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.     

Energy and exergy analyses and optimization study of an integrated solar heliostat field system for hydrogen production

In this paper, we propose an integrated system, consisting of a heliostat field, a steam cycle, an organic Rankine cycle (ORC) and an electrolyzer for hydrogen production. Some parameters, such as the heliostat field area and the solar flux are varied to investigate their effect on the power output, the rate of hydrogen produced, and energy and exergy efficiencies of the individual systems and the overall system. An optimization study using direct search method is also carried out to obtain the highest energy and exergy efficiencies and rate of hydrogen produced by choosing several independent variables. The results show that the power and rate of hydrogen produced increase with increase in the heliostat field area and the solar flux. The rate of hydrogen produced increases from 0.006 kg/s to 0.063 kg/s with increase in the heliostat field area from 8000 m² to 50,000 m². Moreover, when the solar flux is increased from 400 W/m² to 1200 W/m², the rate of hydrogen produced increases from 0.005 kg/s to 0.018 kg/s. The optimization study yields maximum energy and exergy efficiencies and the rate of hydrogen produced of 18.74%, 39.55% and 1571 L/s, respectively.     

Assessment study of a four-step copper-chlorine cycle modified with flash vaporization process for hydrogen production

This paper develops a four-step copper-chlorine cycle for hydrogen production with conceptual modification through flash vaporization and evaluates its economic and environmental performances through exergy approach. The flash vaporization method is employed as a new approach for realizing the anolyte separation under vacuum conditions for reducing the thermal requirement of the anolyte separation step and consequently of the overall cycle. A flash vaporization is usually employed commercially for seawater desalination purposes. However, its utilization in a thermochemical hydrogen production process has not been considered previously which is really one of primary novelties of this investigation. The obtained results for the exergoeconomic and exergoenvironmental analyses of the conceptually modified cycle are also compared with those of the existing integrated cycle at the Ontario Tech University. The exergoeconomic analysis of the cycle has also been carried out for the cycle operating with and without waste heat recovery. In this regard, waste heat recovery from a steel furnace has been considered for supplying the required thermal energy for the hydrolysis step. The cost assessment of the cycle is carried out in the Aspen-plus. Compared with the existing cycle, the cycle with the proposed modification results in a lower unit cost of hydrogen. Moreover, a significant reduction in the unit cost of hydrogen is observed when waste heat recovery is considered for the modified cycle. The average unit hydrogen cost for the modified version of the cycle is evaluated to be 4.7 $/kg which reduces to 2 $/kg with incorporation of waste heat recovery. Furthermore, the overall environmental impact of the existing cycle can be potentially minimized by considering the proposed modification through flash vaporization.     

Investigation of an integrated system with industrial thermal management options for carbon emission reduction and hydrogen and ammonia production

A new integrated energy system employing the cement slag waste heat is uniquely proposed in this study. The core focus of the proposed system is to generate clean hydrogen thermochemically and convert it into ammonia. The designed system consists of the copper–chlorine (Cu–Cl) cycle, a cryogenic air separation unit and a steam Rankine cycle while the useful commodities produced by the proposed system are hydrogen, ammonia, oxygen, hot water and electricity. A CO₂ emission analysis is also conducted to calculate the emissions which can be avoided by recovering this waste heat. The Aspen Plus simulation software is utilized to model and simulate the proposed integrated system. A thermochemical water splitting process is incorporated into the system for hydrogen production. The cryogenic air separation unit is integrated in order to separate nitrogen from the air. This proposed system also reduces the environmental effects of the flue gas emitted by the cement industry. Multiple parametric studies are performed to investigate the system performance by varying operating conditions and state properties. The energy analysis is implemented on each component of the designed system. The overall energy efficiency of the system is concluded as 30.1%. The amount of CO₂ emissions which can be avoided by utilizing this waste heat is 29.64 ktonne/5 years.     

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.     

Thermodynamic assessment of a lab-scale experimental copper-chlorine cycle for sustainable hydrogen production

An integrated lab-scale copper-chlorine (Cu-Cl) thermochemical cycle for hydrogen production at the University of Ontario Institute of Technology (UOIT) is presented and analyzed in this paper. In a practical operation of the Cu-Cl cycle, besides the main steps of hydrolysis, thermolysis, electrolysis and drying, the oxidized anolyte (consumed anolyte at the electrolyzer cell) needs to be recycled to be concentrated sufficiently for the electro-chemical process. Recycling of the oxidized anolyte through the separation processes is achieved by distillation of anolyte, drying unit, separation cell, pressure swing distillation and CuCl₂ concentrator. This study examines the thermodynamic performance of all unit operations in the lab-scale Cu-Cl cycle. A process simulation model with Aspen Plus is used to assess the system by energy and exergy analyses. For the specific system design characteristics, the cycle is capable of producing 100 L/h of hydrogen. From the simulation results, the overall energy and exergy efficiencies of the lab-scale Cu-Cl cycle are determined to be 11.6% and 34.9%, respectively. Furthermore, after the thermolysis and hydrolysis reactors, the quench cell and CuCl₂ concentrator have the highest exergy losses with thermal energy transferred through CuCl solidification and water vaporization phase-change processes at relatively high temperature. Additional results of the processes are presented and discussed.     

Study on an original cobalt-chlorine thermochemical cycle for nuclear hydrogen production

In this paper, a theoretical and experimental study on a novel cobalt-chlorine thermochemical cycle for hydrogen production is presented. The cobalt-chlorine cycle comprises a closed loop of four thermochemical reactions occurring at 700 °C that is a reaction temperature compatible with the present generation of high-temperature gas-cooled reactors. Firstly, a thermodynamic analysis was done for determining whether this cycle is attractive for hydrogen production in terms of both energy and exergy efficiencies. Following, proof-of-principle experiments were carried out at laboratory scale in a batch reactor at temperatures in the range from 550 °C to 950 °C and holding times between 1 h and 72 h. Experimental results complemented by the characterization of condensed compounds deposited on the reactor walls allowed confirm the reaction pathway of thermochemical reactions originally proposed, define the slowest step of the global process, and explain the beneficial effect of increasing the system pressure on the hydrogen yield. Even both performance assessment and proof-of-principle experimental results look like promising more research will be required in the future to confirm these preliminary findings. Finally, a modified version of the cobalt-chlorine cycle is proposed for enhancing the global kinetics, based on the experimental evidence found in the proof-of-principle tests.     

Overview of hydrogen production research in the Clean Energy Research Laboratory (CERL) at UOIT

This paper discusses new hydrogen production methods that have been actively investigated both theoretically and experimentally at UOIT and some recent findings through experimental measurements and analysis. A major cluster of activities at UOIT has developed novel hydrogen production systems from electrolysis to thermochemical cycles and from integrated cycles to solar-light based hydrogen production processes. The results confirm that both thermochemical cycles and photochemical processes offer promising potential for sustainable hydrogen production.     

Multi-objective technoeconomic optimization of an off-grid solar-ground-source driven cycle with hydrogen storage for power and fresh water production

Utilizing renewable sources integrated with thermodynamic cycles has been gaining attention in recent years due to being economical and environment-friendly, among which, renewable-energy driven water and power generation systems have shown promising outcomes. In the field of renewable-energy based multi-generation systems (MGS), many recent works have focused on energy analysis or simple optimization. Therefore, in this study, an off-grid solar-geothermal cogeneration system which is able to produce power by Kalina cycle, hydrogen by proton exchange membrane electrolyzer (PEMEC), and freshwater by a multi-effect desalination (MED) unit, was investigated and optimized in terms of economic and energy viewpoints. Unlike previous studies, in this work, a comprehensive multi-objective optimization (MOO) was employed on the system in order to find the optimal working condition. The decision variables of the optimization include flat plate collector area, water mass flow, and ammonia concentration of the Kalina cycle, and the objective functions were levelized cost of electricity (LCOE), payback period (PBP), the overall energy efficiency of the system, and freshwater production of MED unit. Final results show that the system, in its optimum condition, is able to produce 182.09 m³.day⁻¹ fresh water, with energy efficiency, PBP, and LCOE equal to 6.23%, 5.19 years and 0.238 $.kWh⁻¹, respectively.     

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.     

Energy and exergy analyses of magnesium-chlorine (Mg-Cl) thermochemical cycle

In this paper, we conduct energy and exergy analyses of the magnesium-chlorine (Mg-Cl) thermochemical cycle for hydrogen production and examine the respective cycle energy and exergy efficiencies. We also undertake a parametric study to investigate how the overall cycle performance is affected by changing the reference environment temperature and operating conditions. The results show that Mg-Cl cycle offers a good potential due to its high energy and exergy efficiencies as 63.63% and 34.86%, respectively, based upon the conditions and parameters considered. In this regard, Mg-Cl cycle appears to be a promising low temperature thermochemical cycle. It may, therefore, compete with other low temperature thermochemical and hybrid cycles such as the copper–chlorine cycle.     

Energy and exergy analyses of integrated hybrid sulfur isobutane system for hydrogen production

This paper analyzes an integrated HyS cycle (hybrid sulfur cycle), isobutane cycle and electrolyzer for hydrogen production. The operating parameters such as concentration, pressure and temperature are varied to investigate their effects on the energy and exergy efficiencies of the system with/without heat recovery and integration, as well as the decomposer and rate of hydrogen produced. A new heat exchanger network is also developed to recover heat within the HyS cycle in the most efficient manner. The exergy destruction rate in each component is analyzed and discussed. From the results, increasing the pressure is beneficial up to 3222 kPa, after which the performance remains constant. The exergy efficiency varies more significantly with operating parameters than the energy efficiency. The maximum exergy destruction occurs in the heat exchanger so this component should be the focus to enhance the overall performance of the system.     

Development of an integrated thermochemical cycle-based hydrogen production and effective utilization

In this study, an assessment of a renewable energy-based hybrid sulfur-bromine cycle for hydrogen fuel production and effective utilization is performed since the present era requires lots of hydrogen for fueling many systems. Hydrogen, produced by the hybrid sulfur-bromine cycle, is supplied to the combustion subsystems by blending with natural gas for residential use. Solar and wind energy sources are potentially considered as renewable energies for green hydrogen production. Also, a drying unit is included with an incineration subsystem. A desalination unit is also integrated to produce freshwater for the community. In this way, electricity, heat, and clean water required both for the community and the subsystems are supplied. The integrated system is then assessed in terms of energy and exergy efficiencies. Here, 0.233 kg/s of natural gas and hydrogen blend and 1.338 kg/s of biomass are provided to the system. The energy and exergy efficiencies of the overall system are determined to be 64.43% and 32.24%.     

Thermodynamic viability of a new three step high temperature Cu-Cl cycle for hydrogen production

A new three step high temperature Cu-Cl thermochemical cycle for hydrogen production is presented. The performance of the proposed cycle is investigated through energy and exergy approaches. Furthermore, the effects of various parameters, such as the temperatures of the steps of the cycle and power plant efficiency, on various energy and exergy efficiencies are assessed with parametric studies. The results show that the exergy and energy efficiencies of the proposed cycle are 68.3% and 32.0%, respectively. In addition, the exergy analysis results reveal that the hydrogen production step has the maximum specific exergy destruction with a value of 150.9 kJ/mol. The results suggest that proposed cycle may provide enhanced options for high temperature thermochemical cycles by improving thermal management without causing a sudden temperature jump/fall between the hydrogen production step and other steps.     

Exergoeconomic analysis of a new integrated copper-chlorine cycle for hydrogen production

In this study, an exergoeconomic analysis is performed on an integrated four-step thermochemical copper-chlorine cycle developed at the Ontario Tech. University through exergy, cost, energy, and mass (EXCEM) method. A thermodynamic model is first constructed in Aspen-plus (a process simulation software) to simulate and investigate the integrated cycle through exergy and energy analyses. The capital costs, thermodynamic loss rates, and the ratio of the thermodynamic loss rate to the capital cost of various system's components are also determined. Moreover, the average unit cost of hydrogen is evaluated and the influence of several system's parameters on the unit cost of hydrogen is analyzed. The results show that the cost of hydrogen is strongly dependent on the production capacity of the plant. Based on the analysis, our system generates hydrogen at an average unit cost of 5.54 $/kg with a plant capacity of 1619.3 kg/h considering both internal (operating and maintenance costs, etc.) and external (costs of various inputs, etc.) parameters.     

Energy and exergy analyses of a solar based hydrogen production and compression system

In this study, a solar thermal based integrated system with a supercritical-CO₂ (sCO₂) gas turbine (GT) cycle, a four-step Mg–Cl cycle and a five-stage hydrogen compression plant is developed, proposed for applications and analyzed thermodynamically. The solar data for the considered solar plant are taken for Greater Toronto Area (GTA) by considering both daily and yearly data. A molten salt storage is considered for the system in order to work without interruption when the sun is out. The power and heat from the solar and sCO₂-GT subsystems are introduced to the Mg–Cl cycle to produce hydrogen at four consecutive steps. After the internal heat recovery is accomplished, the heating process at required temperature level is supplied by the heat exchanger of the solar plant. The hydrogen produced from the Mg–Cl cycle is compressed up to 700 bar by using a five-stage compression with intercooling and required compression power is compensated by the sCO₂-GT cycle. The total energy and exergy inputs to the integrated system are found to be 1535 MW and 1454 MW, respectively, for a 1 kmol/s hydrogen producing plant. Both energy and exergy efficiencies of the overall system are calculated as 16.31% and 17.6%, respectively. When the energy and exergy loads of the receiver are taken into account as the main inputs, energy and exergy efficiencies become 25.1%, and 39.8%, respectively. The total exergy destruction within the system is found to be 1265 MW where the solar field contains almost 64% of the total irreversibility with a value of ～811 MW.     

A new integrated renewable energy system for clean electricity and hydrogen fuel production

In this paper, a new renewable energy-based cogeneration system for hydrogen and electricity production is developed. Three different methods for hydrogen production are integrated with Rankine cycle for electricity production using solar energy as an energy source. In addition, a simple Rankine cycle is utilized for producing electricity. This integrated system consists of solar steam reforming cycle using molten salt as a heat carrier, solar steam reforming cycle using a volumetric receiver reactor, and electrolysis of water combined with the Rankine cycle. These cycles are simulated numerically using the Engineering Equation Solver (EES) based on the thermodynamic analyses. The overall energetic and exergetic efficiencies of the proposed system are determined, and the exergy destruction and entropy generation rates of all subcomponents are evaluated. A comprehensive parametric study for evaluating various critical parameters on the overall performance of the system is performed. The study results show that both energetic and exergetic efficiencies of the system reach 28.9% and 31.1%, respectively. The highest exergy destruction rates are found for the steam reforming furnace and the volumetric receiver reforming reactor (each with about 20%). Furthermore, the highest entropy generation rates are obtained for the steam reforming furnace and the volumetric receiver reforming reactor, with values of 174.1 kW/K and 169.3 kW/K, respectively. Additional parametric studies are undertaken to investigate how operating conditions affect the overall system performance. The results report that 60.25% and 56.14% appear to be the highest exergy and energy efficiencies at the best operating conditions.     

A specific exergy costing assessment of the integrated copper-chlorine cycle for hydrogen production

In this study the specific exergy costing (SPECO) approach is employed on a four-step integrated thermochemical copper-chlorine (Cu Cl) cycle for hydrogen production for a second-law based assessment purposes. The Cu–Cl cycle is considered as one of the most environmentally benign and sustainable options of producing hydrogen and is thus investigated in this study due to its potential of ensuring zero greenhouse gas (GHG) emissions. Several conceptual Cu–Cl cycles have been exergoeconomically examined previously, however this study aims at investigating the four-step integrated Cu–Cl cycle developed at the Clean Energy Research Laboratory (CERL) at the Ontario Tech University thereby contributing to the thermo/exergoeconomic assessments of the thermochemical hydrogen production. In this study, the cycle is first thermodynamically modeled and simulated in a process simulation software (Aspen Plus) through exergy and energy approaches. The basic principles of the SPECO methodology are applied to the system and exergetic cost balances are performed for each cycle component. The exergetic costing of each cycle stream is then performed based on the cost balance equations. The purchased equipment cost and the hourly levelized capital cost rates for each cycle component is also obtained. The exergoeconomic factor, relative cost difference and exergy destruction cost rate for various cycle components are also evaluated. Moreover, the effect of several parameters on the total and hourly levelized capital cost rates is analyzed by performing a comprehensive sensitivity analysis. Based on the analysis, the exergy cost, the unit or specific exergy cost, and the unit costs of hydrogen are evaluated to be 6407.55 $/h, 0.042 $/MJ, and 4.94 $/kg respectively.     

Investigations on the hydrolysis step of copper-chlorine thermochemical cycle for hydrogen production

Detailed investigations of CuCl₂ hydrolysis step of Cu–Cl thermochemical cycle were carried out on various aspects: (a) characterization and thermal properties of reactants/products using X-ray diffraction (XRD), thermogravimetry–mass spectrometry (TG-MS), scanning electron microscopy (SEM), temperature-programmed desorption (TPD), and extended X-ray absorption fine structure (EXAFS); (b) performance evaluation of fixed bed hydrolysis; (c) parametric optimization with respect to S/Cu, flow rate (gas hourly space velocity, GHSV), reaction duration, temperature, and particle size; and (d) monitored hydrolysis using isothermal TG experiments at 360°C, 370°C, 380°C, 390°C, and 400°C to derive kinetic parameters rate constant (k) and activation energy (E_a) on the basis of the shrinking-core model. 97% conversion to Cu₂OCl₂ at 17 630 h⁻¹ of GHSV, 400°C was achieved using ball-milled CuCl₂ (BM6), as compared with that of 55% over commercial un–ball-milled reactant, CuCl₂ (UBM). Correspondingly, higher k value of 2.84 h⁻¹ over BM6 as compared with 0.97 h⁻¹ over UBM reactant at 400°C was achieved. E_a for hydrolysis of BM6 was 93 kJ/mol, while it was 106 kJ/mol for UBM as derived from the Arrhenius plot. A probable pathway for CuCl₂ hydrolysis is proposed here. It was found to be diffusion controlled, and the particle size of reactant molecules affects the packing and diffusion length. Based on our investigations, it is very unlikely to get >99% phase pure product (Cu₂OCl₂). Cu₂OCl₂ is labile in nature and tends to transform into structurally similar and stable compounds CuO and CuCl₂.