Cyclic behaviors of a novel design of a metal hydride reactor encircled by cascaded phase change materials

The integration of a phase change material (PCM) with a metal hydride (MH) reactor has received considerable attention recently. In such a system, the exothermic and endothermic processes of the MH reactor can be utilized effectively by enhancing the thermal exchange between the MH reactor and the PCM bed. In this study, a novel design that integrates the MH reactor with cascaded PCM beds is proposed. Magnesium nickel (Mg₂Ni) alloy is used as the hydride reactor. Two different types of PCMs with different melting temperatures and enthalpies are arranged in series. A parametric study is carried out to identify the optimum distribution of the different PCMs. The results indicate that the proposed cascaded MH-PCM sandwich design improves the heat transfer rate which consequently shortens the time duration of the hydrogenation and dehydrogenation processes by 26% and 51%, respectively, compared to an MH-PCM sandwich design that includes only a single PCM.     

Selection of phase change materials,metal foams and geometries for improving metal hydride performance

This paper reports the numerical investigation of the effect of different phase change materials (PCMs) on the metal hydride (MH) behaviour in a reactor bed during the absorption process. The feasibility of integrating metal foams (MFs) into the phase change materials to improve the hydrogen storage performance of the system was also evaluated. A two-dimensional model for a LaNi₅ hydride reactor equipped with different phase change materials has been developed. The selection of five different PCMs having a high latent heat of fusion and a range of melting temperatures were investigated. In addition, the effect of the mass and volume of the different PCMs on the hydrogen performance of the MH reactor was studied. It was found that LiNO₃·3H₂O PCM shown better performance than the other PCMs, its loading time is faster, and its mass within the reactor is enough to absorb the total heat generated from the MH during hydrogenation. Three different metals foam with three different porosities were integrated into the most suitable PCM with the appropriate dimension of a cylindrical reactor that shows the optimum performance. The obtained results indicated that the integration of the metal foams into the PCM show better heat transfer performance than the case of MH-PCM without metal foams. Two different configurations cylindrical and spherical MH reactors were investigated. The obtained results indicated that the two configurations have very similar behaviours. So, both configurations are good for the hydriding process within an MH reactor.     

Optimal design of a metal hydride hydrogen storage bed using a helical coil heat exchanger along with a central return tube during the absorption process

Metal-hydride (MH) reactors are one of the most promising approaches for hydrogen storage because of their low operating pressure, high storage volumetric density and high security. However, the heat transfer performance of the MH reactor for high hydrogenation rate is inferior. In this study, the heat transfer and hydrogen absorption process of metal hydride tank performance in Mg₂Ni bed is analyzed numerically using commercial ANSYS-FLUENT software. The MH reactor is considered a cylindrical bed including a helical tube along with a central straight return tube for the cooling fluid. The effects of geometrical parameters including the tube diameter, the pitch size and the coil diameter as well as operational parameters on the heat exchanged and hydrogen absorption reactive time are evaluated comprehensively. The results showed that the helical heat exchanger along with central return tube could effectively improve heat exchanged between the cooling fluid and the metal alloy and reduce the temperature of the bed results in a higher rate of hydrogen absorption. For a proper configuration and geometry of the helical coil heat exchanger with a central return tube, the absorption reaction time is reduced by 24% to reach 90% of the storage capacity. After the optimization study of the geometrical parameters, a system with the heat exchanger tube diameter of 5 mm, coil diameter of 18 mm and the coil pitch value of 10 mm is recommended to have lower hydrogen absorption time and higher hydrogen storage capacity. The presented MH reactor can be applied for improvement of heat exchange and absorption process in industrial MH reactors.     

Experimental analysis of hydrogen storage performance of a LaNi5–H2 reactor with phase change materials

Energy storage, especially thermal energy storage, has an important place in terms of efficient use of energy. Systems in which phase change materials (PCMs) are used are among the thermal energy storage (TES) options, thanks to their advantages such as energy storage at almost constant temperature. The use of PCM as a TES material in the metal hydride (MH) reactor is an influential method to store the heat released by the exothermic reaction occurring in the hydrogen charging process and to recover this heat with the endothermic reaction occurring in the hydrogen discharge process. In the present study, hydrogen charge and discharge processes in a LaNi₅–H₂ reactor were experimentally investigated and compared with and without PCM. Therefore, a hybrid system was designed by integrating PCM around the cylindrical MH reactor filled with LaNi₅ alloy. The hydration process was carried out at both constant pressure and variable pressure. The temperature changes on the reactor surface and inside the PCM were measured over time. In experiments to determine the change in the amount of hydrogen stored in MH reactors over time, it was determined that the hydrogen storage pressure and reactor design significantly affect the hydrogen charge-discharge rate. Considering the use of MH reactors in transportation vehicles such as automobiles and submarines, designing a hybrid MH-PCM storage system is promising for the development of hydrogen storage technologies and transportation technologies.     

Hydrogen release from a metal hydride tank with phase change material jacket and coiled-tube heat exchanger

Hydrogen fuel cells are received increasingly wide attention in order to develop green ships and reduce greenhouse gas emissions in the field of waterway transportation. Metal hydrides (MHs) can be used to store hydrogen for green ships due to their high volumetric storage capacity and safety. Various measures should be considered in the design and manufacture process of the MH reactor to strengthen its performance of heat and mass transfer and obtain an acceptable hydrogen storage capacity. In this work, LaNi₅ hydride is used as the hydrogen storage material and packed in the reactor. A basic axisymmetric numerical model for the hydrogen storage system without a heat exchanger has been developed and proved to be effective through the comparison between its simulation results and the published data during dehydriding. A hybrid heat exchanger, which is consisted of a phase change material (PCM) jacket and a coiled-tube, has been applied into the hydrogen storage system to relieve the thermal effect of MH in the dehydriding process on system performance. Effects of the heat transfer coefficient between the circulating heating water in the coil-tube and the MH bed, the temperature of circulating heating water and the pressure at the outlet on the dehydriding performance have been investigated. Based on parametric study, the relationships among the average dehydriding rate, the heat transfer coefficient, the heating water temperature and the outlet pressure have been found and fitted as simple equations. These fitted equations can be considered as a reference, which provides an important method to effectively control the dehydriding rate in order to satisfy the fuel requirement of the power unit and ensure the safe navigation of green ships in the future.     

Hydrogen absorption performance of a novel cylindrical MH reactor with combined loop-type finned tube and cooling jacket heat exchanger

A novel cylindrical metal hydride (MH) reactor with loop-type finned tube and jacket heat exchanger was proposed in this work. This MH reactor is expected to possess high performance due to the enhanced heat transfer, compact structure and good gas tightness. A three-dimensional multi-physical model for hydrogen absorption was presented to investigate the evolutions of temperature and concentration in the MH bed, as well as the mean reaction rate of hydrogen absorption process. The effects of different fin configurations on the performance of the proposed MH reactor were also examined. It was indicated that the evolution curve of the mean reaction rate for the whole hydrogen absorption process can be divided into two stages. The reaction rate in the first stage is mainly dependent on the initial conditions (i.e., temperature and gas pressure) of MH bed, whereas the second stage is mainly influenced by the heat dissipation from MH bed to cooling fluid. For the proposed MH reactor, the total charging time for reaching 90% hydrogen saturation can be decreased by 56.8% and 81.9% as compared with that for cylindrical MH reactor with finned double U-shape tube heat exchanger and cylindrical MH reactor with finned single-tube heat exchanger, respectively. Also, it was found that the interlaced layout design of inner and outer fins can improve the uniformity of the temperature distribution inside the MH bed as compared with the parallel layout configuration. Besides, it was showed that increasing the number of fins with keeping the total fin volume constant, the absorption performance of the reactor can be improved.     

Numerical investigation of heat and mass transfer during hydrogen desorption in a large-scale metal hydride reactor coupled to a phase change material with nano-oxide additives

For the object of reducing heat consumption in hydrogen metal hydride (MH) storage units during the discharging cycle, the nano-PCM (i.e. phase change material containing nano-oxides) strategy is adopted herein for accelerating the release of the latent heat (LH) stocked in the PCM to the MH. The process was assessed in a large-scale horizontal cylindrical reactor equipped with 4 PCM tubes distributed homogenously in the MH-bed. Mass and heat transfer were computationally analyzed in the diverse regions of the MH-nano-PCM system using a 2D numerical model developed with Fluent 15.0 CFD-software. Temporal temperature profiles (average and contours), MH-dehydrogenation efficiency, velocity contours and PCMs solidification rate were established in the presence (5% v/v) and absence of four types of nano-oxides (Al₂O₃, MgO, SnO₂ and SiO₂). Remarkable results were obtained. The nano-PCM system participated in the MH-discharging by providing latent heat (LH) and changing its physical phase. The MH was completely discharged within 700 s. Nano-oxides additions improved the solidification rate of the PCM (i.e. accelerating the release of the LH) by more 50%, with a strong dependency on the PCM-tubes position. The PCM-tube above the H₂-charging pipe solidifies more quickly than the other tubes, probably to the gravitational effect. The outcomes of this research provide insight into the use of nano-PCMs as a thermal supplier in MH storage systems during the discharging cycle.     

Investigation of boiling heat transfer for improved performance of metal hydride thermal energy storage

The inherent nature concerning the intermittency of concentrating solar power (CSP) plants can be overcome by the integration of efficient thermal energy storage (TES) systems. Current CSP plants employ molten salts as TES materials although metal hydrides (MH) have proven to be more efficient due to their increased operating temperatures. Nonetheless, the heat exchange between the MH bed and the heat transfer medium used to operate a heat engine is a critical factor in the overall efficiency of the TES system. In this work, a computational study is carried out to investigate the performance of a magnesium hydride TES packed bed using a multiphase (boiling) medium instead of single-phase heat absorption methods. The boiling heat transfer behaviour is simulated by using the Eulerian two-fluid framework. The simulations are conducted at a transient state using SST-k-ω Reynolds-Averaged Navier-Stokes equations. It is observed that, unlike the single-phase heat collection method, the multiphase heat absorption method maintains a constant temperature in the heat transfer fluid throughout the reactor. Consequently, a higher temperature gradient is realised between the MH bed and heat transfer fluid (HTF), leading to improvements in the overall reaction rate of the hydrogenation process.     

Numerical study on hydrogen and thermal storage performance of a sandwich reaction bed filled with metal hydride and thermochemical material

Hydrogen storage and release process of metal hydride (MH) accompany with large amount of reaction heat. The thermal management is very important to improve the comprehensive performance of hydrogen storage unit. In present paper, thermochemical material (TCM) is used to storage and release the reaction heat, and a new sandwich configuration reaction bed of MH-TCM system was proposed and its superior hydrogen and thermal storage performance were numerically validated. Firstly, the optimum TCM distribution with a volume ratio (TCM in inner layer to total) of 0.4 was derived for the sandwich bed. Then, comparisons between the sandwich reaction bed and the traditional reaction bed were performed. The results show that the sandwich MH-TCM system has faster heat transfer and reaction rate due to its larger heat transfer area and smaller thermal resistance, which results in the hydrogen storage time is shortened by 61.1%. The heat transfer in the reaction beds have significant effects on performance of MH-TCM systems. Increasing the thermal conductivity of the reaction beds can further reduce the hydrogen storage time. Moreover, improving the hydrogen inflation pressure can result in higher equilibrium temperature, which is beneficial for the enhancing heat transfer and hydrogen absorption rates.     

Multi-variable optimization of metal hydride hydrogen storage reactor with gradient porosity metal foam and evaluation of comprehensive performance

Hydrogen storage performance for metal hydride (MH) reactor is restricted by the poor thermal conductivity of MH. In this study, the gradient porosity metal foam was added into MH reactor for enhancing heat transportation (GMF reactor), and its hydrogen absorption performance was investigated numerically in detail. Then, thermal resistance analysis was conducted to analyze the heat transportation in GMF reactor, and Genetic Algorithm was applied for optimizing metal foam distribution under different conditions. It was indicated that the hydrogenation performance for optimized two-layer GMF reactor was increased by 11.5% compared with uniform metal foam reactor (UMF reactor). The optimization results indicated that the optimal volumetric fractions of metal foam (VFMF) are about 0.08 for both optimized GMF reactor and UMF reactor with the trade-off of hydrogen storage capacity and hydrogen absorption rate. Then, a new indicator of comprehensive hydrogen storage performance (CHSP) for MH reactor was proposed, which includes the influence of hydrogen storage rate, hydrogen storage capacity, volumetric storage density and gravimetric storage density. Besides, the hydrogenation performance for optimized GMF reactor was improved with metal foam layer increasing, and the optimal porosity distribution was gradually approaching a specific power exponent trend. It was showed that the hydrogenation performance for power-exponent GMF reactor was increased by 2.8% and 18.2% compared with that of optimized four-layer GMF reactor and UMF reactor, respectively.     

Thermal performance simulations of a packed bed cool thermal energy storage system using n-tetradecane as phase change material

The objective of this paper is to study the thermal performance of latent cool thermal energy storage system using packed bed containing spherical capsules filled with phase change material during charging and discharging process. According to the energy balance of the phase change material (PCM) and heat transfer fluid (HTF), a mathematical model of packed bed is conducted. n-tetradecane is taken as PCM and aqueous ethylene glycol solution of 40% volumetric concentration is considered as HTF. The temperatures of the PCM and HTF, solid and melt fraction and cool stored and released rate with time are simulated. The effects of the inlet temperature and flow rate of HTF, porosity of packed bed and diameter of capsules on the melting time, solidification time, cool stored and released rate during charging and discharging process are also discussed.     

Numerical investigation of hydrogen absorption in a stackable metal hydride reactor utilizing compartmentalization

In this paper, a three-dimensional model for hydrogen absorption in a metal alloy has been developed, validated against the experimental data in the literature, and then applied to a novel design for a hydrogen storage unit. The proposed design is similar to the fuel cell stack, but here the Membrane Electrode Assembly (MEA) has been replaced by a metal hydride (MH) reactor placed between the flow-field plates. These are stacked together to achieve the required amount of hydrogen storage. The flow-field plates have channels engraved on one side for hydrogen supply and on the other, for coolant/heating medium. It is known that the effectiveness of a hydrogen storage unit is directly related to its heat transfer area, and therefore, the choice of its geometry is very important. The larger the size, the more the resistance to heat transfer. Although, the internal tubular heat exchangers have proven to be effective in heat transfer, they pose severe challenges such as cooling/heating medium leakage due to tube erosion, stresses generated, etc. and they displace the active metal hydride from the tank. The present stacked MH reactor configuration helps to overcome these challenges by stacking small MH reactors together and there is no chance of the cooling/heating medium leaking into the metal hydride. Numerical simulations were performed to investigate the effect of coolant flow rate and percentage of flow-field plate rib area exposed to the MH reactor on temperature evolution and the amount of hydrogen stored. Further, a detailed study was carried out to understand the effect of compartmentalization of the MH reactor on temperature distribution. The results revealed that compartmentalization substantially helps to uniformly distribute the temperature in the metal bed, which is very important to maintain uniform utilization of the metal powder. Consequently, the uniform metal powder density for repeated absorption-desorption cycles without significant loss of its hydrogen storage capabilities.     

Validation of a CFD model for the simulation of heat transfer in a tubes-in-tank PCM storage unit

A computational fluid dynamics (CFD) model was developed for the simulation of a phase change thermal energy storage process in a 100 l cylindrical tank, horizontally placed. The model is validated with experimental data obtained for the same configuration. The cold storage unit was charged using water as the heat transfer medium, flowing inside a horizontal tube bundle, and the selected phase change material (PCM) was microencapsulated slurry in 45% w/w concentration. The mathematical model is based on the three-dimensional transient Navier–Stokes equations with nonlinear temperature dependent thermo-physical properties of the PCM during the phase change range. These properties were experimentally determined using analytical methods. The governing equations were solved using the ANSYS/FLUENT commercial software package. The mathematical model is validated with experimental data for three different flow rates of the heat transfer fluid during the charging process. Bulk temperature, heat transfer rate and amount of energy stored were used as performance indicators. It was found that the PCM bulk temperatures were predicted within 5% of the experimental data. The results have also shown that the total accumulated energy was within 10% of the observed value, and thus it can be concluded that the model predicts the heat transfer inside the storage system with good accuracy.     

Development of a heat storage demonstration unit on the basis of Mg2FeH6 as heat storage material and molten salt as heat transfer media

The development and preliminary tests of a 5 kg Mg₂FeH₆ heat storage system which is useable for short and long-term storage applications at temperatures around 500 °C are described. The heat transfer for the heat storage process (dehydrogenation of the hydride Mg₂FeH₆) and heat release (hydrogenation of the hydride precursor 2Mg-Fe) is done by the flow of molten salt in appropriate heat exchangers serving as heat source or heat sink. The construction of the tube bundle reactor as a heat storage tank is presented. 1.6 kWh of heat could be released and 1.5 kWh of heat could be stored during the first experimental tests. Difficulties, which occured during the preliminary tests, are described.     

Hydrogen storage using liquid organic carriers: Equilibrium simulation and dehydrogenation reactor design

Liquid organic hydrogen carriers (LOHC) are unsaturated organic compounds used for chemical hydrogen storage. Using an equilibrium model of the LOHC N-ethylcarbazole, we discuss potential efficiency increases of hydrogen storage systems based on N-ethylcarbazole by the integration of low-temperature waste heat. N-ethylcarbazole is well suited for pressure swing operation with heat exchange between hydrogenation and dehydrogenation. We present and discuss kinetic data of the dehydrogenation reaction gathered in a tubular reactor that was mounted in different orientations and flow configurations. Similar maximum values of power density are reached in vertical and in horizontal orientation. Vertical orientation allows the favorable operation with counter-flow of the liquid carrier and the evolved hydrogen gas and radial heat transfer is significantly better than in horizontal orientation. In vertical reactor configurations, catalyst efficiency and operational stability are impaired at high void fractions. This issue can be reduced by dehydrogenation at elevated pressure and intermediate gas separation from the catalyst bed.     

Analysis of hydrogen storage performance of metal hydride reactor with phase change materials

Using phase change materials (PCM) as thermal energy storage material in metal hydride reactor bed is an effective method to store the heat emitted during hydrogen charging and retrieving it later during discharging. The present work examines the effect of a PCM on the behaviour of the metal hydride in the reactor bed. A two-dimensional model was developed to describe the mass and heat transfer inside the metal hydride and the PCM as well as the interaction between them. The results were compared with other numerical simulation and experimental data. In the simulations, thermal conductivity and the latent heat were varied in order to evaluate the effect of these parameters on the kinetics of absorption, desorption and melting of the phase change material.     

相变蓄热供热装置热性能试验研究与系统经济性分析

为分析相变蓄热装置在充热和放热过程中的热性能,设计并搭建一套相变蓄热供热装置中试实验系统,研究主要运行参数对相变蓄热装置热性能的影响;在此基础上,结合项目案例,对相变蓄热供热系统经济性进行分析。结果表明：相变材料(Phase Change Material, PCM)凝固过程中的传热主要受相变介质内部导热控制;而在其熔化过程中自然对流对传热起重要控制作用;蓄热装置充热速率快于放热速率。提高传热流体流量有助于增强PCM中的热传递,缩短充/放热时间,但蓄热装置内PCM温度分布均匀性有所降低;为降低系统能耗,提高储放热效率,优先选用小流量进行充/放热。该相变蓄热供热项目的动态投资回收期为3.55年,具有良好的经济性。研究结果可对相变蓄热供热系统的设计及应用推广提供参考依据。     

Dehydrogenation reactor for a vehicle equipped with a hydrogen engine: a simulation study

A simulation study on the possibility of the utilization of cyclohexane as a vector for hydrogen storage in transport vehicles equipped with hydrogen engine has been carried out. The results of this study for the Pd/Al₂O₃ catalyst indicate that a dehydrogenation multi-tube reactor for cyclohexane is feasible. Nevertheless, a good heat transfer, which is a limiting factor of the process, has to be assured. To heat this reactor, part of the hydrogen combustion energy normally wasted by the engine cooling system can be used. A system of heat pipes was proposed to transfer the waste heat from the wall of engine cylinders to the wall of the dehydrogenation reactor.     

Integration of hydrogenation and dehydrogenation based on dibenzyltoluene as liquid organic hydrogen energy carrier

The heat transfer oil dibenzyltoluene (DBT) offered an intriguing approach for the scattered storage of renewable excess energy as a novel Liquid Organic Hydrogen Carrier (LOHC). The integration of hydrogenation and dehydrogenation in H0-DBT/H18-DBT pairs demonstrated that the feasibility of hydrogenation and dehydrogenation reaction conducted in one reactor with the same catalyst, which would be proposed to simplify the hydrogen storage process. The optimal reaction temperature based on the inhibition of ring opening and cracking was investigated combined with the ¹H NMR analysis. Meanwhile, the ideal catalyst 3 wt% Pt/Al₂O₃ for high hydrogen storage efficiency was screened out. Cycle tests of hydrogenation and dehydrogenation integration reaction had shown that the hydrogen storage efficiency was 84.6% after five cycle tests. The integration of hydrogenation and dehydrogenation reaction based on DBT exhibited the ideal thermal stability, which demonstrated its potential as a reversible H₂ carrier.     

Dynamic discharging characteristics simulation on solar heat storage system with spherical capsules using paraffin as heat storage material

The dynamic characteristics of solar heat storage system with spherical capsules packed bed during discharging process are studied. According to the energy balance of solar heat storage system, the dynamic discharging processes model of packed bed with spherical capsules is presented. Paraffin is taken as phase change material (PCM) and water is used as heat transfer fluid (HTF). The temperatures of PCM and HTF, solid fraction and heat released rate are simulated. The effects of inlet temperature of HTF, flow rate of HTF and porosity of packed bed on the time for discharging and heat released rate are also discussed. The following conclusion can be drawn: (1) the heat released rate is very high and decreases rapidly with time during the liquid cooling stage, it is stable at the solidification cooling stage, then it decreases to zero at the solid cooling stage. (2) The time for complete solidification decreases when the HTF flow rate increases, but the effect is not so obvious when the HTF flow rate is higher than 13 kg/min; (3) compared to the HTF inlet temperature and flow rate, the influence of porosity of packed bed on the time for complete solidification is not so significant.