Entropy generation and its relation to heating and cooling requirements of a metal hydride hydrogen storage reactor

In this paper a metal hydride hydrogen storage reactor is analyzed from heat and mass transfer and entropy generation points of view. A transient two dimensional energy equation along with suitable reaction kinetics and entropy balance equation is solved numerically. Results are obtained keeping hydrogen flow rates constant during absorption and desorption. For a fixed mass of metal hydride in the reactor the amount of hydrogen transferred and the time in which the transfer takes place are kept fixed. Using the mathematical model the entropy generated during the process and the external cooling and heating fluid requirements are obtained. Results show how improvement in the design and/or operating conditions leads to reduced cooling and heating requirements and lower entropy generation. For the system considered in the study the internal heat transfer characteristics of the hydride bed are seen to influence the reactor performance significantly. With improved bed heat transfer the required heat transfer fluid temperature during desorption can be reduced and that during absorption can be increased significantly. This automatically leads to lower entropy generation and a more economic system operation. It is expected that the methodology proposed and the results presented in this study will be useful in the optimal design of metal hydride reactors for a variety of practical applications, including hydrogen storage.     

Performance analysis of LaNi5 added with expanded natural graphite for hydrogen storage system

This paper presents a comparative study of two cases of metal hydride hydrogen storage units working on (i) LaNi₅ (ii) Compacts of LaNi₅ incorporated with expanded natural graphite (ENG). It has been observed from the previous studies that the hydriding/dehydriding reactions eventually causes large strain changes, due to which the hydride forming metal alloys disintegrate and form a powder bed. Such reactor beds usually have a low thermal conductivity which minimizes the heat transfer phenomenon occurring during the absorption of hydrogen gas. Therefore, there is a need to implement heat augmentation methods to significantly enhance the thermal conductivity. The objective of this research is to present a 2-D numerical model using Finite Volume Method (FVM) and estimate the hydrogen storage performance of a cylindrical metal hydride bed for both the cases, i.e. powdered metal hydride bed and ENG compacts-based reactor bed at different values of inlet pressure and heat transfer fluid temperature. In this study, a detailed investigation on the absorption process reveals that reactor beds with compacted disks of LaNi₅ and ENG demonstrate an enhanced effective thermal conductivity and efficient mass transfer. The simulation results show that a remarkable improvement in the heat transfer and hydrogen storage capacity with reduced absorption time can be achieved by using LaNi₅ and ENG compacts. It was observed that the average reactor bed temperature dropped from 345.13 K to 337.37 K when the ENG based compacted disks was introduced into the reactor bed. Moreover, for supply pressure of 24 bar and fluid temperature of 293 K, the time taken to absorb hydrogen into the rector to achieve stabilized hydrogen storage capacity was estimated to be 446s and 232 s for the case of metal hydride and ENG compacts-based bed, respectively.     

Enhancement of hydrogen charging in metal hydride-based storage systems using heat pipe

Heat transfer in metal hydride bed significantly affects the performance of metal hydride reactors (MHRs). Enhancing heat transfer within the reaction bed improves the hydriding rate. This study presents performance analysis in terms of storage capacity and time of three different cylindrical MHR configurations using storage media LaNi₅: a) reactor cooled with natural convection, b) reactor with a heat pipe on the central axis, c) reactor with finned heat pipe. This study shows the impact of using heat pipes and fins for enhancing heat transfer in MHRs at varying hydrogen supply pressures (2–15 bar). At any absorption temperature, hydrogen absorption rate and hydrogen storage capacity increase with the supply pressure. Results show that using a heat pipe improves hydrogen absorption rate. It was found that finned heat pipe has a significant effect on the hydrogen charge time, which reduced by approximately 75% at 10 bar hydrogen supply pressure.     

Experimental analysis of a metal hydride hydrogen storage system with hexagonal honeycomb-based heat transfer enhancements-part B

This study is a continuation of the computational analysis of the reactor equipped with hexagonal honeycomb based heat transfer enhancements, performed in Part A of the study. In the present study, the performance of the metal alloy and the reactor is investigated experimentally. The gravimetric capacity and reaction kinetics of the alloy La_0.9Ce_0.1Ni₅ are determined. The performance of the reactor under different external environments is noted. The influence of operating conditions such as supply pressure, heat transfer fluid, heat transfer fluid temperature on the reactor performance is investigated. Evaporative cooling as a heat removal technique for metal hydride based hydrogen storage reactors is tested for the first time and compared to conventional heat removal methods. It is found to improve the heat transfer from the alloy bed significantly.     

Heat and mass transfer studies on plate fin-and-elliptical tube type metal hydride reactors

In the present work a two-dimensional transient model to study the heat and mass transfer characteristics of plate fin-and-elliptical tube type metal hydride reactors is presented. The relevant governing equations are solved numerically. The heat transfer coefficient and pressure drop on external fin side are estimated using available correlations. Effects of external fluid flow rate and temperature on the fin-and-tube metal hydride reactor are studied. Results show that the use of elliptical metal hydride tubes in place of the standard circular tubes give rise to compact systems in addition to considerably lower fan power consumption, with very little change in the average heat and hydrogen transfer rates. Even though the performance of the reactor depends very much on the fin-and-tube arrangement, for all the arrangements considered here, the reactors with elliptical tubes were found to perform better in terms of compactness, weight and fan power consumption. Considering the aspects of mean hydride bed thickness, tube wall thickness, tube mass, compactness, heat and hydrogen transfer rates and fan power consumption, elliptical tubes of 0.6 eccentricity appear to offer the best solution for the given application.     

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.     

Study of heat and mass transfer in MmNi4.6Al0.4 during desorption of hydrogen

In this paper, a numerical investigation of two-dimensional coupled heat and mass transfer during desorption of hydrogen in a cylindrical metal hydride reactor containing MmNi_6.4Al_0.4 is presented. By considering the variation in heat transfer fluid temperature along the axial direction (variable wall temperature boundary condition), the changes in hydride bed temperature at different axial locations are presented. The effect of variable wall temperature boundary condition on hydrogen desorption rate for different hot fluid temperatures and hydride bed thicknesses is investigated. The rate of hydrogen desorption at different hot fluid temperatures showed good agreement with the experimental data reported in the literature. As the desorption progresses, the change in heat transfer fluid temperature along the axial direction is found to decrease with time and becomes unchanged at the end of the process. The effect of variable wall temperature boundary condition on desorption time is found to be significant for the hydride bed thicknesses of about 7.5 mm and more. For a given bed thickness of 17.5 mm, the maximum difference in desorption time between variable wall and constant wall temperature convective boundary conditions is about 375 s at 303 K.     

Design and investigation of hydriding alloy based hydrogen storage reactor integrated with a pin fin tube heat exchanger

The reaction between metal hydride (MH) and hydrogen gas generates substantial amount of heat. It must be removed rapidly to sustain the reaction in the metal hydride hydrogen storage reactor. Previous studies indicate that the performance of the reactor can be improved by inserting an efficient heat exchanger design inside the metal hydride bed. In the present study, a cylindrical shaped metal hydride system containing LaNi₅, integrated with a finned tube heat exchanger assembly made of copper pin fins and tubes, is presented. A 3-D numerical model is formulated in COMSOL Multiphysics 4.4 to study the transient behavior of sorption process inside the reactor. Experimental data obtained from the literature is used to approve the legitimacy of the proposed model. Influence of various operating and geometric parameters on the total absorption time of the reactor has been investigated. It is found that hydrogen supply pressure is the most influencing factor to increase the absorption rate of hydrogen. Total absorption time of the reactor is found to be 636 s with maximum storage capacity of 1.4 wt% at the operating conditions of 15 bar H₂ gas supply pressure, heat transfer fluid temperature of 298 K and flow rate of 6.75 l/min.     

Finite element-based simulation of a metal hydride-based hydrogen storage tank

In this paper, a novel 3D flexible tool for simulation of metal hydrides-based (LaNi₅) hydrogen storage tanks is presented. The model is Finite Element-Based and considers coupled heat and mass transfer resistance through a non-uniform pressure and temperature metal hydride reactor. The governing equations were implemented and solved using the COMSOL Multiphysics simulation environment. A cylindrical reactor with different cooling system designs was simulated. The shortest reactor fill time (15 min) was obtained for a cooling design configuration consisting of twelve inner cooling tubes and an external cooling jacket. Additional simulations demonstrated that an increase of the hydride thermal conductivity can further improve the reactor dynamic performance, provided that the absorbent bed is sufficiently permeable to hydrogen.     

Thermal Modeling of Mg2Ni-Based Solid-State Hydrogen Storage Reactor

In this paper, a numerical study of coupled heat and hydrogen transfer characteristics in an annular cylindrical hydrogen storage reactor filled with Mg₂Ni is presented. An unsteady, two-dimensional (2-D) mathematical model of a metal hydride reaction bed of cylindrical configuration is developed for predicting the hydrogen storage capacity. The effect of volumetric radiation is accounted in the thermal model. Effects of hydride bed thickness, initial absorption temperature, hydride bed thermal conductivity, and hydrogen supply pressure on the hydrogen storage capacity are studied. A thinner hydride bed is found to enhance the hydriding rate, accomplishing a rapid reaction. At an operating condition of 20 bar supply pressure and 573 K initial absorption temperature, Mg₂Ni stores about 36.7 g hydrogen per kg alloy. For a given bed thickness and an overall heat transfer coefficient, there exists an optimum value of hydride bed thermal conductivity. The present numerical results are compared with the experimental data reported in the literature, and good agreement was observed.     

Study of a metal hydride based thermal energy storage system using multi-phase heat exchange for the application of concentrated solar power system

Thermal energy storage system is of great significance for the concentrated solar power system to keep the balance between power generation and demand. Metal hydride based thermal energy storage system is regarded as a promising method due to its good reversibility, low cost, and no by-product. Multi-phase heat exchange has much higher heat transfer coefficient than single-phase fluid heat exchange, thus facilitating the steam generation. In this study, a two-dimensional model of the metal hydride reactor using multi-phase heat exchange is proposed to estimate the performance and its feasibility of application in the concentrated solar power system. The results show that the velocity of the heat transfer fluid should match well with the thermal conductivity of the metal hydride bed to maintain the heat flux at a relatively constant value. The match of thermal conductivity of 3 or 5 W/(m·K) and fluid velocity of 0.0050 m/s results in the heat flux up to about 19 kW/m², which is increased by 3 orders of magnitude than single-phase heat exchange. In the thermal energy storage system, the reheating cycle is recommended to improve the utilization of the thermal energy. The efficiency of the system could be improved from 18.4% to 30.8% using the reheating cycle. The increased efficiency is comparable to the previously reported efficiency of 39.2%. Besides, the operation strategy of raising the steam temperature by increasing the hydrogen pressure or the superheater temperature is suggested for the system to obtain higher efficiency.     

Optimization of heat exchanger designs in metal hydride based hydrogen storage systems

Design of the heat exchanger in a metal hydride based hydrogen storage system influences the storage capacity, gravimetric hydrogen storage density, and refueling time for automotive on-board hydrogen storage systems. The choice of a storage bed design incorporating the heat exchanger and the corresponding geometrical design parameters is not obvious. A systematic study is presented to optimize the heat exchanger design using computational fluid dynamics (CFD) modeling. Three different shell and tube heat exchanger designs are chosen. In the first design, metal hydride is present in the shell and heat transfer fluid flows through straight parallel cooling tubes placed inside the bed. The cooling tubes are interconnected by conducting fins. In the second design, heat transfer fluid flows through helical tubes in the bed. The helical tube design permits use of a specific maximum distance between the metal hydride and the coolant for removing heat during refueling. In the third design, the metal hydride is present in the tubes and the fluid flows through the shell. An automated tool is generated using COMSOL-MATLAB integration to arrive at the optimal geometric parameters for each design type. Using sodium alanate as the reference storage material, the relative merits of each design are analyzed and a comparison of the gravimetric and volumetric hydrogen storage densities for the three designs is presented.     

Numerical analysis of heat and mass transfer during absorption of hydrogen in metal hydride based hydrogen storage tanks

In this paper, hydriding in a cylindrical metal hydride hydrogen storage tank containing HWT5800 (Ti_0.98Zr_0.02V_0.43Fe_0.09Cr_0.05Mn_1.5) is numerically studied with a two-dimensional mathematical model. The heat and mass transfer of this model is computed by finite difference method. The effects of supply pressure, cooling fluid temperature, overall heat transfer coefficient and height to the radius ratio of the tank (H/R) on the hydriding in the hydrogen storage tank are studied. It is found that hydride formation initially takes place uniformly all over the bed and hydriding processes take place at a slower rate at the core region. Supply pressure, cooling fluid temperature and overall heat transfer coefficient play significant roles during the absorption of hydrogen. At the H/R = 2 both maximum bed temperature and the average bed temperature are the highest, and the hydride bed takes the longest time to saturate.     

Experimental study of a metal hydride vessel based on a finned spiral heat exchanger

The reaction time of hydrogen in metal hydride vessels (MHVs for short) is strongly influenced by the heat transfer from/to the hydride bed. In the present work an experimental study of the geometric and the operating parameters of a finned spiral heat exchanger has been carried out to identify their influence on the performance of the charging process of the MHV. The experimental results show that the charge time of the reactor is considerably reduced, when finned spiral heat exchanger is used. In addition, the effect of different parameters (flow mass and temperature of the cooling fluid, applied pressure, and hydrogen tank volume) has been discussed and obtained results show that a good choice of these parameters is important.     

Bio-inspired leaf-vein type fins for performance enhancement of metal hydride reactors

Hydrogenation of metals is an exothermic and reversible process. Thus, metal hydride reactors/devices become essentially heat-driven. Excellent heat control in the MH reactor is required to develop metal hydride devices such as H2 storage systems successfully. Few attempts at nature-inspired designs have proven to have good heat transfer capabilities. Based on this idea, the present study investigates novel bio-inspired leaf-vein type fins for the metal hydride reactor. Two reactor designs are proposed for heat transfer fluid flow, namely (i) central straight tube and (ii) narrow trapezoidal channels with 10 kg of LaNi₅ as a sample alloy. Compared to longitudinal finned single tube reactors (LFSTR), these designs provided better heat transmission and temperature uniformity. For LFSTR, Case-1, and Case-2, 90% storage capacity was reached in 210, 145, and 80 s. Different fin configurations, such as parallel, inclined fins, and fins of different thicknesses, are investigated further in the design with narrow trapezoidal channels. The inclined fin configuration shows better performance, and it is further optimized by varying the inclination angle from 3 to 9° and the fin number from 2 to 4. The optimized design with a 7° inclination angle and four fins required 57 s to attain 90% storage capacity and reduced absorption time by 73% compared to LFSTR. The influence of operating parameters such as hydrogen supply pressure, inlet temperature, and velocity of the heat transfer fluid on the performance is evaluated for the optimized design.     

Performance analysis of a high-temperature magnesium hydride reactor tank with a helical coil heat exchanger for thermal storage

Metal hydrides are regarded as one of the most attractive options for thermal energy storage (TES) materials for concentrated solar thermal applications. Improved thermal performance of such systems is vitally determined by the effectiveness of heat exchange between the metal hydride and the heat transfer fluid (HTF). This paper presents a numerical study supported by experimental validation on a magnesium hydride reactor fitted with a helical coil heat exchanger for enhanced thermal performance. The model incorporates hydrogen absorption kinetics of ball-milled magnesium hydride, with titanium boride and expanded natural graphite additives obtained by Sievert's apparatus measurements and considers thermal diffusion within the reactor to the heat transfer fluid for a realistic representation of its operation. A detailed parametric analysis is carried out, and the outcomes are discussed, examining the ramifications of hydrogen supply pressure and its flow rate. The study identifies that the enhancement of thermal conductivity in magnesium hydride has an insignificant impact on current reactor performance.     

Modelling and experimental results of heat transfer in a metal hydride store during hydrogen charge and discharge

A numerical model for the transient hydrogen charge/discharge rates and thermal behaviour of metal hydride stores was developed and verified against experiments using a cylindrical reactor filled with AB₅-type metal hydride. The model assumes local thermal equilibrium between the gas and solid phases, and incorporates the pressure and temperature-dependent hydrogen reaction rates, as well as heat transfer in the porous metal hydride bed. The model was verified through experimental data. The experiments were performed using a unit with hydrogen storage capacity of 130 Nl H₂; the store was submerged in an isothermal water bath. Experiments at different water bath temperatures and charge/discharge hydrogen pressures indicated a relation between charge/discharge time and these parameters. The reactor's ability to deliver a constant hydrogen flow at different water bath temperatures was experimentally investigated. During simulations it was found that the model applied is sensitive to perturbations of some of its parameters; activation energy of absorption, effective conductivity and heat of reaction were found to be the most important ones. The charge and discharge performances of the store are controlled by the reaction rate in the first half-part of the H absorption/desorption experiments and by a heat transfer in the second half-part of charge/discharge.     

Thermal modeling of LmNi4.91Sn0.15 based solid state hydrogen storage device with embedded cooling tubes

A 2-D mathematical model is developed for predicting the minimum charging/discharging time of the metal hydride based hydrogen storage device by varying the number of cooling tubes embedded in it. This study is extended to 3-D mathematical model for predicting the hydriding and dehydriding characteristics of LmNi_4.91Sn_0.15 based hydrogen storage device with 60 embedded cooling tubes (ECT) using COMSOL Multiphysics 4.3. The performance of the hydrogen storage device during hydriding/dehydriding process is presented for different supply pressure (10–35 bar), hot fluid temperature (30–60 °C) and effective thermal conductivity of hydride bed (0.2–2.5 W/(m?K)). It is observed that the rate of heat transfer and the hydriding and dehydriding rates are enhanced when the number of ECT is increased from 24 to 70. For the reactor with 60 ECT, the rate of hydrogen absorption is rapid for the supply pressure of 35 bar and hydride bed effective thermal conductivity of 2.5 W/(m?K). The numerically predicted hydrogen storage capacity (wt%) and amount of hydrogen desorbed (wt%) are compared with experimental data and found a good accord between them.     

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.     

Experiments on solid state hydrogen storage device with a finned tube heat exchanger

The absorption and desorption performances of a solid state (metal hydride) hydrogen storage device with a finned tube heat exchanger are experimentally investigated. The heat exchanger design consists of two “U” shaped cooling tubes and perforated annular copper fins. Copper flakes are also inserted in between the fins to increase the overall effective thermal conductivity of the metal hydride bed. Experiments are performed on the storage device containing 1 kg of hydriding alloy LaNi₅, at various hydrogen supply pressures. Water is used as the heat transfer fluid. The performance of the storage device is investigated for different operating parameters such as hydrogen supply pressure, cooling fluid temperature and heating fluid temperature. The shortest charging time found is 490 s for the absorption capacity of 1.2 wt% at a supply pressure of 15 bar and cooling fluid temperature and velocity of 288 K and 1 m/s respectively. The effect of copper flakes on absorption performance is also investigated and compared with a similar storage device without copper flakes.