Thermochemical hydrogen production from a two-step solar-driven water-splitting cycle based on cerium oxides

A new thermochemical cycle for H₂ production based on CeO₂/Ce₂O₃ oxides has been successfully demonstrated. It consists of two chemical steps: (1) reduction, 2CeO₂ → Ce₂O₃ + 0.5O₂; (2) hydrolysis, Ce₂O₃ + H₂O → 2CeO₂ + H₂. The thermal reduction of Ce(IV) to Ce(III) (endothermic step) is performed in a solar reactor featuring a controlled inert atmosphere. The feasibility of this first step has been demonstrated and the operating conditions have been defined (T = 2000 °C, P = 100–200 mbar). The hydrogen generation step (water-splitting with Ce(III) oxide) is studied in a fixed bed reactor and the reaction is complete with a fast kinetic in the studied temperature range 400–600 °C. The recovered Ce(IV) oxide is then recycled in first step. In this process, water is the only material input and heat is the only energy input. The only outputs are hydrogen and oxygen, and these two gases are obtained in different steps avoiding a high temperature energy consuming gas-phase separation. Furthermore, pure hydrogen is produced (it is not contaminated by carbon products like CO, CO₂), thus it can be used directly in fuel cells. The results have shown that the cerium oxide two-step thermochemical cycle is a promising process for hydrogen production.     

Solar thermochemical plant analysis for hydrogen production with the copper–chlorine cycle

In this article, a solar-based method of generating hydrogen from the copper–chlorine water-splitting cycle is developed and evaluated. An analysis is performed for solar plants with different hydrogen production capacities at three locations across Canada. Operating parameters of the solar field and the storage units are presented. The thermal efficiency and cost parameters of the hydrogen plant are also examined. A binary mixture of 60% NaNO₃ and 40% KNO₃ is used as the molten salt for solar energy storage. Different hydrogen production rates are analyzed. Since the solar irradiation in Calgary is much less than Toronto and Sarnia in the winter, it is found that a larger storage unit is required. The size of the storage unit increases for larger hydrogen production rates. The results support the feasibility of solar thermochemical Cu–Cl cycle as a promising and efficient pathway for large-scale production of hydrogen.     

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.     

Multi-objective optimization of a hydrogen production through the HyS process powered by solar energy in different scenarios

Thermochemical or hybrid cycles powered by concentrated solar energy are a very promising way to produce an effective clean hydrogen through the water splitting, in terms of greenhouse gas (GHG) emissions and power production sustainability. SOL2HY2 is an European project focused on this goal. It deepens the so-called HyS process in a closed or partially open version using a proper SO₂ depolarized electrolyser, and moreover, it investigates key materials and process solutions, along the entire production chain. However, the identification of the best solution to obtain a suitable hydrogen in terms of cost, efficiency, availability of energy and material, sharing of renewable energy source, continuity of operation in different locations and plant sizes, poses many challenges in terms of flexibility and complexity of the system. In fact, it involves various chemical equipment, different solar and thermal storage technologies, and variable operative conditions with different reaction temperatures and mixture concentrations. Hence it arises the importance to have a tool for the investigation of this system.In this paper, data analysis and multi-objective techniques are used to study and optimize the process under consideration. Several mathematical methods have been exploited to make the best use of the available data, such as Design of Experiments techniques, meta-modeling strategies and genetic algorithms. All these methods have been implemented in the open source environments Scilab and R.     

Reactivity of Ni,Cr and Zr doped ceria in CO2 splitting for CO production via two-step thermochemical cycle

This work focuses on modification and screening of ceria-based oxides for solar H₂O/CO₂ splitting via two-step thermochemical cycle. Ce_1-xM_xO_2-δ (M = Zr, Ni, Cr; x = 0, 0.05, 0.10, 0.15, 0.20) were synthesized via sol-gel method and tested for CO₂-splitting via two-step thermochemical cycles. Reduction was conducted at 1500 °C through a ramp rate of 10 °C/min and oxidation was performed at 1000 °C isothermally. Both Ni and Cr showed low solubility in ceria and no or very limited promoting effect on CO productivity. Cr could be reduced in the first reduction step but cannot be oxidized by CO₂ in the following oxidation step. Zr doped sample showed advantages in both CO productivity and lattice stability. 15% Zr doped exhibited the best performance with the CO productivity of 315.40 μmol/g. However, the oxidation rate of Zr doped samples was much lower than that of pure ceria. Compromise between fuel productivity and fast kinetics should be made in practical application.     

Test operation of a 100 kW pilot plant for solar hydrogen production from water on a solar tower

The present work describes the realisation and successful test operation of a 100 kW pilot plant for two-step solar thermo-chemical water splitting on a solar tower at the Plataforma Solar de Almería, which aims at the demonstration of the feasibility of the process on a solar tower platform under real conditions. The process applies multi-valent iron based mixed metal oxides as reactive species which are coated on honeycomb absorbers inside a receiver-reactor. By the introduction of a two-chamber reactor it is possible to run both process concepts in parallel and thus, the hydrogen production process in a quasi-continuous mode. In summer 2008 an exhaustive thermal qualification of the pilot plant took place, using uncoated ceramic honeycombs as absorbers. Some main aspects of these tests were the development and validation of operational and measurement strategy, the gaining of knowledge on the dynamics of the system, in particular during thermal cycling, the determination of the controllability of the whole system, and the validation of practicability of the control concept. The thermal tests enabled to improve, to refine and finally to prove the process strategy and showed the feasibility of the control concept implemented. It could be shown that rapid changeover between the modules is a central benefit for the performance of the process.In November of 2008 the absorber was replaced and honeycombs coated with redox material were inserted. This allowed carrying out tests of hydrogen production by water splitting. Several hydrogen production cycles and metal oxide reduction cycles could be run without problems. Significant concentrations of hydrogen were produced with a conversion of steam of up to 30%.     

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.     

High-temperature solar chemistry for converting solar heat to chemical fuels

This paper reviews the recent developments on thermochemical conversion of concentrated solar high temperature heat to chemical fuels. The conversion has the advantage of producing long term storable energy carriers from solar energy. This conversion also enables solar energy transportation from the sunbelt to remote population centers. The thermochemical pathway is characterized by a theoretical high efficiency. However, there are solar peculiarities in comparison to conventional thermochemical processes—high thermal flux density and frequent thermal transients because of the fluctuating insolation—, and conventional industrial thermochemical processes are generally not suitable for solar driven processes. Therefore, the adaptation to such peculiarities of solar thermochemical processes has been the important R&D task in this research field. Thermochemical water splitting, steam or CO₂ gasification of coal, steam or CO₂ reforming of methane, and hydrogenetive coupling of methane, are industrially important, endothermic processes to produce useful chemical fuels such as hydrogen, synthesis gas and C₂-hydrocarbons, which have been examined as solar thermochemical processes. The technical developments and feasibilities to conduct these endothermic processes by utilizing concentrated solar radiation as the process heat are discussed here. My recent experimental results to improve the advanced solar thermochemical technologies are also given.     

Prospects for solar only operation of the hybrid sulphur cycle for hydrogen production

The hybrid sulphur process is one of the most promising thermochemical water splitting cycles for large scale hydrogen production. While the process includes an electrolysis step, the use of sulphur dioxide in the electrolyser significantly reduces the electrical demand compared to conventional alkaline electrolysis. Solar operation of the cycle with zero emissions is possible if the electricity for the electrolyser and the high temperature thermal energy to complete the cycle are provided by solar technologies.This paper explores the possible use of photovoltaics (PV) to supply the electrical demand and examines a number of configurations. Production costs are determined for several scenarios and compared with base cases using conventional technologies. The hybrid sulphur cycle has promise in the medium term as a viable zero carbon production process if PV power is used to supply the electrolyser. However, the viability of this process is dependent on a market for hydrogen and a significant reduction in PV costs to around $1/W_p.     

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.     

Hydrogen production by water splitting on manganese ferrite-sodium carbonate mixture: Feasibility tests in a packed bed solar reactor-receiver

The sodium manganese mixed ferrite thermochemical cycle Na(Mn_1/3Fe_2/3)O₂/(MnFe₂O₄ + Na₂CO₃) for sustainable hydrogen production has been implemented in a solar reactor-receiver, packed with indirectly heated MnFe₂O₄/Na₂CO₃ mixture pellets, with the aim of verifying its feasibility and of determining the critical aspects of the process. The reactor operates at nearly constant temperature in the range 750–800 °C; the shift between the hydrogen-producing and regeneration steps is obtained by switching the reactive gas from water to carbon dioxide. Hydrogen produced during 1-h operation of the reactor is in the range of 130–460 μmol/g of mixture, depending on experimental conditions. Compared to other existing prototypes, the implemented process obtains comparable production efficiencies while operating at lower temperature both in the hydrogen production and regeneration phases.     

Construction materials development in sulfur–iodine thermochemical water-splitting process for hydrogen production

The sulfur iodine (SI) water splitting cycle for hydrogen production consists of three coupled chemical reactions, which includes the generation and decomposition of HI. The _HIx${\mathrm{HI}}_x$ environment is extremely corrosive and the severity increases with temperature. Immersion coupon corrosion screening tests were performed on materials selected from four classes of corrosion resistant materials: refractory metal, reactive metal, superalloys and ceramics. Of the materials tested, only Ta and Nb-based refractory metals and ceramic mullite can tolerate the extreme _HIx${\mathrm{HI}}_x$ environment. Severe pitting and dissolution was observed in two different reactive metal zirconium. A nickel based superalloy, C-276, also showed severe dissolution in _HIx${\mathrm{HI}}_x$ solution. The materials which showed good corrosion behavior will undergo further long-term immersion testing to assess performance. In addition, C-ring, U-bend and DCB test samples fabricated from qualified materials will be tested under stress corrosion conditions to investigate their crack initiation and growth properties.     

Liquid hydrogen

It would be helpful were it economically acceptable to liquefy hydrogen. However, methanol is a liquid and could be written CH₄O. The Nobel Laureate, George Olah along with two co-enthusiasts, published a book (2006) entitled “A Methanol ECONOMY”.³ If the methanol is synthesized from hydrogen and CO₂ from the atmosphere, burning it as a fuel would merely replace in the atmosphere the CO₂ taken from it and in the synthesis of the methanol.Let us, therefore, add “LIQUID HYDROGEN”³ to the subdivisions of uses of HYDROGEN.     

Likely near-term solar-thermal water splitting technologies

Thermodynamic and materials considerations were made for some two- and three-step thermochemical cycles to split water using solar-thermal processing. The direct thermolysis of water to produce H₂ using solar-thermal processing is unlikely in the near term due to ultra-high-temperature requirements exceeding 3000 K and the need to separate H₂ from O₂ at these temperatures. However, several lower temperature (<2500 K) thermochemical cycles including ZnO/Zn, Mn₂O₃/MnO, substituted iron oxide, and the sulfur–iodine route (S–I) provide an opportunity for high-temperature solar-thermal development. Although zirconia-based materials are well suited for metal oxide routes in terms of chemical compatibility at these temperatures, thermal shock issues are a major concern for solar-thermal applications. Hence, efforts need to be directed towards methods for designing reactors to eliminate thermal shock (ZrO₂ based) or that use graphite (very compatible in terms of temperature and thermal shock) with designs that prevent contact of chemical species with graphite materials at high temperatures. Fluid-wall reactor configurations where inert gases provide a blanket to protect the graphite wall appear promising in this regard, but their use will impact process efficiency. For the case of S–I up to 1800 K, silicon carbide appears to be a suitable material for the high-temperature H₂SO₄ dissociation. There is a need for a significant amount of work to be done in the area of high-temperature solar-thermal reactor engineering to develop thermochemical water splitting processes.     

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.