Geothermal‐based hydrogen production using thermochemical and hybrid cycles: A review and analysis

Geothermal‐based hydrogen production, which basically uses geothermal energy for hydrogen production, appears to be an environmentally conscious and sustainable option for the countries with abundant geothermal energy resources. In this study, four potential methods are identified and proposed for geothermal‐based hydrogen production, namely: (i) direct production of hydrogen from the geothermal steam, (ii) through conventional water electrolysis using the electricity generated through geothermal power plant, (iii) by using both geothermal heat and electricity for high temperature steam electrolysis and/or hybrid processes, and (iv) by using the heat available from geothermal resource in thermochemical processes. Nowadays, most researches are focused on high‐temperature electrolysis and thermochemical processes. Here we essentially discuss some potential low‐temperature thermochemical and hybrid cycles for geothermal‐based hydrogen production, due to their wider practicality, and examine them as a sustainable option for hydrogen production using geothermal heat. We also assess their thermodynamic performance through energy and exergy efficiencies. The results show that these cycles have good potential and attractive overall system efficiencies over 50% based on a complete reaction approach. The copper‐chlorine cycle is identified as a highly promising cycle for geothermal‐hydrogen production. Copyright © 2009 John Wiley & Sons, Ltd.     

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.     

Hybrid systems to address seasonal mismatches between electricity production and demand in nuclear renewable electrical grids

A strategy to enable zero-carbon variable electricity production with full utilization of renewable and nuclear energy sources has been developed. Wind and solar systems send electricity to the grid. Nuclear plants operate at full capacity with variable steam to turbines to match electricity demand with production (renewables and nuclear). Excess steam at times of low electricity prices and electricity demand go to hybrid fuel production and storage systems. The characteristic of these hybrid technologies is that the economic penalties for variable nuclear steam inputs are small. Three hybrid systems were identified that could be deployed at the required scale. The first option is the gigawatt-year hourly-to-seasonal heat storage system where excess steam from the nuclear plant is used to heat rock a kilometer underground to create an artificial geothermal heat source. The heat source produces electricity on demand using geothermal technology. The second option uses steam from the nuclear plant and electricity from the grid with high-temperature electrolysis (HTR) cells to produce hydrogen and oxygen. Hydrogen is primarily for industrial applications; however, the HTE can be operated in reverse using hydrogen for peak electricity production. The third option uses variable steam and electricity for shale oil production.     

Upgrading waste heat from a cement plant for thermochemical hydrogen production

A calcium oxide/steam chemical heat pump (CHP) is presented in the study as a means to upgrade waste heat from industrial processes for thermochemical hydrogen production. The CHP is used to upgrade waste heat for the decomposition of copper oxychloride (CuO.CuCl₂) in a copper–chlorine (Cu–Cl) thermochemical cycle. A formulation is presented for high temperature steam electrolysis and thermochemical splitting of water using waste heat of a cement plant. Numerical models are presented for verifying the availability of energy for potential waste heat upgrading in cement plants. The optimal hydration and decomposition temperatures for the calcium oxide/steam reversible reaction of 485 K and 565 K respectively are obtained for the combined heat pump and thermochemical cycle. The coefficient of performance and overall efficiency of 4.6 and 47.8% respectively are presented and discussed for the CHP and hydrogen production from the cement plant.     

Advances in hydrogen production by thermochemical water decomposition: A review

Hydrogen demand as an energy currency is anticipated to rise significantly in the future, with the emergence of a hydrogen economy. Hydrogen production is a key component of a hydrogen economy. Several production processes are commercially available, while others are under development including thermochemical water decomposition, which has numerous advantages over other hydrogen production processes. Recent advances in hydrogen production by thermochemical water decomposition are reviewed here. Hydrogen production from non-fossil energy sources such as nuclear and solar is emphasized, as are efforts to lower the temperatures required in thermochemical cycles so as to expand the range of potential heat supplies. Limiting efficiencies are explained and the need to apply exergy analysis is illustrated. The copper–chlorine thermochemical cycle is considered as a case study. It is concluded that developments of improved processes for hydrogen production via thermochemical water decomposition are likely to continue, thermochemical hydrogen production using such non-fossil energy will likely become commercial, and improved efficiencies are expected to be obtained with advanced methodologies like exergy analysis. Although numerous advances have been made on sulphur–iodine cycles, the copper–chlorine cycle has significant potential due to its requirement for process heat at lower temperatures than most other thermochemical processes.     

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.     

A critical pathway energy efficiency analysis of the thermochemical UT-3 cycle

Numerous thermochemical cycles for the production of hydrogen have been proposed in the literature, and of these the UT-3 cycle is a leading exponent. The primary objective of such processes is to be more energy efficient than water electrolysis in converting heat to hydrogen. This paper presents a critical assessment of the actual energy efficiency that could be realised in a thermochemical cycle, taking the UT-3 cycle as the basis for the study. It is concluded that the upper efficiency for this process lies around 12%, on the basis of the lower heating value of the hydrogen product, comparable to current hydrogen production techniques using photovoltaics followed by water electrolysis. The practical upper efficiency may however be lower, even much lower, as several uncertainties exist in key aspects of the process. This in-depth analysis of one thermochemical process brings to the fore issues of whether such cycles can—on the basis of efficiency—compete with electricity generation followed by electrolysis. In view of the renewed interest in thermochemical cycles, analyses such as the one presented in this paper must be carried out and published in the open literature, so that the wider research community can realistically assess the prospects of this intriguing route to hydrogen production.     

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.     

Life cycle assessment of alternatives for hydrogen production from renewable and fossil sources

New processes under development for producing hydrogen have been assessed using a life cycle methodology and compared to conventional ones. The aim of this paper is to determine the main obstacles to be beaten or the critical aspects to be addressed to ensure the feasibility of these processes. Water photosplitting, solar two-step thermochemical cycles and automaintained methane decomposition with different lay-outs were studied. They have been compared to methane steam reforming with CCS and electrolysis with different electricity sources.     

Comparison of sulfur–iodine and copper–chlorine thermochemical hydrogen production cycles

Sulfur–iodine and copper–chlorine water splitting cycles are promising methods of thermochemical hydrogen production. In this paper, these two cycles are compared from the perspectives of heat quantity, heat grade, thermal efficiency, related engineering challenges, and hydrogen production cost. The heat quantity and grade required by each step of the cycles are evaluated and the thermal efficiencies are approximated from the heat requirements. It is found that the overall heat requirements of the two cycles do not have significant differences and the overall efficiencies of the two cycles are similar, between 37 and 54%, depending on the portion of heat recovery. The copper–chlorine cycle has the advantage of a lower maximum temperature of 803 K, which is 300 K lower than the maximum temperature of 1123 K in the sulfur–iodine cycle. This indicates that the copper–chlorine cycle can link more readily with various heat sources, such as grade Generation IV nuclear and fossil fuel power stations. It is also reported that the copper–chlorine cycle can have fewer challenges of equipment materials and product separation. A cost analysis shows that the copper–chlorine and sulfur–iodine cycles have similar hydrogen production costs, which are lower than steam-methane reforming, and conventional and high temperature electrolysis, due to less use of electricity, no carbon related charges and no methane requirement in the thermochemical cycles.     

Hydrogen producing cycles using electricity and heat-hydrogen halide cycles: Electrolysis of HBr

An alternative to water electrolysis or thermochemical water splitting for hydrogen production could be a process using both electricity and heat. The electrolysis of hydrogen halides may be an important step of such hybrid processes. Some preliminary results obtained by electrolyzing concentrated hydrobromic acid with different electrode materials and at different temperatures are presented. High current densities were obtained at 1 V and less with electrodes of noble metals at low bromine concentrations.     

Possibilities of improving the efficiency of power generation with regard to electrolytic water splitting

The efficiency of power generation has a considerable influence on the upper limit of the total efficiency of electrolytic water splitting. This paper deals with the energetic potential of power generation processes and therefore with the water electrolysis processes. In the investigations reported here, it was assumed that the heat source is always the same (high-temperature nuclear reactor). For comparing thermochemical or hybrid water splitting cycles and water electrolysis, the upper limit of process temperatures must be comparable, too. Therefore high-temperature processes for power generation have been investigated. A detailed energy and exergy balance is presented for the following cycles: (1) steam turbine cycles; (2) helium gas turbine cycles; (3) combined gas/steam turbine cycles. For these different processes an exergy analysis was performed in order to localize the process units, which make a considerable contribution to the decrease in total efficiency.     

Global warming potential of the sulfur–iodine process using life cycle assessment methodology

A life cycle assessment (LCA) of one proposed method of hydrogen production – thermochemical water-splitting using the sulfur–iodine cycle couple with a very high-temperature nuclear reactor – is presented in this paper. Thermochemical water-splitting theoretically offers a higher overall efficiency than high-temperature electrolysis of water because heat from the nuclear reactor is provided directly to the hydrogen generation process, instead of using the intermediate step of generating electricity. The primary heat source for the S–I cycle is an advanced nuclear reactor operating at temperatures corresponding to those required by the sulfur–iodine process. This LCA examines the environmental impact of the combined advanced nuclear and hydrogen generation plants and focuses on quantifying the emissions of carbon dioxide per kilogram of hydrogen produced. The results are presented in terms of global warming potential (GWP). The GWP of the system is 2500 g carbon dioxide-equivalent (CO₂-eq) per kilogram of hydrogen produced. The GWP of this process is approximately one-sixth of that for hydrogen production by steam reforming of natural gas, and is comparable to producing hydrogen from wind- or hydro-electric conventional electrolysis.     

Efficiency of hydrogen production systems using alternative nuclear energy technologies

Nuclear energy can be used as the primary energy source in centralized hydrogen production through high-temperature thermochemical processes, water electrolysis, or high-temperature steam electrolysis. Energy efficiency is important in providing hydrogen economically and in a climate friendly manner. High operating temperatures are needed for more efficient thermochemical and electrochemical hydrogen production using nuclear energy. Therefore, high-temperature reactors, such as the gas-cooled, molten-salt-cooled and liquid-metal-cooled reactor technologies, are the candidates for use in hydrogen production. Several candidate technologies that span the range from well developed to conceptual are compared in our analysis. Among these alternatives, high-temperature steam electrolysis (HTSE) coupled to an advanced gas reactor cooled by supercritical CO₂ (S-CO₂) and equipped with a supercritical CO₂ power conversion cycle has the potential to provide higher energy efficiency at a lower temperature range than the other alternatives.     

Comparative assessment of hydrogen production methods from renewable and non-renewable sources

In this study, we present a comparative environmental impact assessment of possible hydrogen production methods from renewable and non-renewable sources with a special emphasis on their application in Turkey. It is aimed to study and compare the performances of hydrogen production methods and assess their economic, social and environmental impacts, The methods considered in this study are natural gas steam reforming, coal gasification, water electrolysis via wind and solar energies, biomass gasification, thermochemical water splitting with a Cu–Cl and S–I cycles, and high temperature electrolysis. Environmental impacts (global warming potential, GWP and acidification potential, AP), production costs, energy and exergy efficiencies of these eight methods are compared. Furthermore, the relationship between plant capacity and hydrogen production capital cost is studied. The social cost of carbon concept is used to present the relations between environmental impacts and economic factors. The results indicate that thermochemical water splitting with the Cu–Cl and S–I cycles become more environmentally benign than the other traditional methods in terms of emissions. The options with wind, solar and high temperature electrolysis also provide environmentally attractive results. Electrolysis methods are found to be least attractive when production costs are considered. Therefore, increasing the efficiencies and hence decreasing the costs of hydrogen production from solar and wind electrolysis bring them forefront as potential options. The energy and exergy efficiency comparison study indicates the advantages of biomass gasification over other methods. Overall rankings show that thermochemical Cu–Cl and S–I cycles are primarily promising candidates to produce hydrogen in an environmentally benign and cost-effective way.     

Assessment of sustainable high temperature hydrogen production technologies

Apart from being a major feedstock for chemical production, hydrogen is also a very promising energy carrier for the future energy. Currently hydrogen is predominantly produced via fossil routes, but as green energy sources are gaining a larger role in the energy mix, novel and green production routes are emerging. The most abundant renewable hydrogen sources are water and biomass, which allow several possible processing routes, such as electrolysis, thermochemical cycles and gasification. By introducing heat to the process the required electricity demand can be reduced (high temperature electrolysis) or practically eliminated (thermochemical cycles). Each renewable hydrogen production route has its own strength and weaknesses; the choice of the most suitable method is always dependent on the economical potentials and the location. The aim of this paper is to evaluate the different high temperature, renewable hydrogen production technologies.     

A review on integrated thermochemical hydrogen production from water

Hydrogen production from water splitting is considered one of the most environmentally friendly processes for replacing fossil fuels. Among the various technologies to produce hydrogen from water splitting, thermochemical cycles using chemical reagents have the advantage of scale up compared to other specific facilities or geological conditions required. According to thermochemical processes using chemical redox reactions, 2-, 3-, 4-step thermochemical water splitting cycles can generate hydrogen more efficiently due to reducing temperatures. Increasing the number of cycles or steps of thermochemical hydrogen production could reduce the required maximum temperature of the facility. In addition, recently developed hybrid thermochemical processes combined with electricity or solar energy have been studied on a large scale because of the reduced cost of hydrogen production. Additionally, hybrid thermochemical water splitting combined with renewable energy can result in not only reducing the cost, but also increasing hydrogen production efficiency in terms of energy. As for a green energy, hydrogen production from water splitting using sustainable and renewable energy is significant to protect biological environment and human health. Additionally, hybrid thermochemical water splitting is conducive to large scale hydrogen production. This paper reviews the multi-step and highly developed hybrid thermochemical technologies to produce hydrogen from water splitting based on recently published literature to understand current research achievements.     

A comparative life cycle analysis of hydrogen production via thermochemical water splitting using a Cu-Cl cycle

In this paper, a comparative environmental study is reported of the Cu-Cl water-splitting cycle with various other hydrogen production methods: the sulphur-iodine (S-I) water-splitting cycle, high temperature water electrolysis, conventional steam reforming of natural gas and hydrogen production from renewable resources. The investigation uses life cycle assessment (LCA), which is an analytical tool to identify and quantify environmentally critical phases during the life cycle of a system or a product and/or to evaluate and decrease the overall environmental impact of the system or product. The LCA results for the hydrogen production processes indicate that the thermochemical cycles have lower environmental impacts while steam reforming of natural gas has the highest.     

Comparison of thermochemical,electrolytic, photoelectrolytic and photochemical solar-to-hydrogen production technologies

Hydrogen produced from solar energy is one of the most promising solar energy technologies that can significantly contribute to a sustainable energy supply in the future. This paper discusses the unique advantages of using solar energy over other forms of energy to produce hydrogen. Then it examines the latest research and development progress of various solar-to-hydrogen production technologies based on thermal, electrical, and photon energy. Comparisons are made to include water splitting methods, solar energy forms, energy efficiency, basic components needed by the processes, and engineering systems, among others. The definitions of overall solar-to-hydrogen production efficiencies and the categorization criteria for various methods are examined and discussed. The examined methods include thermochemical water splitting, water electrolysis, photoelectrochemical, and photochemical methods, among others. It is concluded that large production scales are more suitable for thermochemical cycles in order to minimize the energy losses caused by high temperature requirements or multiple chemical reactions and auxiliary processes. Water electrolysis powered by solar generated electricity is currently more mature than other technologies. The solar-to-electricity conversion efficiency is the main limitation in the improvement of the overall hydrogen production efficiency. By comparison, solar powered electrolysis, photoelectrochemical and photochemical technologies can be more advantageous for hydrogen fueling stations because fewer processes are needed, external power sources can be avoided, and extra hydrogen distribution systems can be avoided as well. The narrow wavelength ranges of photosensitive materials limit the efficiencies of solar photovoltaic panels, photoelectrodes, and photocatalysts, hence limit the solar-to-hydrogen efficiencies of solar based water electrolysis, photoelectrochemical and photochemical technologies. Extension of the working wavelength of the materials is an important future research direction to improve the solar-to-hydrogen efficiency.