Integration of hydrogenation and dehydrogenation system for hydrogen storage and electricity generation – simulation study

The present study combines methylcyclohexane dehydrogenation and toluene hydrogenation systems to produce steam for power generation. Methylcyclohexane dehydrogenation requires heat input, which has been accomplished using heat, released from toluene hydrogenation system, and heat exchange with steam, produced from the steam generator. The integration of these systems results in the generation of 5 MW electricity, which is used to run the electrolysis unit. The overall process does not require an extra source of energy, decreasing the external utility requirement. Both the systems have been investigated against various catalysts for the selection of best catalyst, thus enhancing overall process efficiency. The study has been carried out using Aspen HYSYS v 9. Aspen Energy Analyzer v 9 has been used to do the energy analysis of the system. Overall plant costing has been carried out using Aspen Economic Analyzer v 9.     

Coiled-tube heat exchanger for high-pressure metal hydride hydrogen storage systems – Part 2. Computational model

This second part of a two-part study presents a transient, three-dimensional numerical model for a high-pressure metal hydride (HPMH) hydrogen storage system that is cooled by a coiled-tube heat exchanger. The model uses the same geometry examined in the first part of the study and its predictions are compared to experimental results also discussed in the first part. The model involves solving coupled heat diffusion and hydriding reaction equations for Ti_1.1CrMn. These equations are solved to determine the spatial distribution of hydride temperature as a function of time over the entire duration of the hydriding reaction, which is shown to agree favorably with the experimental data. The model also serves as an effective means for tracking the detailed temporal variations of the heat exchanger’s key performance parameters for different hydride locations relative to the coolant tube. These variations can aid in determining optimum placement of the coolant tube relative the hydride powder. Like the experimental study, the model proves that coolant temperature has the greatest influence on the time needed to complete the hydriding reaction.     

Enhanced heat exchanger design for hydrogen storage using high-pressure metal hydride – Part 2. Experimental results

Hydrogen storage systems utilizing high-pressure metal hydrides (HPMHs) require a highly effective heat exchanger to remove the large amounts of heat released once the hydrogen is charged into the system. Aside from removing the heat, the heat exchanger must be able to accomplish this task in an acceptably short period of time. A near-term target for this ‘fill-time’ is less than 5 min. In this two-part study, a new class of heat exchangers is proposed for automobile hydrogen storage systems. The first part discussed the design methodology and a 2-D computational model that was constructed to explore the thermal and kinetic behavior of the metal hydride. This paper discusses the experimental setup and testing of a prototype heat exchanger using Ti_1.1CrMn as HPMH storage material. Tests were performed to examine the influence of pressurization profile, coolant flow rate and coolant temperature on metal hydride temperature and reaction rate. The experimental data are compared with predictions of the 2-D model to validate the model, calculate reaction progress and determine fill time. The prototype heat exchanger successfully achieved a fill time of 4 min 40 s with a combination of fast pressurization and low coolant temperature. A parameter termed non-dimensional conductance (NDC) is shown to be an effective tool in designing HPMH heat exchangers and estimating fill times achievable with a particular design.     

Coiled-tube heat exchanger for High-Pressure Metal Hydride hydrogen storage systems – Part 1. Experimental study

This two-part study explores the development and thermal performance of a coiled-tube heat exchanger for hydrogen fuel cell storage systems utilizing High-Pressure Metal Hydride (HPMH). The primary purpose of this heat exchanger is to tackle the large amounts of heat released from the exothermic hydriding reaction that occurs when the hydrogen is charged into the storage vessel and is absorbed by the HPMH. The performance of heat exchanger was tested using 4 kg of Ti_1.1CrMn at pressures up to 280 bar. Tests were performed to assess the influence of different operating conditions on the effectiveness of the heat exchanger at removing the heat in a practical fill time (time required to complete 90% of the hydriding reaction). It is shown that distance of metal hydride particles from the coolant tube has the most dominant influence on hydriding rate, with particles closer to the tube completing their hydriding reaction sooner. Faster fill times were achieved by reducing coolant temperature and to a lesser extent by increasing pressurization rate. By comparing tests with and without coolant flow, it is shown that the heat exchanger reduces fill time by 75% while occupying only 7% of the storage pressure vessel volume. The second part of this study will present a 3D computational heat transfer model of the storage vessel and heat exchanger, and compare the model predictions to the experimental data.     

Comparative study on the numerical simulation of hydrogen separation through palladium and palladium–copper membranes

The hydrogen (H₂) diffusion through palladium (Pd) and Pd–copper (Cu) membranes was numerically investigated by developing a two-dimensional computational fluid dynamics model for predicting the performance of H₂ separation. The momentum and mass transport phenomena in the laminar flow conditions were solved at different operating conditions in a vertical cylindrical-type reactor. The effect of feed-gap distance, H₂ concentration, and reactor heating temperature on the H₂ permeation processes were simulated and compared for both Pd-based membranes. The concentration, velocity, and convective and diffusion mass transfer flux distributions were analyzed using the designed model. The H₂ concentration was proportional to the feed-gap distance/cross-sectional area. The smaller the feed-gap distance, the greater the probability of a H₂ molecule being adsorbed by the membrane surface and the ionization energy increasing, leading to further H₂ dissociation through the Pd-based membranes. It was found that the diffusion flux of all feed concentrations was substantially decreased 50 s after the start of the permeation process. Moreover, the diffusion flux of the Pd–Cu40% membrane was relatively larger than that of the pure Pd membrane under the same operating conditions. The distributions of the convective flux, diffusion mass transfer flux, and concentration of the Pd–Cu40% membrane were substantially increased up to 350 °C, then fell to a lower value at higher temperatures. The simulation results were validated with the experimental results, with analysis indicating a good agreement with the experimental results under the same operating conditions. It can be concluded that the simulation modeling for Pd-based membranes was able to predict the optimum operating conditions at high H₂ diffusion rates.     

Thermal–fluid behavior of the hydriding and dehydriding processes in a metal hydride hydrogen storage canister

A study of the hydrogen absorption and desorption processes using LaNi₅ metal hydride is presented for investigation on the influences of expansion volume and heat convection. The hydrogen storage canister comprises a cylindrical metal bed and a void of expansion volume atop the metal. The expansion volume is considered as a domain of pure hydrogen gas. The gas motion in the metal hydride bed is treated as porous medium flow. Concepts of mass and energy conservation are incorporated in the model to depict the thermally coupled hydrogen absorption and desorption reactions. Simulation results show the expansion volume reduces the reaction rates by increasing thermal resistance to the heat transfer from the outside cooling/heating bath. The assumption usually adopted in simulating heat transfer in a metal hydride tank that heat convection in the reaction bed may be ignored is not valid when expansion volume is used because heat convection dominates the heat transfer through the expansion volume as well as the metal bed. The details of the thermal flow pattern are demonstrated. It is found that, due to the action of thermal buoyancy, circulations are likely to happen in the expansion volume. The hydrogen gas accordingly, instead of going directly between the inlet/outlet and the metal bed, tends to move with the circulation along the boundary of the expansion volume.     

The effect of a perforated plate on the propagation of laminar hydrogen flames in a channel – A numerical study

Laminar hydrogen flame propagation in a channel with a perforated plate is investigated using 2D reactive Navies-Stokes simulations. The effect of the perforated plate on flame propagation is treated with a porous media model. A one step chemistry model is used for the combustion of the stoichiometric H₂–air mixture. Numerical simulations show that the perforated plate has considerable effect on the flame propagation in the region downstream from the perforated plate and marginal effect on the upstream region. It is found to squeeze the flame front and result in a ring of unburned gas pocket around the flame neck. The resulting abrupt change in flow directions leads to the formation of some vortices. Downstream of the perforated plate, a wrinkled “M”-shape flame is observed with “W” shape flame speed evolution, which lastly turns back to a convex curved flame front. Parametric studies have also been carried out on the inertial resistance factor, porosity, perforated plate length and its location to investigate their effects on flame evolution. Overall, for parameter range studied, the perforated plate has an effect of reducing the flame speed downstream of it.     

Numerical and experimental analysis of falling-film exchangers used in a LiBr–H2O interseasonal heat storage system

This paper investigates heat and mass transfer occurring in an interseasonal absorption heat storage system using LiBr/H₂O as the sorption couple. It focuses on the poor performances of the falling film exchangers with vertical tubes, which are characterized by low flow rate compared to conventional absorption machines. A numerical model was developed for the study and validated with specific experimental results. Comparison of the numerical model to experimental results from the heat storage prototype shows the presence of abnormally high thermal resistance between the falling films and the exchanger surfaces. The deterioration in performance appears to originate in the low wetting rate of the surfaces. A new design of the exchangers is proposed to solve this problem and thus attain the desired performance.     

Theoretical study on the structural evolution and hydrogen storage in NbHn (n = 2–15) clusters

Niobium hydrides are attractive superconductors. Exploring the formation process of niobium hydrides is essential to elucidate the mechanism of superconductivity. One of the key issues is to clarify the atomic stacking patterns of Nb and H atoms, i.e., the structural evolution of Nb–H clusters. Here, the low-energy structural isomers of NbH_n (n = 2–15) clusters are determined using the CALYPSO method combined with density functional theory calculations. Geometries were fully optimized at the B3LYP/LANL2DZ/6–311++G(d) level of theory to determine global minimum structures for each size. The results indicate that NbH₁₃ is the most stable cluster in this size range. The 4d atomic orbital of Nb and the hydrogen 1s atomic orbital participate largely to the internal binding of the NbH₁₃ cluster. They hydrogen storage density and adsorption energy of this cluster are calculated to be 12.4 wt% and 2.58 eV, respectively. The high hydrogen storage density, suitable hydrogen adsorption energy, and high stability of NbH₁₃ shows promise as a hydrogen storage material. These results provide fundamental information for further design of metal hydrogen storage materials.     

Analyses of non-Fourier heat conduction in 1-D cylindrical and spherical geometry – An application of the lattice Boltzmann method

This article deals with the implementation of the lattice Boltzmann method (LBM) for the analyses of non-Fourier heat conduction in 1-D cylindrical and spherical geometries. Evolution of the wave like temperature distributions in the medium is obtained, and analysed for the effects of different sets of thermal perturbations at the inner and the outer boundaries of the geometry. The LBM results are validated against those available in the literature, and those obtained by solving the same problems using the finite volume method (FVM). Results of the LBM are in excellent agreement with those reported in the literature, and with the results from the FVM. Computationally, the LBM has an advantage over the FVM.     

An empirical study on heat transfer and pressure drop characteristics of CuO–base oil nanofluid flow in a horizontal helically coiled tube under constant heat flux

An experimental investigation has been carried out to study the heat transfer and pressure drop characteristics of nanofluid flow inside horizontal helical tube under constant heat flux. The nanofluid is prepared by dispersion of CuO nanoparticle in base oil and stabilized by means of an ultrasonic device. Nanofluids with different particle weight concentrations of 0.5%, 1% and 2% are used. The effect of different parameters such as flow Reynolds number, fluid temperature and nanofluid particle concentration on heat transfer coefficient and pressure drop of the flow are studied. Observations show that by using the helically coiled tube instead of the straight one, the heat transfer performance is improved. Also, the curvature of the tube will result in the pressure drop enhancement. In addition, the heat transfer coefficient as well as pressure drop is increased by using nanofluid instead of base fluid. Furthermore, the performance evaluation of the two enhanced heat transfer techniques studied in this investigation shows that applying helical tube instead of the straight tube is a more effective way to enhance the convective heat transfer coefficient compared to the second method which is using nanofluids instead of the pure liquid.     

A density functional theory and grand canonical Monte Carlo simulations study the hydrogen storage on the Li-decorated net-τ

To find ideal hydrogen storage media, hydrogen storage performance of Li decorated net-τ has been investigated by first-principles calculations. Maximum 6 Li atoms are adsorbed on net-τ, with the average binding energy of 2.15 eV for per Li atom. Based on 6Li-decorated net-τ, up to twenty H₂ molecules are adsorbed, with a high H₂ storage capacity of 12.52 wt% and an appropriate adsorption energy of 0.21 eV/H₂. Finally, H₂ uptake performance is measured by GCMC simulations. Our results suggest that Li-decorated net-τ may be a promising hydrogen storage medium under realistic conditions.     

Immersed boundary method for the simulation of heat transfer and fluid flow based on vorticity–velocity formulation

ABSTRACT

The present paper, based on the vorticity–velocity formulation of the Navier–Stokes equations, proposes an immersed boundary method for the simulation of heat transfer problems within a geometrically complex domain. The desired boundary conditions are imposed by the direct modification of the initial conditions of vorticity transport and energy equations using smooth interpolations. The time advancement of both transport equations is performed by the explicit fourth-order Runge–Kutta method. One of the main objectives of this paper is to present global smooth interpolations to evaluate the local Nusselt number. The forced convection of moving and fixed circular cylinders, natural convection problem in complex geometries, and the mixed convection between two concentric cylinders—at various Reynolds numbers—are studied.     

An assessment on the planning and construction of an island renewable energy system – A case study of Kinmen Island

During the last 50 years, Kinmen's economy has gone from military-based to increasingly tourism-based, Kinmen has been putting various constructions into action, and hence, the demand for electricity supply is getting higher relatively while the province is pushing various constructions. Nowadays, Kinmen County Government has made directions for future developments already and kept on promoting the sustainable development of Kinmen Island in order to make it a suitable place for living. According to the development blueprint, the future resident population will increase to around 150 ～ 200 thousand people so the relative electricity consumption in Kinmen Island will cause serious problems for Taipower in addition to large scale environmental pollution. The present study researches on both the limitation and independence of this particular island and presumes the electricity power supply will be provided through renewable energy sources, such as solar energy, wind energy, and tidal power generation and so on, whereby it will achieve the target of energy saving and carbon reduction successfully soon. Upon the construction process of the renewable energy sources, this study will simultaneously assess the eco-environment and social conditions on the island to evaluate the feasibility of existing renewable energy technologies which are more mature and determine the optimum renewable energy system that shall be constructed in the Kinmen region in the near future, in order to replace traditional energy sources. Meanwhile, it will assist the related energy industries to create an ultra-clean environment in Kinmen with self-developing power and enhance international competition forces so as to establish a positive international image of environmental protection by achieving a habitat with energy self-sufficiency, and ultimately the empirical model can be duplicated and promoted to other islands.     

Theoretical study on hydrogen solubility and diffusivity in the γ-TiAl L10 structure

The present work is a discussion on hydrogen solubility and diffusivity in the TiAl-L1₀ system using first-principles calculations. First, ground-state properties of the TiAl-L1₀ system are presented and discussed using elastic, phonon and thermal properties. They are compared with literature results. After having analyzed the geometry of L1₀ using the space-group theory, ten potential interstitial sites for hydrogen insertion were identified (among which the various octahedral and tetrahedral sites). After relaxation, only three configurations remained stable, but one site was significantly more stable than the others. The interactions between hydrogen and metal atoms are then described and analyzed by computing different quantities such as phonon properties, charge transfers, formation volumes and elastic dipoles. Diffusion mechanisms were then studied by analyzing the possible displacements at the atomic scale, and the diffusion coefficient of H atoms in TiAl was finally computed. Results how that H diffusion is strongly anisotropic.     

A solid oxide fuel cell operating on liquid organic hydrogen carrier-based hydrogen – A kinetic model of the hydrogen release unit and system performance

In this paper, a kinetic model for the catalytic dehydrogenation of perhydro dibenzyltoluene (H18-DBT), a well-established Liquid Organic Hydrogen Carrier (LOHC) compound, is presented. Kinetic parameters for hydrogen release at a Pt on alumina catalyst in a temperature range between 260 °C and 310 °C are presented. A Solid Oxide Fuel Cell (SOFC) system model was coupled to the hydrogen release from H18-DBT in order to validate the full sequence of LOHC-bound hydrogen-to-electric power. A system layout is described and investigated according to its transient operating behavior and its efficiency. We demonstrate that the maximum efficiency of LOHC-bound hydrogen-to-electricity is 45% at full load, avoiding any critical conditions for the system components.     

The effect of the discharge rate on the electrochemical properties of AB3-type hydrogen storage alloy as anode in nickel–metal hydride batteries

In this work, the ternary CeY₂Ni₉ alloy was prepared and served as anode materials in the Ni–MH battery system. The effect of the discharge rate on the electrochemical proprieties of CeY₂Ni₉, such as activation capability, polarization, discharge capacities, hydrogen atomic diffusion capability and redox parameters, were also investigated systematically during activation and long cycling. Charge–discharge measurement showed that this alloy is characterized by fast activation and requires only three cycles to be activated regardless of the discharge rate, the maximum discharge capacity was obtained for the medium discharge rate (C/10). An important correlation was observed between the evolution of the electrochemical parameters and that of the kinetic parameters, such as the hydrogen atomic diffusion capability and the exchange current density.The total substitution of La by Ce in LaY₂Ni₉ parent alloy enhanced its activation, polarization and stability despite the decrease of its discharge capacities, especially at high rates.     

Wind hydrogen energy system and the gradual replacement of natural gas in the State of Ceará – Brazil

The original model for the solar hydrogen energy system created by Veziroglu and Basar in the 70’s was adapted to the State of Ceará – Brazil. The State of Ceará has one of the greatest wind potentials in Brazil and it is estimated to be around 35 GW. At the present year, there are 494 MW wind farms in operation. The aforementioned State also has a natural gas grid of pipelines serving a great number of consumers. There are studies in literature considering the injection of hydrogen into the natural gas pipeline up to 20% in volume without substantial modifications in the natural gas infrastructure. The main objective of this article is to use that model in order to evaluate long term scenarios in which the off peak wind generated hydrogen gradually replaces natural gas in such important State of Brazil. The system is supposed to start in the year 2015 and the economical revenue when it is fully implemented can reach respectively US$ 730 million or US$ 1 billion in the slow or fast scenario of hydrogen introduction into the energy matrix of that important State of Brazil.     

Formation of alloys in the Ti–Nb system by hydride cycle method and synthesis of their hydrides in self-propagating high-temperature synthesis

In this work the results of investigation of mechanism of alloy formation in Ti–Nb system by “Hydride cycle” (HC) method are presented. The temperature regime of dehydrogenation-sintering is defined; the dependences of phase composition of the synthesized alloys on the dispersity and ratio of source reagents (TiH₂ and NbH_x powders) are studied. X-ray method is used for determination of structural characteristics of synthesized alloys and their hydrides. The results indicate that the crystal lattice and morphology of Ti–Nb alloys are sensitive to the content of Nb: at increasing of NbH portion in the charge, the β-phase becomes prevailing in the formed BCC alloy. The BCC alloys have been estimated as effective hydrogen storage materials. Therefore, we studied the interaction of synthesized alloys with hydrogen in combustion regime to obtain their hydrides.     

Hydrothermal co-gasification of sorghum biomass and çan lignite in mild conditions: An optimization study for high yield hydrogen production

In this study, response surface methodology (RSM) combined with a 3–factor and 3–level Box–Behnken design (BBD) was performed to obtain high yield hydrogen production from hydrothermal co–gasification of sorghum biomass and low rank Çan lignite in a batch type reactor at 500 °C. The individual and the combined effects of the process parameters of coal amount (%) of the coal/biomass mixtures, initial water volume (mL) of the reactor and amount of the coal/biomass mixtures (kg) on system pressure, total gas yield, hydrogen production and product distribution were determined. Water volume directly affected the system pressure and the reaction medium was supercritical water medium above 48.2 mL with a pressure of 22.06 MPa. The highest values of both total gas volume and hydrogen gas volume were reached by gasification of 5.0 g of feedstock. It has been observed that total gas volume and hydrogen volume were directly affected by the water volume in the reactor and the coal ratio of the coal-biomass mixtures. The highest total gas and hydrogen volumes can be achieved under the conditions where the higher levels of water volume of the reactor and lower levels of coal percentage of the coal/biomass mixture were combined. Optimum conditions for maximum hydrogen production with 5.0 g of coal/biomass mixture were determined with numerical optimization as coal percentage of 25.6% and initial water volume of 68.5 mL. By combining the impregnated K₂CO₃ (3%, (w/w)) and CaO catalysts an excellent hydrogen selectivity was achieved. The hydrogen selectivity was drastically increased from 32.0% to 70.8% by capturing more than 99% of CO₂ with a H₂/CO₂ mol ratio of 88.5.