Experimental study of metal–hydrogen reactor behavior during desorption under heating by electromagnetic induction

The objective of this work is to study experimentally the behavior of a metal–hydrogen reactor (MHR) during hydrogen desorption by the LaNi₅ hydride. The reactor is surrounded by a small coil traversed by an alternative sinusoidal current. The effect of the voltage applied to the coil is studied. Two kinds of tests are done. In the first one, the reactor is heated to the desired temperature and then it was put in contact with a tank at weak pressure (desorption), and in the second one, desorption and heating start simultaneously. Desorbed mass and temperature evolution within the hydride bed and in the reactor wall, as a function of time, are plotted. A comparison of results obtained by the electromagnetic induction heater and by heat exchanger provisioned by a hot fluid shows an improvement of the efficiency of the reactor when compared to the traditional hot system (fluid system).     

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.     

Prediction of transient heat and mass transfer in a closed metal–hydrogen reactor

The metal–hydrogen reactor is usually composed of a porous medium (hydride bed) and an expansion volume (gaseous phase). During the sorption process, the hydrogen flow and the heat transfer in the expansion part are badly known and can have some effects on the sorption phenomena in the hydride medium. At our knowledge, the hypothesis that neglects those effects is typically used. In this paper, a 2D study of heat and mass transfer has been carried out to investigate the transient transport processes of hydrogen in the two domains of a closed cylindrical reactor. A theoretical model is conducted and solved numerically by the control-volume-based finite element method (CVFEM). The result on temperature and hydride density distribution are presented and discussed. Moreover, this paper discusses in detail the effects of some governing operating conditions, such as dimensions of the expansion volume, height to the radius reactor ratio, and the initial hydrogen to metal atomic ratio, on the evolution of the pressure, fluid flow, temperature and the hydrogen mass desorbed.     

Study of two-dimensional and dynamic heat and mass transfer in a metal–hydrogen reactor

To analyse heat and mass transfer in a metal–hydrogen reactor, the hypothesis that disregards the radiative heat transfer in the reactor, is typically used. In this paper, we take into account the radiative heat transfer and we test the validity of this hypothesis in the case of the LaNi₅ and in the case of the magnesium. A theoretical model is conducted for the two-dimensional system where conduction, convection radiation and chemical reaction take place simultaneously. This model is solved by the finite volume method. The numerical simulation is used to present the time–space evolutions of the temperature and the hydride density in the reactor and to determinate the sensitivity to some parameters (absorption coefficient, scattering coefficient, reactor wall emissivity).     

Experimental and theoretical study of ametal–hydrogen reactor

An experimental and theoretical study of a metal–hydrogen reactor (LaNi₅–H₂) is presented. The first goal of this study is to experimentally determine the effectivethermal conductivity, the conductance between the hydride bed and the fluid around the reactor,the equilibrium pressure and the expression of the reaction kinetics, taking into account the initialcondition, the temperature and the applied hydrogen pressure temporal evolution. The secondgoal is to test the validity of the theoretical model by comparison between theoretical andexperimental results.     

Stress measurement of MlNi4.5Cr0·45Mn0.05 alloy during hydrogen absorption-desorption process in a cylindrical reactor

Hydrogen stored in a solid state form of metal hydrides offers a safe and efficient storage technique for hydrogen application. In a closed metal hydride tank, stresses may occur on the tank wall due to hydride expansion during hydrogen absorption process. In the present investigation, a novel testing system for stress evolution of MlNi_4.5Cr_0.45Mn_0.05 alloy in a closed cylindrical reactor during hydrogen absorption-desorption process was built. The results show that considerable swelling stress is developed on the inner reactor wall during activation process though a high free space of 45% is presented. Increasing hydrogen charging pressure and alloy loading fraction increase the as-generated swelling stress. The metal hydride particle expansion caused by hydrogen absorption is the intrinsic factor for swelling stress evolution. The presence of particle agglomerate in a closed tank in which its expansion is constrained is responsible for the observed swelling stress accumulation.     

The application of membrane reactor technology in hydrogen production using S–I thermochemical process: A roadmap

Thermochemical cycle using water as raw material and nuclear/renewable energies as sources of energy is believed to be a safe, stable and sustainable route of hydrogen production. Amongst the well-studied thermochemical cycles, the sulfur–iodine (S–I) cycle is capable of achieving an energy efficiency of 50%, making it one of the most efficient cycles among all water-splitting processes.     

Experimental study of a metal –hydrogen reactor's behavior under the action of an external magnetostatic field during absorption and desorption

The aim of this work is to experimentally study, the behavior of a metal-hydrogen reactor (MHR) subjected to the action of an external magnetostatic field, during hydrogen absorption and desorption by the LaNi5 hydride. The reactor was surrounded by a copper coil crossed by a continuous current delivered by a DC generator. In this study, the mass of the absorbed and desorbed hydrogen was measured and plotted for different initial temperatures and pressures functions of the applied magnetostatic field. The ratio of the hydrogen mass absorbed or desorbed with and without supplying a magnetostatic field was estimated after which the change in the saturation magnetization per 1 mol of desorbed hydrogen atom (ΔM_s), for the LaNi₅ compound; was determined.The results demonstrated that while the increase in temperature was not beneficial for the absorption reaction, it improved the desorption process. The increase in pressure leads to an increase in the absorbed hydrogen mass. The effect of the applied magnetostatic field was observed especially for the lowest temperatures in the case of the absorption reaction. In fact, we noticed a small increase in the absorbed mass, which decreased and disappeared in the highest temperatures. It was found that the magnetostatic field had no effect on the desorption reaction for the tested fields and temperatures. The low value of ΔM_s confirmed the paramagnetic nature of the sample.     

Dynamic process of hydrogen and heat generation from reaction of Al–Li alloy powders and water vapor at moderate temperatures

As one of the alternative clean fuels, aluminum is suitable for generating hydrogen and power via metal hydrolysis. The reaction process characteristics were studied in a cylindrical reactor with 5 g of Al–Li alloy powder as fuel at moderate temperatures. The test performed good results with 1,130 mL/g alloy of H₂ yield, 86% of the reaction efficiency, and 54.5% of usable heat ratio. The dynamic change of temperature distribution was measured by 12 thermocouples in the reactor, and the maximum was not beyond 892°C. On the basis of the temperature characteristics, the reaction propagation speed was calculated and in the range of 0.57–0.95 mm/s. Moreover, the micromorphology and ingredients presented obvious differences between top product and bottom product, which was resulted from water vapor diffusion. The reaction of Al–Li alloy and steam was determined by both water vapor diffusion and heat transfer, which led to the distinct temperature trends near the vapor inlet, away from the vapor inlet, on the top and at the bottom. On the basis of the results, a mild and controllable hydrogen generation can be achieved at moderate temperatures by optimizing vapor inlet arrangement.     

Air exposure improving hydrogen desorption behavior of Mg–Ni-based hydrides

It is well established that H₂O and O₂ have an inauspicious influence on hydrogen reactivity of hydrogen storage alloys. In this work, an unexpected improvement of the desorption behavior was discovered by just exposing the magnesium rich Mg–Ni hydrides into the air for a certain period. Upon an exposure duration of 4 months, the dehydrogenation peak and onset temperature were sharply lowered by 150 °C and 130 °C. Furthermore, the air-exposed sample could quickly absorb 3.08 wt% H₂ and desorb 2.81 wt% H₂ within 400 s at 300 °C. Besides the refinement of the powders due to the spontaneous hydrolysis reaction, the in-situ formed magnesium hydroxide layer and Ni are thought to be responsible for the remarkable improvement. This work gives interesting insights that the self-generating surface passivation is not necessarily harmful in the solid-state hydrogen storage area, especially for the cases where active sites of catalysis are present.     

Synthesis and hydrogen-storage behavior of metal–organic framework MOF-5

Metal–organic framework MOF-5 (Zn₄O(BDC)₃), a microporous material with a high surface area and large pore volume, was synthesized by three approaches: direct mixing of triethylamine (TEA), slow diffusion of TEA, and solvothermal synthesis. The obtained materials were characterized by X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, and nitrogen adsorption, and their hydrogen-storage capacities were measured. The different synthesis methods influenced the pore-structure parameters, morphologies and hydrogen-storage behavior of the obtained MOF-5. MOF-5 synthesized by the solvothermal approach showed a higher surface area and larger pore volume than the samples prepared by the other two approaches. Measurements of the hydrogen-storage behavior showed that the hydrogen-storage capacity was correlated with the specific surface area and pore volume of MOF-5.     

The potential of transition metal–methylidynes as high-capacity hydrogen storage media

With respect to density functional predictions, TM–methylidynes (TM = Sc, Ti, V, and Cr) bind high-density hydrogen at ambient conditions. TM–methylidyne complexes can adsorb up to seven hydrogen molecules. The predicted maximal retrievable hydrogen storage density is 16.7 wt% for ScCH, a record high value so far, larger than the 16.0 wt% for TiCH, 13.2 wt% for VCH, and 13.0 wt% for CrCH. Dimerization and oligomerization of scandium–methylidyne lower the hydrogen storage capacity to 9.2 wt% for the dimer and to 7.9 wt% for the hexamer. These predictions provide useful guidance for designing novel hydrogen storage materials with optimal gravimetry and kinetics and for devising possible schemes by which the hydrogen/host material interactions can be manipulated.     

Multi-tube Pd–Ag membrane reactor for pure hydrogen production

An experimental apparatus carrying out a membrane process for producing pure hydrogen via ethanol steam reforming has been tested in order to measure the hydrogen production by varying operative parameters such as temperature, pressure and membrane sweeping mode.     

Multiphase reactor scale-up for Cu–Cl thermochemical hydrogen production

This paper examines selected design issues associated with reactor scale-up in the thermochemical copper–chlorine (Cu–Cl) cycle of hydrogen production. The thermochemical cycle decomposes water into oxygen and hydrogen, through intermediate copper and chlorine compounds. In this paper, emphasis is focused on the hydrogen, oxygen and hydrolysis reactors. A sedimentation cell for copper separation and HCl gas absorption tower are discussed for the thermochemical hydrogen reactor. A molten salt reactor is investigated for decomposition of an intermediate compound, copper oxychloride (CuO·Cl₂), into oxygen gas and molten cuprous chloride. Scale-up design issues are examined for handling three phases within the molten salt reactor, i.e., solid copper oxychloride particles, liquid (melting salt) and exiting gas (oxygen). Also, different variations of hydrolysis reactions are compared, including 5, 3 and 2-step Cu–Cl cycles that utilize reactive spray drying, instead of separate drying and hydrolysis processes. The spray drying involves evaporation of aqueous feed by mixing the spray and drying streams. Results are presented for the required capacities of feed materials for the multiphase reactors, steam and heat requirements, and other key design parameters for reactor scale-up to a pilot-scale capacity.     

Effects of the preparative parameters of hydriding combustion synthesis on the properties of Mg–Ni–C as hydrogen storage material

Magnesium may be the most promising solid-state hydrogen storage material owing to its high storage capacity (7.6 wt%) and highest volumetric density (2 times of liquid H₂). On the other hand, suffers from its sluggish absorption/desorption characteristics. In the present study, the simple/cost-effective hydriding combustion synthesis (HCS) was used to prepare highly-active Mg-based-samples. The preparative parameters of HCS were varied, and its effects on the micro-structural and hydrogen storage properties were determined. The results and its analysis showed that the simple HCS process possesses a multifaceted dependence on a range of experimental factors and affect the final product. The estimated dependence enabled us to explain the combined effect of individual experimental factors on the prepared samples. The Mg–Ni–C sample prepared at 610 °C with 6%wt-nano-Ni and 4 wt%-multi-walled-CNTs as reactants, resulted in sample with a surface area as high as 19.01 m²/g and a desorption capacity of 5.77 wt%, highlighting the promising characteristics of HCS to prepare highly-active Mg-based-materials.     

Self-ignition of hydrogen–nitrogen mixtures during high-pressure release into air

This paper demonstrates experimental and numerical study on spontaneous ignition of H₂–N₂ mixtures during high-pressure release into air through the tubes of various diameters and lengths. The mixtures included 5% and 10% (vol.) N₂ addition to hydrogen being at initial pressure in range of 4.3–15.9 MPa. As a point of reference pure hydrogen release experiments were performed with use of the same experimental stand, experimental procedure and extension tubes. The results showed that N₂ addition may increase the initial pressure necessary to self-ignite the mixture as much as 2.12 or 2.85 – times for 5% and 10% N₂ addition, respectively. Additionally, simulations were performed with use of Cantera code (0-D) based on the ideal shock tube assumption and with the modified KIVA3V code (2-D) to establish the main factors responsible for ignition and sustained combustion during the release.     

Microstructural evolution of ball-milled Mg–Ni powder during hydrogen sorption

Ball-milling of Mg₇₅Ni₂₅ powder blends were carried out in a SPEX-8000 shaker mill. The morphology and microstructure of the milled powders were studied by scanning electron microscopy and X-ray diffraction, respectively. The dehydrogenation process of the sample milled for 10 h was stopped at different hydrogen contents (25, 50 and 75 percent of the maximum capacity) in a Sieverts' type apparatus, in order to achieve partially desorbed states. For comparison, the fully hydrided (100 percent) and the fully dehydrided (0 percent) states were also obtained. Convolutional multiple whole profile fitting analysis of the corresponding X-ray powder diffractograms was carried out in order to monitor the evolution of microstructural parameters during desorption, such as average coherent crystallite size and size distribution of two hydrides (Mg₂NiH₄ and Mg₂NiH_0.3) that nucleate during the hydrogenation of Mg–Ni powders. The desorption induced changes in the relative amount of the hydride phases were also quantified.     

Life cycle greenhouse gases emission analysis of hydrogen production from S–I thermochemical process coupled to a high temperature nuclear reactor

A methodology for assessing the environmental impact of products and services is the life cycle analysis (LCA); which is a versatile tool to define the inclusion process and the scope of the production system, for different scenarios and selective comparison of environmental burdens. For the LCA developed in this work, the S–I thermochemical cycle coupled to a high temperature gas nuclear reactor was selected. The defined system function is the production of hydrogen using nuclear energy and the functional unit is 1 kg of hydrogen at the plant gate. The product system was defined by the following steps: (i) extraction and manufacturing of raw materials (upstream flows), (ii) external energy supplied to the system, (iii) nuclear power plant, and (iv) hydrogen production plant. Particular attention was placed to those processes where there was limited information from literature about inventory data, like the TRISO fuel manufacture, and the production of iodine from caliches, which is supplied to the thermochemical process for hydrogen generation. The environmental impact assessment focuses on the emissions of greenhouse gases as comparative parameter related to global warming. The results showed low emissions when electric power was supplied from nuclear energy. When the electric power supply was changed to a mix of fossil fuels, the emissions were significantly higher.