Prospects of solar thermal hydrogen production processes

This article provides a critical discussion of prospects of solar thermal hydrogen production in terms of technological and economic potentials and their possible role for a future hydrogen supply. The study focuses on solar driven steam methane reforming, thermochemical cycles, high temperature water electrolysis and solar methane cracking. Development status and technological challenges of the processes and objectives of ongoing research are described. Estimated hydrogen production costs are shown in comparison to other options. A summary of current discussions and today's scenarios of future use of hydrogen as an energy carrier and a brief overview on the development status of end-use technologies characterise uncertainties whether hydrogen could emerge as important energy carrier until 2050. Another focus is on industrial hydrogen demand in areas with high direct solar radiation which may be the main driver for the further development of solar thermal hydrogen production processes in the coming decades.     

Potential methods for geothermal-based hydrogen production

In this study, four potential methods are identified for geothermal-based hydrogen production, namely, (i) directly from the geothermal steam, (ii) through conventional water electrolysis using the electricity generated from geothermal power plant, (iii) using both geothermal heat and electricity for high temperature steam electrolysis and/or hybrid processes, (iv) using the heat available from geothermal resource in thermochemical processes to disassociate water into hydrogen and oxygen. Here we focus on relatively low-temperature thermochemical and hybrid cycles, due to their greater application possibility, and examine them as a potential option for hydrogen production using geothermal heat. We also present a brief thermodynamic analysis to assess their performance through energy and exergy efficiencies for comparison purposes. The results show that these cycles have good potential and become attractive due to the overall system efficiencies over 50%. The copper–chlorine cycle is identified as a highly promising cycle for geothermal hydrogen production. Furthermore, three types of industrial electrolysis methods, which are generally considered for hydrogen production currently, are also discussed and compared with the above mentioned cycles.     

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.     

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.     

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%.     

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.     

Life cycle analysis of processes for hydrogen production

Hydrogen is considered to be an ideal energy carrier in the foreseeable future and can play a very important role in the energy system. A variety of technologies can be used to produce hydrogen. One of the most remarkable methods for large-scale hydrogen production is thermo-chemical water decomposition using heat energy from nuclear, solar and other sources. Detailed simulations of the two most promising water splitting thermo-chemical cycles (the Westinghouse cycle and the Sulphur-Iodine cycle) were performed in Aspen Plus code and obtained results were used for life cycle analysis. They were compared with two different processes for hydrogen production (coal gasification and coal pyrolysis). Some of the results obtained from LCA are also reported in the paper.     

Lab-scale water-splitting hydrogen production test of modified hybrid sulfur process working at around 550 °C

A hydrogen production process based on a well-known hybrid sulfur process is under development; the process employs two electrolyzers, one of which uses a unique gaseous sulfur trioxide electrolysis. The goal is to lower the top-end reaction temperature to around the operating temperature of sodium cooled fast breeder reactors (500-550 °C). Three key engineering issues were examined using a laboratory-stage apparatus. (1) An operating procedure for maintaining mass balance was proven through stoichiometric, continuous hydrogen production at 0.2 NL/h. (2) The functionality and material adaptability of the sulfur trioxide electrolyzer were also demonstrated with no serious malfunctions. (3) The thermal efficiency acquired from operation data was considerably low (0.5%). However, calculations exploring its potential suggested that a thermal efficiency greater than that of ordinary alkaline water electrolysis powered by existing light-water reactors (28%) could be achieved by regulating the flow rate of sulfuric acid vaporization, concentrating sulfuric acid with a multiple-effect evaporator, and reducing the cell voltages of the electrolyzers.     

Thermodynamic analysis and optimization of an integrated solar thermochemical hydrogen production system

In this study, thermodynamic analysis of solar-based hydrogen production via copper-chlorine (Cu–Cl) thermochemical water splitting cycle is presented. The integrated system utilizes air as the heat transfer fluid of a cavity-pressurized solar power tower to supply heat to the Cu–Cl cycle reactors and heat exchangers. To achieve continuous operation of the system, phase change material based on eutectic fluoride salt is used as the thermal energy storage medium. A heat recovery system is also proposed to use the potential waste heat of the Cu–Cl cycle to produce electricity and steam. The system components are investigated thoroughly and system hotspots, exergy destructions and overall system performance are evaluated. The effects of varying major input parameters on the overall system performance are also investigated. For the baseline, the integrated system produces 343.01 kg/h of hydrogen, 41.68 MW of electricity and 11.39 kg/s of steam. Overall system energy and exergy efficiencies are 45.07% and 49.04%, respectively. Using Genetic Algorithm (GA), an optimization is performed to evaluate the maximum amount of produced hydrogen. The optimization results show that by selecting appropriate input parameters, hydrogen production rate of 491.26 kg/h is achieved.     

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.     

Development and test of a solar reactor for decomposition of sulphuric acid in thermochemical hydrogen production

Decomposition of sulphuric acid is a key step of sulphur based thermochemical cycles for hydrogen production by thermal splitting of water. The Hybrid Sulphur Cycle (HyS) consisting of two reaction steps is considered as one of the most promising cycles: firstly, sulphuric acid is decomposed by high temperature heat of 800–1200 °C forming sulphur dioxide, which in a second step is used to electrochemically split water. Compared to conventional water electrolysis only about a tenth of the theoretical voltage is required making the HyS one of the most efficient processes to produce hydrogen by concentrated solar radiation. As a result, this thermochemical cycle has the potential to significantly reduce the amount of energy required for water splitting and to efficiently generate hydrogen free of carbon dioxide emissions. The European research project HycycleS aims at a technical realisation of the HyS. One objective of the project is to develop and qualify a solar interface, meaning a device to couple concentrated solar radiation into the endothermal steps of the chemical process. Therefore, a test reactor for decomposition of sulphuric acid by concentrated solar radiation was developed and tested in the solar furnace of DLR in Cologne. Tests in concentrated solar radiation were carried out for temperatures of the honeycomb up to 950 °C decomposing sulphuric acid of 50 and 96 weight-percent. Mass and energy flow of the process were calculated in order to determine energy efficiency and chemical conversion. The influence of process parameters like temperature, flow rates and space velocity on chemical conversion and reactor efficiency was analysed in detail. If catalysts like iron oxide (Fe₂O₃) and mixed oxides (i.e. CuFe₂O₄) were used a conversion of SO₃ to SO₂ of more than 80% at a thermal efficiency of over 25% could be reached.     

Economic comparison of solar hydrogen generation by means of thermochemical cycles and electrolysis

Hydrogen is acclaimed to be an energy carrier of the future. Currently, it is mainly produced by fossil fuels, which release climate-changing emissions. Thermochemical cycles, represented here by the hybrid-sulfur cycle and a metal oxide based cycle, along with electrolysis of water are the most promising processes for ‘clean’ hydrogen mass production for the future. For this comparison study, both thermochemical cycles are operated by concentrated solar thermal power for multistage water splitting. The electricity required for the electrolysis is produced by a parabolic trough power plant. For each process investment, operating and hydrogen production costs were calculated on a 50 MW_th scale. The goal is to point out the potential of sustainable hydrogen production using solar energy and thermochemical cycles compared to commercial electrolysis. A sensitivity analysis was carried out for three different cost scenarios. As a result, hydrogen production costs ranging from 3.9–5.6 €/kg for the hybrid-sulfur cycle, 3.5–12.8 €/kg for the metal oxide based cycle and 2.1–6.8 €/kg for electrolysis were obtained.     

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.     

Clean hydrogen production with the Cu-Cl cycle - Progress of international consortium, I: Experimental unit operations

Advancement of the thermochemical copper-chlorine (Cu-Cl) cycle for hydrogen production is reviewed and discussed in this paper. Individual unit operations and their linkage into an integrated cycle are being developed by a Canadian consortium, as part of the Generation IV International Forum (GIF) for hydrogen production with the next generation of nuclear reactors. This paper focuses on the consortium’s latest advances on the Cu-Cl cycle, particularly with respect to hydrogen production with Canada’s Generation IV reactor, called SCWR (Super-Critical Water Reactor). Other heat sources may also be utilized for the Cu-Cl cycle, such as solar energy or industrial waste heat. In this first of two companion papers, recent developments in Canada’s nuclear hydrogen program are reported, specifically unit operation experiments of the Cu-Cl cycle and system integration. The following second companion paper will present system modeling with Aspen Plus, corrosion resistant materials, thermochemistry, safety, and reliability aspects of the Cu-Cl cycle.     

Environmental impacts of a standalone solar water splitting system for sustainable hydrogen production: A life cycle assessment

Hydrogen is broadly utilized in various industries. It can also be considered as a future clean energy carrier. Currently, hydrogen is mainly produced from typical fuels such as coal; however, there exist some other clean alternatives which use water decomposition techniques. Water splitting via the copper-chlorine (Cu–Cl) thermochemical cycle is a superb option for producing clean carbon-free fuel. Here, the life cycle assessment (LCA) technique is used to investigate the environmental consequences of an integrated solar Cu–Cl fuel production facility for large-scale hydrogen production. The impact of varying important input parameters including irradiation level, plant lifetime, and solar-to-hydrogen efficiency on various environmental impacts are investigated next. For instance, an improve in the solar-to-hydrogen efficiency from 15% to 30%, results in a reduction in the GWP from 1.25 to 6.27E-01 kg CO₂ eq. An uncertainty analysis using Monte Carlo simulation is conducted to deal with the study uncertainties. The results of the LCA show that the potential of acidification and global warming potential (GWP) of the current system are 8.27E-03 kg SO₂ eq. and 0.91 kg CO₂ eq./kg H₂, respectively. According to the sensitivity analysis, the plant lifetime has the highest effect on the total GWP of the plant with a range of 0.63–1.88 kg of CO₂ eq./kg H₂. Results comparison with past thermochemical-based studies shows that the GWP of the current integrated system is 7% smaller than that of a solar sulfur-iodine thermochemical cycle.     

Present status of r&d for hydrogen production from water in Japan

At present, big projects for promoting the development of new energy resources are being conducted on a national scale by both the Ministry of International Trade and Industry and the Ministry of Education in Japan. This paper outlines the state of the art in hydrogen production research supported by these projects. Results of electrolysis and thermochemical methods are described and the target required to implement the hydrogen society is discussed.     

A comprehensive comparative energy and exergy analysis in solar based hydrogen production systems

In the presented paper, energy and exergy analysis is performed for thermochemical hydrogen (H₂) production facility based on solar power. Thermal power used in thermochemical cycles and electricity production is obtained from concentrated solar power systems. In order to investigate the effect of thermochemical cycles on hydrogen production, three different cycles which are low temperature Mg–Cl, H₂SO₄ and UT-3 cycles are compared. Reheat-regenerative Rankine and recompression S–CO₂ Brayton power cycles are considered to supply electricity needed in the Mg–Cl and H₂SO₄ thermochemical cycles. Furthermore, the effects of instant solar radiation and concentration ratio on the system performance are investigated. The integration of S–CO₂ Brayton power cycle instead of reheat-regenerative Rankine enhances the system performance. The maximum exergy efficiency which is obtained in the system with Mg–Cl thermochemical and recompression S–CO₂ Brayton power cycles is 27%. Although the energy and exergy efficiencies decrease with the increase of the solar radiation, they increase with the increase of the concentration ratio. The highest exergy destruction occurred in the solar energy unit.     

Methanol production using hydrogen from concentrated solar energy

Concentrated solar thermal technology is considered a very promising renewable energy technology due to its capability of producing heat and electricity and of its straightforward coupling to thermal storage devices. Conventionally, this approach is mostly used for power generation. When coupled with the right conversion process, it can be also used to produce methanol. Indeed methanol is a good alternative fuel for high compression ratio engines. Its high burning velocity and the large expansion occurring during combustion leads to higher efficiency compared to operation with conventional fuels. This study is focused on the system level modeling of methanol production using hydrogen and carbon monoxide produced with cerium oxide solar thermochemical cycle which is expected to be CO₂ free. A techno-economic assessment of the overall process is done for the first time. The thermochemical redox cycle is operated in a solar receiver-reactor with concentrated solar heat to produce hydrogen and carbon monoxide as the main constituents of synthesis gas. Afterwards, the synthesis gas is turned into methanol whereas the methanol production process is CO₂ free. The production pathway was modeled and simulations were carried out using process simulation software for MW-scale methanol production plant. The methanol production from synthesis gas utilizes plug-flow reactor. Optimum parameters of reactors are calculated. The solar methanol production plant is designed for the location Almeria, Spain. To assess the plant, economic analysis has been carried out. The results of the simulation show that it is possible to produce 27.81 million liter methanol with a 350 MW_th solar tower plant. It is found out that to operate this plant at base case scenario, 880685 m² of mirror's facets are needed with a solar tower height of 220 m. In this scenario a production cost of 1.14 €/l Methanol is predicted.     

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).