as a promising route. In this process, the oxide of interest is cyclically exposed to an inert gas, which induces (partial) reduction of the oxide at a high temperature, and to an oxidizing gas of either H₂O or CO₂ at the same or lower temperature, which reoxidizes the oxide, releasing H₂ or CO. Thermochemical cycling of porous ceria was performed here under realistic conditions to identify the limiting factor for hydrogen production rates. The material, with 88% porosity and moderate specific surface area, was reduced at 1500 °C under inert gas with 10 ppm residual O₂, then reoxidized with H₂O under flow of 600 sccm g^?1 of 20% H₂O in Ar to produce H₂. The fuel production process transitions from one controlled by surface reaction kinetics at temperatures below ～1000 °C to one controlled by the rate at which the reactant gas is supplied at temperatures above ～1100 °C. The reduction of ceria, when heated from 800 to 1500 °C, is observed to be gas limited at a temperature ramp rate of 50 °C min^?1 at a flow of 1000 sccm g^?1 of 10 ppm O₂ in Ar. Consistent with these observations, application of Rh catalyst particles improves the oxidation rate at low temperatures, but provides no benefit at high temperatures for either oxidation or reduction. The implications of these results for solar thermochemical reactors are discussed.     

Evaluation of a solar intermittent refrigeration system for ice production operating with ammonia/lithium nitrate

A novel solar intermittent refrigeration system for ice production developed in the Centro de Investigación en Energía of the Universidad Nacional Autónoma de México is presented. The system operates with the ammonia/lithium nitrate mixture. The system developed has a nominal capacity of 8 kg of ice/day. It consists of a cylindrical parabolic collector acting as generator-absorber. Evaporator temperatures as low as −11 °C were obtained for several hours with solar coefficients of performance up to 0.08. It was found that the coefficient of performance increases with the increment of solar radiation and the solution concentration. A dependency of the coefficient of performance was not founded against the cooling water temperature. Also it was found that the maximum operating pressure increases meanwhile the generation temperature decreases with an increase of the solution concentration.