Thermodynamic performance assessment of boron based thermochemical water splitting cycle for renewable hydrogen production

The present study is related with the thermodynamic performance assessment of renewable hydrogen production through Boron thermochemical water splitting cycle. Therefore, all step efficiencies and overall cycle efficiency are calculated based on complete reaction. Additionally, a parametric study is conducted to determine the effect of the reference environment temperature on the overall cycle efficiency. In this regard, exergy efficiencies, exergy destruction rates and also inlet and outlet exergy rates of the cycle are calculated and presented for various reference temperatures. The exergy efficiency of the cycle is calculated as 0.4393 based on complete reaction and occurs at 298 K. This study has shown that Boron thermochemical water splitting cycle has a great potential due to cycle performance. As a result, Boron based thermochemical water splitting cycle can help achieve better environment and sustainability due to high exergetic efficiency. By the way, economic and technical issues of the storage and transportation of the hydrogen can find a proper solution if the hydrogen production reaction of the Boron thermochemical water splitting cycle takes place on-board of a vehicle.     

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%.     

Commercial activated carbon for the catalytic production of hydrogen via the sulfur-Iodine thermochemical water splitting cycle

Eight commercial activated carbon catalysts were examined for their catalytic activity to decompose hydroiodic acid (HI) to produce hydrogen; a key reaction in the sulfur-iodine (S-I) thermochemical water splitting cycle. Activity was examined under a temperature ramp from 473 to 773 K. No statistically significant correlation was found between the measured catalyst sample properties and catalytic activity. Four of the eight samples were examined for one week of continuous operation at 723 K. All samples appeared to be stable over the period of examination.     

Iron precipitated onto ceria-zirconia nanoparticle mixtures for the production of hydrogen via two-step thermochemical water splitting

Several novel materials were synthesized by precipitating iron oxide (using the previously optimized 10% Fe loading by weight) onto mixtures of nanoparticle zirconia and ceria to investigate the effects of adding CeO₂ to FeO_x/ZrO₂ materials in the thermochemical water splitting reaction. At water splitting temperatures of 1000 °C (after thermal reduction at 1450 °C), the stability of the CeO₂-containing materials was lower than for the FeO_x/ZrO₂ material, and there was no advantage to adding CeO₂ to the FeO_x/ZrO₂ material. However, when operating at a water splitting (WS) temperature of 1200 °C, the stability increased and the hydrogen production was significantly higher over most materials compared with a water splitting temperature of 1000 °C. At a WS temperature of 1200 °C the FeO_x/Zr₇₅Ce₂₅O₂ (75% Zr₇₅O₂ and 25% CeO₂ by weight) and FeO_x/Zr₅₀Ce₅₀O₂ materials performed slightly better than the FeO_x/ZrO₂ material, and X-ray photoelectron spectroscopy data revealed that the surface concertation of iron is less important compared with water splitting at 1000 °C. The temperature programmed reduction data indicated that the FeO_x-CeO₂ interactions were weaker compared with FeO_x-ZrO₂ interactions, since the FeO_x reduction occurred at lower temperatures for the CeO₂-containing materials. The weaker interactions can explain why the stability was lower for the materials containing CeO₂ (sintering of FeO_x was likely more pronounced) The X-ray diffraction data revealed that ZrO₂-CeO₂ solid solutions formed after activation at 1450 °C and lattice volume calculations indicated that iron did incorporate into the ZrO₂-CeO₂ matrices. More incorporation was observed after water-splitting at 1200 °C compared with a lower temperature (1000 °C), and likely explains why the materials were more stable during water-splitting at 1200 °C.     

Environmental evaluation of hydrogen production via thermochemical water splitting using the Cu-Cl Cycle: A parametric study

Variations of environmental impacts with lifetime and production capacity are reported for nuclear based hydrogen production plants using the three-, four- and five-step (copper-chlorine) Cu-CI thermochemical water decomposition cycles. Life cycle assessment is utilized which is essential to evaluate and to decrease the overall environmental impact of any system and/or product. The life cycle assessments of the hydrogen production processes indicate that the four-step Cu-Cl cycle has lower environmental impacts than the three- and five-step cycles due to its lower thermal energy requirement. Parametric studies show for the four-step Cu-Cl cycle that acidification and global warming potentials can be reduced from 0.0031 to 0.0028 kg SO₂-eq and from 0.63 to 0.55 kg CO₂-eq, respectively, if the lifetime of the system increases from 10 to 100 years.     

Hydrogen production via solar-aided water splitting thermochemical cycles: Combustion synthesis and preliminary evaluation of spinel redox-pair materials

Redox-pair-based thermochemical cycles are considered as a very promising option for the production of hydrogen via renewable energy sources like concentrated solar energy and raw materials like water. This work concerns the synthesis of various spinel materials of the iron and aluminum families via combustion reactions in the solid and in the liquid-phase and the testing of their suitability as redox-pair materials for hydrogen production by water splitting via thermochemical cycles. The effects of reactants' stoichiometry (fuel/oxidizer) on the combustion synthesis reaction characteristics and on the products' phase composition and properties were studied. By fine-tuning the synthesis parameters, a wide variety of single-phase, pure and well crystallized spinels could be controllably synthesized. Post-synthesis, high-temperature calcination studies under air and nitrogen at the temperature levels encountered during solar-aided thermochemical cyclic operation have eliminated several material families due to phase composition instabilities and identified among the various compositions synthesized NiFe₂O₄ and CoFe₂O₄ as the two most suitable for cyclic water splitting – thermal reduction operation. First such thermochemical cyclic tests between 800 and 1400 °C with NiFe₂O₄ and CoFe₂O₄ in powder form in a fixed bed laboratory reactor have demonstrated capability for cyclic operation and alternate hydrogen/oxygen production at the respective cycle steps for both materials. Under the particular testing conditions the two materials exhibited hydrogen/oxygen yields of the same magnitude and similar temperatures of oxygen release during thermal reduction.     

First-principles investigation of BiVO3 for thermochemical water splitting

Thermochemical water splitting is a promising clean method of hydrogen production of high relevance in a society heavily reliant on fossil fuels. Using evolutionary methods and density functional theory, we predict the structure and electronic properties of BiVO₃. We build on previous literature to develop a framework to evaluate the thermodynamics of thermochemical water splitting cycles for hydrogen production. We use these results to consider the feasibility of BiVO₃ as a catalyst for thermochemical water splitting. We show that for BiVO₃, both the thermal reduction and gas splitting reactions are thermodynamically favorable under typical temperature conditions. We predict that thermochemical water splitting cycles employing BiVO₃ as a catalyst produce hydrogen yields comparable to those of commonly used catalysts.     

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.     

Analysis of solar chemical processes for hydrogen production from water splitting thermochemical cycles

This paper presents a process analysis of ZnO/Zn, Fe₃O₄/FeO and Fe₂O₃/Fe₃O₄ thermochemical cycles as potential high efficiency, large scale and environmentally attractive routes to produce hydrogen by concentrated solar energy. Mass and energy balances allowed estimation of the efficiency of solar thermal energy to hydrogen conversion for current process data, accounting for chemical conversion limitations. Then, the process was optimized by taking into account possible improvements in chemical conversion and heat recoveries. Coupling of the thermochemical process with a solar tower plant providing concentrated solar energy was considered to scale up the system. An economic assessment gave a hydrogen production cost of 7.98$ kg⁻¹ and 14.75$ kg⁻¹ of H₂ for, respectively a 55 MW_th and 11 MW_th solar tower plant operating 40 years.     

Techno-economic assessment of green hydrogen valley providing multiple end-users

A techno-economic analysis of a hydrogen valley is carried out in this paper. A hydrogen generator fed by a wind farm (WF) and/or a photovoltaic (PV) plant supplies four end-users: a stationary fuel cell, a hydrogen refuelling station, the injection in the natural gas pipeline and, in case of sufficient hydrogen surplus, a biological hydrogen methanation (BHM) process.The results demonstrated that an efficiency improvement and a reduction in hydrogen production costs arise from a balanced supply from wind and solar energy. Without the inclusion of a BHM process, hydrogen production costs lower than 7 €/kg were achieved by a hydrogen generator using 10–12% of the PV + WF annual energy with a PV share of 20%–50%. The hydrogen production costs were further reduced to 5 €/kg by introducing a BHM process and increasing the percentage of electrical energy supplied by the PV + WF system to 25% of its overall production.     

Novel two-step thermochemical cycle for hydrogen production from water using germanium oxide: KIER 4 thermochemical cycle

This paper proposes a novel two-step thermochemical cycle for hydrogen production from water using germanium oxide. The thermochemical cycle is herein referred to as KIER 4. KIER 4 consists of two reaction steps: the first is the decomposition of GeO₂ to GeO at approximately 1400–1800 °C, the second is hydrogen production by hydrolysis of GeO below 700 °C. A 2nd-law analysis was performed on the KIER 4 cycle and a maximum exergy conversion efficiency was estimated at 34.6%. Thermodynamic analysis of GeO₂ decomposition and hydrolysis of GeO confirmed the possibility of this cycle. To demonstrate the cycle, the thermal reduction of GeO₂ was performed in a TGA with mass-spectroscopy. Results suggest GeO₂ decomposition and oxygen gas evolution. To confirm the thermal decomposition of GeO₂, the effluent from GeO₂ decomposition was quenched, filtered and analyzed. SEM analysis revealed the formation of nano-sized particles. XRD analysis for the condensed-filtered particles showed the presence of Ge and GeO₂ phases. The result can be explained by thermodynamic instability of GeO. It is believed that GeO gas disproportionates to ½Ge and ½GeO₂ during quenching. 224 ml hydrogen gas per gram of reduced GeO₂ was produced from the hydrolysis reaction.     

Techno-economic assessment of green hydrogen and ammonia production from wind and solar energy in Iran

This paper presents a comprehensive technical and economic assessment of potential green hydrogen and ammonia production plants in different locations in Iran with strong wind and solar resources. The study was organized in five steps. First, regarding the wind density and solar PV potential data, three locations in Iran were chosen with the highest wind power, solar radiation, and a combination of both wind/solar energy. All these locations are inland spots, but since the produced ammonia is planned to be exported, it must be transported to the export harbor in the South of Iran. For comparison, a base case was also considered next to the export harbor with normal solar and wind potential, but no distance from the export harbor. In the second step, a similar large-scale hydrogen production facility with proton exchange membrane electrolyzers was modeled for all these locations using the HOMER Pro simulation platform. In the next step, the produced hydrogen and the nitrogen obtained from an air separation unit are supplied to a Haber-Bosch process to synthesize ammonia as a hydrogen carrier. Since water electrolysis requires a considerable amount of water with specific quality and because Iran suffers from water scarcity, this paper, unlike many similar research studies, addresses the challenges associated with the water supply system in the hydrogen production process. In this regard, in the fourth step of this study, it is assumed that seawater from the nearest sea is treated in a desalination plant and sent to the site locations. Finally, since this study intends to evaluate the possibility of green hydrogen export from Iran, a detailed piping model for the transportation of water, hydrogen, and ammonia from/to the production site and the export harbor is created in the last step, which considers the real routs using satellite images, and takes into account all pump/compression stations required to transport these media. This study provides a realistic cost of green hydrogen/ammonia production in Iran, which is ready to be exported, considering all related processes involved in the hydrogen supply chain.     

Recent advances of hydrogen production through particulate semiconductor photocatalytic overall water splitting

Solar energy-driven photocatalytic water splitting has been investigated for decades to produce clean and renewable green hydrogen. In this paper, the cutting-edge research within the overall water splitting system is summarized from the one-step photocatalytic overall water splitting (POWS) system to the two-step system and the cocatalysts research in this field. In addition, the photocatalytic reaction engineering study is also reviewed which is crucial for future scale-up. This mini-review provides a picture of survey of recent progress of relevant overall water splitting system, with particular attention paid to material system and mechanistic breakthroughs, and highlights the challenge and opportunity of the current system.     

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.     

Current R&D status of thermochemical water splitting iodine-sulfur process in Japan Atomic Energy Agency

Current R&D on the thermochemical water splitting iodine-sulfur (IS) process in Japan Atomic Energy Agency (JAEA) is summarized. Reactors were fabricated with industrial materials and verified by test operations: a Bunsen reactor, a H₂SO₄ decomposer, and a HI decomposer. Component materials of the reactors were stable in the operation environment. Small amount of H₂SO₄ in the anolyte solution in an electro-electrodialysis (EED) cell had no negative impact on cell performance parameters. Relationship between cell solution composition and temperature and cell parameters was formulated by experimental data. Demonstration of the test facility with process design of 100 L/h hydrogen production is performed to verify integrity of process components and stability of hydrogen production. Tests of sections were first conducted individually to show material processing rates were controllable. Based on the result, an 8-h continuous operation of the total IS process was performed in February 2016 with H₂ production rate of 10 L/h. Demonstrations are planned for longer operation period and higher H₂ production rate after improvement of components to prevent troubles.     

Techno-economic assessment of hydrogen production from seawater

Population growth and the expansion of industries have increased energy demand and the use of fossil fuels as an energy source, resulting in release of greenhouse gases (GHG) and increased air pollution. Countries are therefore looking for alternatives to fossil fuels for energy generation. Using hydrogen as an energy carrier is one of the most promising alternatives to replace fossil fuels in electricity generation. It is therefore essential to know how hydrogen is produced. Hydrogen can be produced by splitting the water molecules in an electrolyser, using the abondand water resources, which are covering around ? of the Earth's surface. Electrolysers, however, require high-quality water, with conductivity in the range of 0.1–1 μS/cm. In January 2018, there were 184 offshore oil and gas rigs in the North Sea which may be excellent sites for hydrogen production from seawater. The hydrogen production process reported in this paper is based on a proton exchange membrane (PEM) electrolyser with an input flow rate of 300 L/h. A financially optimal system for producing demineralized water from seawater, with conductivity in the range of 0.1–1 μS/cm as the input for electrolyser, by WAVE (Water Application Value Engine) design software was studied. The costs of producing hydrogen using the optimised system was calculated to be US$3.51/kg H₂. The best option for low-cost power generation, using renewable resources such as photovoltaic (PV) devices, wind turbines, as well as electricity from the grid was assessed, considering the location of the case considered. All calculations were based on assumption of existing cable from the grid to the offshore, meaning that the cost of cables and distribution infrastructure were not considered. Models were created using HOMER Pro (Hybrid Optimisation of Multiple Energy Resources) software to optimise the microgrids and the distributed energy resources, under the assumption of a nominal discount rate, inflation rate, project lifetime, and CO₂ tax in Norway. Eight different scenarios were examined using HOMER Pro, and the main findings being as follows:The cost of producing water with quality required by the electrolyser is low, compared with the cost of electricity for operation of the electrolyser, and therefore has little effect on the total cost of hydrogen production (less than 1%).The optimal solution was shown to be electricity from the grid, which has the lowest levelised cost of energy (LCOE) of the options considered. The hydrogen production cost using electricity from the grid was about US$ 5/kg H₂.Grid based electricity resulted in the lowest hydrogen production cost, even when costs for CO₂ emissions in Norway, that will start to apply in 2025 was considered, being approximately US$7.7/kg H₂.From economical point of view, wind energy was found to be a more economical than solar.     

H2 production by thermochemical water splitting with reticulated porous structures of ceria-based mixed oxide materials

In this work, we present for the first time the preparation and evaluation of Ceria-based mixed oxides reticulated porous ceramic (RPC) structures for H₂ production by thermochemical water splitting. After appropriate screening of the powder materials, ceria-based materials modified with Co, Mn and Zr were discarded due to their low cyclability and/or hydrogen productivity, derived from segregation of active phases or sintering during the thermal reduction and reoxidation. Sponge replica method has been optimized to allow obtaining a Ce_0.9Fe_0.1O_y RPC sponge structure with an outstanding hydrogen production of 15 STPcm³/g_material·cycle at a maximum temperature of 1300 °C. This better performance, comparing to the powder, can be attributed to the open macroporosity of the reticulated porous structure which enhances both heat and mass transfer. The H₂ production is maintained along several consecutive cycles without loss of activity, reinforcing the favorable prospects for large-scale hydrogen production.