Assessment of system variations for hydrogen transport by liquid organic hydrogen carriers

One option to transport hydrogen over longer distances in the future is via Liquid Organic Hydrogen Carriers (LOHC). They can store 6.2 wt% hydrogen by hydrogenation. The most promising LOHCs are toluene and dibenzyltoluene. However, for the dehydrogenation of the LOHCs – to release the hydrogen again – temperatures above 300 °C are needed, leading to a high energy demand. Therefore, a Life Cycle Assessment (LCA) and Life Cycle Costing are conducted. Both assessments concentrate on the whole life cycle rather than just direct emissions and investments. In total five different systems are analysed with the major comparison between conventional transport of hydrogen in a liquefied state of matter and LOHCs. Variations include electricity supply for liquefaction, heat supply for dehydrogenation and the actual LOHC compound. The results show that from an economic point of view transport via LOHCs is favourable while from an environmental point of view transport of liquid hydrogen is favourable.     

Performance analysis of vapor-cooled shield insulation integrated with para-ortho hydrogen conversion for liquid hydrogen tanks

A composite thermal insulation system consisting of variable-density multi-layer insulation (VDMLI) and vapor-cooled shields (VCS) integrated with para-ortho hydrogen (P-O) conversion is proposed for long-term storage of liquid hydrogen. High-performance thermal insulation is realized by minimizing the thermal losses via the VDMLI design and fully recovering the cold energy released from the sensible heat and P-O conversion of the vented gas. Effects of different design considerations on the thermal insulation performance are studied. The results show that the maximum reduction of the heat leak with multiple VCSs can reach 79.9% compared to that without VCS. The heat leak with one VCS is reduced by 61.1%, and further reduced by 11.6% after adding catalysts. It is found that the deterioration of the insulation performance has an almost linear relationship with catalytic efficiency. A unified criterion with relative optimization efficiency is finally proposed to evaluate the improvement of the VCS number.     

Thermodynamic analysis and assessment of a novel integrated geothermal energy-based system for hydrogen production and storage

In this paper, thermodynamic analysis and assessment of a novel geothermal energy based integrated system for power, hydrogen, oxygen, cooling, heat and hot water production are performed. This integrated process consists of (a) geothermal subsystem, (b) Kalina cycle, (c) single effect absorption cooling subsystem and (d) hydrogen generation and storage subsystems. The impacts of some design parameters, such as absorption chiller evaporator temperature, geothermal source temperature, turbine input pressure and pinch point temperature on the integrated system performance are investigated to achieve more efficient and more effective. Also, the impacts of reference temperature and geothermal water temperature on the integrated system performance are studied in detail. The energetic and exergetic efficiencies of the integrated system are then calculated as 42.59% and 48.24%, respectively.     

Thermodynamic analysis of high‐temperature helium heated fuel reforming for hydrogen production

In order to take full advantage of the heat from high temperature gas cooled reactor, thermodynamic analysis of high‐temperature helium heated methane, ethanol and methanol steam reforming for hydrogen production based on the Gibbs principle of minimum free energy has been carried out using the software of Aspen Plus. Effects of the reaction temperature, pressure and water/carbon molar ratio on the process are evaluated. Results show that the effect of the pressure on methane reforming is small when the reaction temperature is over 900 °C. Methane/CO conversion and hydrogen production rate increase with the water/carbon molar ratio. However the thermal efficiency increases first to the maximum value of 61% and then decreases gradually. As to ethanol and methanol steam reforming, thermal efficiency is higher at lower reaction pressures. With an increase in water–carbon molar ratio, hydrogen production rate increases, but thermal efficiency decreases. Both of them increase with the reaction temperature first to the highest values and then decrease slowly. At optimum operation conditions, the conversion of both ethanol and methanol approaches 100%. For the ethanol and methanol reforming, their highest hydrogen production rate reaches, respectively, 88.69% and 99.39%, and their highest thermal efficiency approaches, respectively, 58.58% and 89.17%. With the gradient utilization of the high temperature helium heat, the overall heat efficiency of the system can reach 70.85% which is the highest in all existing system designs. Copyright © 2014 John Wiley & Sons, Ltd.     

Effect of compression on liquid water transport and microstructure of PEMFC gas diffusion layers

This work explores how the degradation of the gas diffusion layer (GDL) under compression contributes to the formation of preferential pathways for water transport. Fluorescence microscopy is used to provide ex situ visualization of liquid water transport through the GDL placed beneath an optically transparent clamping plate. Transient image data obtained with a CCD camera indicates that areas of compression in the GDL coincide with preferential pathways for water transport and break-through. Preferential flow of water through the smaller pores resulting from GDL compression is contrary to the expected behaviour in a hydrophobic medium, and this suggests a loss of hydrophobicity. Scanning electron microscopy (SEM) is used to investigate the effect of compression on the morphology of the GDL. These SEM images show that compressing the GDL causes the breakup of fibers and, indeed, deterioration of the hydrophobic coating.     

The performance and degradation of Pt electrocatalysts on novel carbon carriers for PEMFC applications

Electrocatalyst stability is an important factor influencing the performance of polymer electrolyte membrane (PEM) fuel cells and is essential in maintaining the cell output. The aim of this work was to elucidate factors which influence the stability of platinum supported onto graphitic nanofibres (Pt/GNFs) and to compare the performance of these materials with the commonly used Pt/Vulcan electrocatalyst. Platinum nanoparticles (average diameter of 6.9 nm) were supported on GNFs which were prepared by chemical vapour deposition over an unsupported nickel oxide (NiO) catalyst precursor. The performance of Pt/GNFs based electrodes were studied by cyclic voltammetry and a single-cell fuel cell test and were compared with a commercially available carbon nanostructure, Vulcan XC-72, which was also impregnated with Pt nanoparticles. Characterisation of the pre- and post-operation of the Pt/GNFs by XRD and TEM showed that structural changes of the Pt had occurred during testing. It was found that the average diameter of each grain and the degree of agglomeration among particles was increased, creating elongated clusters of Pt along the carbon fibre. Analysis of electrocatalyst post-operation also identified that the sulphate from the Nafion membrane was reacting with the Pt surface forming platinum sulphide (PtS). These phases were confirmed by the presence of low intensity, but sharp XRD peaks, attributed to a few large diameter particles (49 nm). These two factors resulted in current density dropping from 0.2 A/cm² to 0.1 A/cm² (at 0.70 V) over a 25 h test period.     

Assessment of power and hydrogen production performance of an integrated system based on middle-grade geothermal source and solar energy

In this study, power and hydrogen production performance of an integrated system is investigated. The system consists of an organic Rankine cycle (ORC), parabolic trough solar collectors (PTSCs) having a surface area of 545 m², middle-grade geothermal source (MGGS), cooling tower and proton exchange membrane (PEM). The final product of this system is hydrogen that produced via PEM. For this purpose, the fluid temperature of the geothermal source is upgraded by the solar collectors to drive the ORC. To improve the electricity generation efficiency, four working fluids namely n-butane, n-pentane, n-hexane, and cyclohexane are tried in the ORC. The mass flow rate of each working fluid is set as 0.1, 0.2, 0.3, 0.4 kg/s and calculations are made for 16 different situations (four types of working fluids and four different mass flow rates for each). As a result, n-butane with a mass flow rate of 0.4 kg/s is found to be the best option. The average electricity generation is 66.02 kW between the hours of 11⁰⁰-13⁰⁰. The total hydrogen production is 9807.1 g for a day. The energy and exergy efficiency is calculated to be 5.85% and 8.27%, respectively.     

Thermodynamic assessment of modified Organic Rankine Cycle integrated with parabolic trough collector for hydrogen production

Hydrogen is one of the most clean energy carrier and the best alternative for fossil fuels. In this study, thermodynamic analysis of modified Organic Rankine Cycle (ORC) integrated with Parabolic Trough Collector (PTC) for hydrogen production is investigated. The integrated system investigated in this study consists of a parabolic trough collector, a modified ORC, a single effect absorption cooling system and a PEM electrolyzer. By using parabolic trough collector, solar energy is converted heat energy and then produced heat energy is used in modified ORC to produce electricity. Electricity is then used for hydrogen production. The outputs of this integrated system are electricity, cooling and hydrogen. By performing a parametric study, the effects of design parameters of PTC, modified ORC and PEM electrolyzer on hydrogen production is evaluated. According to the analysis results, solar radiation is one of the most important factor affecting system exergy efficiency and hydrogen production rate. As solar radiation increases from 400?W/m² to 1000?W/m², exergy efficiency of the system increases 58%–64% and hydrogen production rate increases from 0.1016?kg/h to 0.1028?kg/h.     

Comparative assessment of greenhouse gas mitigation of hydrogen passenger trains

This paper examines a comparative assessment in terms of CO₂ emissions from a hydrogen passenger train in Ontario, Canada, particularly comparing four specific propulsion technologies: (1) conventional diesel internal combustion engine (ICE), (2) electrified train, (3) hydrogen ICE, and (4) hydrogen PEM fuel cell (PEMFC) train. For the electrified train, greenhouse gases from electricity generation by natural gas and coal-burning power plants are taken into consideration. Several hydrogen production methods are also considered in this analysis, i.e., (1) steam methane reforming (SMR), (2) thermochemical copper–chlorine (Cu–Cl) cycle supplied partly by waste heat from a nuclear plant, (3) renewable energies (solar and wind power) and (4) a combined renewable energy and copper–chlorine cycle. The results show that a PEMFC powertrain fueled by hydrogen produced from combined wind energy and a copper–chlorine plant is the most environmentally friendly method, with CO₂ emissions of about 9% of a conventional diesel train or electrified train that uses a coal-burning power plant to generate electricity. Hydrogen produced with a thermochemical cycle is a promising alternative to further reduce the greenhouse gas emissions. By replacing a conventional diesel train with hydrogen ICE or PEMFC trains fueled by Cu-Cl based-hydrogen, the annual CO₂ emissions are reduced by 2260 and 3318 tonnes, respectively. A comparison with different types of automobile commuting scenarios to carry an equivalent number of people as a train is also conducted. On an average basis, only an electric car using renewable energy-based electricity that carries more than three people may be competitive with hydrogen trains.     

Exergy analysis and optimization of methanol generating hydrogen system for PEMFC

An exergy analysis of methanol autothermal generating hydrogen system for PEMFC is presented. The process combines a catalytic combustion heat exchanger (CCHE), using partial off-gases containing hydrogen as feedstock, with an auto-thermal reformer (ATR), two water gas shift (WGS) reactors and four preferential oxidation (PROX) reactors. Energy and exergy of system were calculated and analyzed. The results demonstrated that inner exergy losses resulted from the irreversible heat transfer and reaction were the dominant factors. The most important destruction of exergy within the system was found to occur in the reformer and the catalytic combustion heat exchanger. Their ratios of exergy loss accounted for 25.03% and 24.95%, respectively, of the whole system. Based on results of thermodynamic and exergetic analysis, the reformer was optimized. The optimal W/M$W/M$ (molar water to methanol) is around 1.5–2.0 and A/M$A/M$ (molar air to methanol) is around 1.5. Certain recommendations were posed. The conclusions could help to optimize methanol autothermal generating hydrogen system for PEMFC.     

4E analysis of efficient waste heat recovery from SOFC using APC: An effort to reach maximum efficiency and minimum emission through an application of grey wolf optimization

This article presents an innovative combined heat and power system comprising a solid oxide fuel cell (SOFC), a heat recovery unit, and a lithium bromide absorption power cycle (APC). The energy, exergy, economic, and environmental perspectives of the proposed system are compared against the same configuration using an organic Rankine cycle (ORC), recovering the waste heat of the SOFC. A multi-criteria optimization based on the Grey Wolf approach is applied to each system to specify the best operation conditions having the exergy efficiency and total cost rate as the objectives. Furthermore, a parametric investigation is conducted to assess the effects of changing the decision variables on the systems proficiencies. The results indicate that although the ORC-based cycle is economically very slightly superior, the integration of the SOFC with the APC offers a much higher exergy efficiency due to the better temperature matching between the working fluid and heat source. Optimization can increase the exergy efficiencies of the SOFC-ORC and the SOFC-APC systems by about 13.8% and 14.7% while reducing the total cost rate by 11.2 $/h and 11.0 $/h, respectively, compared to the base system. Environmental analysis results reveal that APC use leads to a lower emission of 2.8 kg/MWh.     

Performance assessment of an electrochemical hydrogen production and storage system for solar hydrogen refueling station

This paper investigates the performance of a hydrogen refueling system that consists of a polymer electrolyte membrane electrolyzer integrated with photovoltaic arrays, and an electrochemical compressor to increase the hydrogen pressure. The energetic and exergetic performance of the hydrogen refueling station is analyzed at different working conditions. The exergy cost of hydrogen production is studied in three different case scenarios; that consist of i) off-grid station with the photovoltaic system and a battery bank to supply the required electric power, ii) on-grid station but the required power is supplied by the electric grid only when solar energy is not available and iii) on-grid station without energy storage. The efficiency of the station significantly increases when the electric grid empowers the system. The maximum energy and exergy efficiencies of the photovoltaic system at solar irradiation of 850 W m-2 are 13.57% and 14.51%, respectively. The exergy cost of hydrogen production in the on-grid station with energy storage is almost 30% higher than the off-grid station. Moreover, the exergy cost of hydrogen in the on-grid station without energy storage is almost 4 times higher than the off-grid station and the energy and exergy efficiencies are considerably higher.     

Design and simulation of a solar-hydrogen system for different situations

In recent years, hybrid photovoltaic–fuel cell energy systems have been popular as energy production systems for different applications. A typical solar-hydrogen system can be modeled the electricity supplied by PV panels is used to meet the demand directly to the maximum extent possible. If there is any surplus PV power over demand, and capacity left in the tank for accommodating additional hydrogen, this surplus power is supplied to the electrolyser to produce hydrogen for storage. When the output of the PV array is not sufficient to supply the demand, the fuel cell draws on hydrogen from storage and produces electricity to meet the supply deficit.     

Exergoeconomic analysis and multi objective optimization of a solar based integrated energy system for hydrogen production

In the current study, an integrated renewable based energy system consisting of a solar flat plate collector is employed to generate electricity while providing cooling load and hydrogen. A parametric study is carried out in order to determine the main design parameters and their effects on the objective functions of the system. The outlet temperature of generator, inlet temperature to organic Rankine cycle turbine, solar irradiation intensity $\left(I\right)$, collector mass flow rate $\left({\dot{m}}_{col}\right)$ and flat plate collector area $\left(A_P\right)$ are considered as five decision variables. The results of parametric study show that the variation of collector mass flow rate between 3 kg/s and 8 kg/s has different effects on exergy efficiency and total cost rate of the system. In addition, the result shows that increment of inlet temperature to the ORC evaporator has a negative effect on cooling capacity of the system. It can lead to a decrease the cooling capacity from 44.29 kW to 22.6 kW, while the electricity generation and hydrogen production rate of the system increase. Therefore, a multi objective optimization is performed in order to introduce the optimal design conditions based on an evolutionary genetic algorithm. Optimization results show that exergy efficiency of the system can be enhanced from 1.72% to 3.2% and simultaneously the cost of the system can increase from 19.59 $/h to 22.28 $/h in optimal states.     

Power management strategies for a stand-alone power system using renewable energy sources and hydrogen storage

A stand-alone power system based on a photovoltaic array and wind generators that stores the excessive energy from renewable energy sources (RES) in the form of hydrogen via water electrolysis for future use in a polymer electrolyte membrane (PEM) fuel cell is currently in operation at Neo Olvio of Xanthi, Greece. Efficient power management strategies (PMSs) for the system have been developed. The PMSs have been assessed on their capacity to meet the power load requirements through effective utilization of the electrolyzer and fuel cell under variable energy generation from RES (solar and wind). The evaluation of the PMS has been performed through simulated experiments with anticipated conditions over a typical four-month time period for the region of installation. The key decision factors for the PMSs are the level of the power provided by the RES and the state of charge (SOC) of the accumulator. Therefore, the operating policies for the hydrogen production via water electrolysis and the hydrogen consumption at the fuel cell depend on the excess or shortage of power from the RES and the level of SOC. A parametric sensitivity analysis investigates the influence of major operating variables for the PMSs such as the minimum SOC level and the operating characteristics of the electrolyzer and the fuel cell in the performance of the integrated system.     

Thermodynamic assessment of carbazole-based organic polycyclic compounds for hydrogen storage applications via a computational approach

Liquid organic hydrogen carriers (LOHCs) are promising candidates for storage and transport of renewable energy due to their reversible reaction characteristics. For the proper assessment of candidate molecules, various thermochemical properties are required, and significant experimental efforts are necessary. In this work, we suggest a systematic method for the estimation of thermochemical properties for LOHC candidate molecules combining Density Functional Theory (DFT) calculations, Conductor-like Screening Model (COSMO) and Molecular Dynamics (MD) simulations. We applied the suggested method for the assessment of previously reported LOHC materials. Based on the analysis, new candidates of carbazole-derivative compounds (N-acetylcarbazole, N-phenylcarbazole, N-benzoylcarbazole, and 4-methyl-4H-benzocarbazole) are suggested, and their properties are estimated and reviewed. Calculation results show that these candidates can provide high theoretical hydrogen uptake capacities above 6 wt% and optimal heats of dehydrogenation in the liquid phase. Analysis on the stereoisomerism showed that the structure-selectivity toward less stable stereoisomers of the hydrogen-rich form is preferable for the dehydrogenation process.     

Thermodynamic analysis and performance optimization of organic rankine cycles for the conversion of low‐to‐moderate grade geothermal heat

The present study considers a thermodynamic analysis and performance optimization of geothermal power cycles. The proposed binary‐cycles operate with moderately low temperature and liquid‐dominated geothermal resources in the range of 110°C to 160°C, and cooling air at ambient conditions of 25°C and 101.3 kPa reference temperature and atmospheric pressure, respectively. A thermodynamic optimization process and an irreversibility analysis were performed to maximize the power output while minimizing the overall exergy destruction and improving the First‐law and Second‐law efficiencies of the cycle. Maximum net power output was observed to increase exponentially with the geothermal resource temperature to yield 16–49 kW per unit mass flow rate of the geothermal fluid for the non‐regenerative organic Rankine cycles (ORCs), as compared with 8–34 kW for the regenerative cycles. The cycle First‐law efficiency was determined in the range of 8–15% for the investigated geothermal binary power cycles. Maximum Second‐law efficiency of approximately 56% was achieved by the ORC with an internal heat exchanger. In addition, a performance analysis of selected pure organic fluids such as R123, R152a, isobutane and n‐pentane, with boiling points in the range of ?24°C to 36°C, was conducted under saturation temperature and subcritical pressure operating conditions of the turbine. Organic fluids with higher boiling point temperature, such as n‐pentane, were recommended for non‐regenerative cycles. The regenerative ORCs, however, require organic fluids with lower vapour specific heat capacity (i.e. isobutane) for an optimal operation of the binary‐cycle. Copyright © 2015 John Wiley & Sons, Ltd.     

Modeling,analysis and control system development for the Italian hydrogen house

This paper provides an analysis of the “Hydrogen from the Sun” project at the “Ecological House” in northern Italy. The modeling and analysis work is being performed in conjunction with the International Energy Agency Hydrogen Implementing Agreement Annex 18: Integrated Systems Evaluation. A customized library of Matlab/Simulink component models is used to simulate the system and evaluate the hydrogen economics and energy production efficiencies. Two control algorithms are developed for the house using a fuzzy logic and an adaptive control strategy. The economic and steady state effects of these two strategies are compared as are the energy sources used to supply the energy demand of the house. The hydrogen production system consists of an electrolyzer, a photo-voltaic collector, and a battery, linked to both a metal hydride and high pressure gas storage system. The hydrogen supplies a fuel cell, which powers a residential estate. The analysis shows the contribution of the different system components to the overall efficiency and cost of hydrogen. However, the control systems presented also have a significant effect on the hydrogen and electricity cost. Reduction of these costs and an increase in system efficiency require optimal use of the hydrogen stored, as well as the optimized distribution of power supply from the generating components. The analysis shows the initial cost of hydrogen to be 9.36 $/kg, with electricity produced at 0.65 $/kWh using a fuzzy logic control system at an electrical efficiency of 50% (of the full hydrogen house system), based on the lower heating value of hydrogen. The result of using an active control strategy is presented.     

Thermodynamic studies of a novel heat pipe evacuated tube solar collectors based integrated process for hydrogen production

In this study, the detailed thermodynamic assessment of an integrated process based on heat pipe evacuated tube solar collectors for hydrogen production is provided for more efficiently process designs. An integrated process consists of the solar heat pipe collector, photovoltaic panels, PEM electrolyzer and Linde-Hampson hydrogen liquefaction process are considered and analyzed thermodynamically for hydrogen production and liquefaction aims. The energetic and exergetic efficiencies of this integrated process are calculated as 0.2297 and 0.1955, respectively. Based on the parametric study, the effectiveness of the solar energy based integrated process is also highly dependent on the solar flux and ambient conditions.     

Research and development of liquid hydrogen (LH2) temperature monitoring system for marine applications

Monitoring the temperature in liquid hydrogen (LH₂) storage tanks on ships is important for the safety of maritime navigation. In addition, accurate temperature measurement is also required for commercial transactions. Temperature and pressure define the density of liquid hydrogen, which is directly linked to trading interests. In this study, we developed and tested a liquid hydrogen temperature monitoring system that uses platinum resistance sensors with a nominal electrical resistance of approximately 1000 Ω at room temperature, PT-1000, for marine applications. The temperature measurements were carried out using a newly developed temperature monitoring system under different pressure conditions. The measured values are compared with a calibrated reference PT-1000 resistance thermometer. We confirm a measurement accuracy of ±50 mK in a pressure range of 0.1 MPa–0.5 MPa.