Transmission, Distribution & Storage
Quantitative Evaluations of Hydrogen Diffusivity in V-X (X = Cr, Al, Pd) Alloy Membranes Based on Hydrogen Chemical Potential
Jan 2021
Publication
Vanadium (V) has higher hydrogen permeability than Pd-based alloy membranes but exhibits poor resistance to hydrogen-induced embrittlement. The alloy elements are added to reduce hydrogen solubility and prevent hydrogen-induced embrittlement. To enhance hydrogen permeability the alloy elements which improve hydrogen diffusivity in V are more suitable. In the present study hydrogen diffusivity in V-Cr V-Al and V-Pd alloy membranes was investigated in view of the hydrogen chemical potential and compared with the previously reported results of V-Fe alloy membranes. The additions of Cr and Fe to V improved the mobility of hydrogen atoms. In contrast those of Al and Pd decreased hydrogen diffusivity. The first principle calculations revealed that the hydrogen atoms cannot occupy the first-nearest neighbour T sites (T1 sites) of Al and Pd in the V crystal lattice. These blocking effects will be a dominant contributor to decreasing hydrogen diffusivity by the additions of Al and Pd. For V-based alloy membranes Fe and Cr are more suitable alloy elements compared with Al and Pd in view of hydrogen diffusivity.
Adsorption-Based Hydrogen Storage in Activated Carbons and Model Carbon Structures
Jul 2021
Publication
The experimental data on hydrogen adsorption on five nanoporous activated carbons (ACs) of various origins measured over the temperature range of 303–363 K and pressures up to 20 MPa were compared with the predictions of hydrogen density in the slit-like pores of model carbon structures calculated by the Dubinin theory of volume filling of micropores. The highest amount of adsorbed hydrogen was found for the AC sample (ACS) prepared from a polymer mixture by KOH thermochemical activation characterized by a biporous structure: 11.0 mmol/g at 16 MPa and 303 K. The greatest volumetric capacity over the entire range of temperature and pressure was demonstrated by the densest carbon adsorbent prepared from silicon carbide. The calculations of hydrogen density in the slit-like model pores revealed that the optimal hydrogen storage depended on the pore size temperature and pressure. The hydrogen adsorption capacity of the model structures exceeded the US Department of Energy (DOE) target value of 6.5 wt.% starting from 200 K and 20 MPa whereas the most efficient carbon adsorbent ACS could achieve 7.5 wt.% only at extremely low temperatures. The initial differential molar isosteric heats of hydrogen adsorption in the studied activated carbons were in the range of 2.8–14 kJ/mol and varied during adsorption in a manner specific for each adsorbent.
Commercialisation of Energy Storage
Mar 2015
Publication
This report was created to ensure a deeper understanding of the role and commercial viability of energy storage in enabling increasing levels of intermittent renewable power generation. It was specifically written to inform thought leaders and decision-makers about the potential contribution of storage in order to integrate renewable energy sources (RES) and about the actions required to ensure that storage is allowed to compete with the other flexibility options on a level playing field.<br/>The share of RES in the European electric power generation mix is expected to grow considerably constituting a significant contribution to the European Commission’s challenging targets to reduce greenhouse gas emissions. The share of RES production in electricity demand should reach about 36% by 2020 45-60% by 2030 and over 80% in 2050.<br/>In some scenarios up to 65% of EU power generation will be covered by solar photovoltaics (PV) as well as on- and offshore wind (variable renewable energy (VRE) sources) whose production is subject to both seasonal as well as hourly weather variability. This is a situation the power system has not coped with before. System flexibility needs which have historically been driven by variable demand patterns will increasingly be driven by supply variability as VRE penetration increases to very high levels (50% and more).<br/>Significant amounts of excess renewable energy (on the order of TWh) will start to emerge in countries across the EU with surpluses characterized by periods of high power output (GW) far in excess of demand. These periods will alternate with times when solar PV and wind are only generating at a fraction of their capacity and non-renewable generation capacity will be required.<br/>In addition the large intermittent power flows will put strain on the transmission and distribution network and make it more challenging to ensure that the electricity supply matches demand at all times.<br/>New systems and tools are required to ensure that this renewable energy is integrated into the power system effectively. There are four main options for providing the required flexibility to the power system: dispatchable generation transmission and distribution expansion demand side management and energy storage. All of these options have limitations and costs and none of them can solve the RES integration challenge alone. This report focuses on the question to what extent current and new storage technologies can contribute to integrate renewables in the long run and play additional roles in the short term.
Quantitative Risk Analysis of a Hazardous Jet Fire Event for Hydrogen Transport in Natural Gas Transmission Pipelines
Jan 2021
Publication
With the advent of large-scale application of hydrogen transportation becomes crucial. Reusing the existing natural gas transmission system could serve as catalyst for the future hydrogen economy. However a risk analysis of hydrogen transmission in existing pipelines is essential for the deployment of the new energy carrier. This paper focuses on the individual risk (IR) associated with a hazardous hydrogen jet fire and compares it with the natural gas case. The risk analysis adopts a detailed flame model and state of the art computational software to provide an enhanced physical description of flame characteristics.<br/>This analysis concludes that hydrogen jet fires yield lower lethality levels that decrease faster with distance than natural gas jet fires. Consequently for large pipelines hydrogen transmission is accompanied by significant lower IR. Howbeit ignition effects increasingly dominate the IR for decreasing pipeline diameters and cause hydrogen transmission to yield increased IR in the vicinity of the pipeline when compared to natural gas.
Brittle Fracture Manifestation in Gas Pipeline Steels after Long-term Operation
Dec 2020
Publication
Gas pipelines are exposed to operational loads combined with corrosive environment action during their long-term service. Complicated service conditions lead to a worsening of steel properties a reduction of serviceability of the whole object therefore a risk of its premature failure rises. Aware of the importance of the existing problem the aim of this study is the analysis of various mechanical properties of steels after their long-term operation on gas pipelines and detecting and evaluating fractographic signs of this degradation.<br/>Mechanical properties of operated pipe steels characterizing their brittle fracture resistance were significantly decreased. Delamination areas as one of a feature of brittle fracture were identified on the fracture surfaces of specimens after SSRT of the operated steels in corrosive environment. Fracture was initiated from the outer surface of the specimens along the boundaries of ferrite and pearlite grains with significant secondary cracking.<br/>The obvious texture in the steels affects noticeably the results of the impact tests. Higher KCV values for the specimens cut in the longitudinal direction relative to the pipe axis comparing with the specimens of transversal orientation were obtained. This was explained by different length of narrow pearlite strips alternated by wide ferrite bands and interrupted by individual ferrite grains depending on the orientation of the specimen fracture surface relative to the pipe axis. Thus a proper direction of specimen cutting to achieve the maximum sensitivity of KCV parameter to operational degradation of steels is discussed. The effect of specimen orientation on the results of the Charpy testing becomes much more pronounced with steel operation. Defects accumulated in steels during their service are preferentially oriented in the pipe axial direction along the boundaries between ferrite and pearlite strips. Analyzing the fracture surfaces of the Charpy specimens after their impact testing certain signs of embrittlement were found for long term operated steels in the form of delaminations varying in size and shape and some cleavage fragments. Furthermore their percentage of total fracture surface (generally formed by dimples) correlates well with a drop in the impact toughness. The established relationship could be the basis for the introduction of fractographic criteria of the steel serviceability.
Materials Towards Carbon-free, Emission-free and Oil-free Mobility: Hydrogen Fuel-cell Vehicles—Now and in the Future
Jul 2010
Publication
In the past material innovation has changed society through new material-induced technologies adding a new value to society. In the present world engineers and scientists are expected to invent new materials to solve the global problem of climate change. For the transport sector the challenge for material engineers is to change the oil-based world into a sustainable world. After witnessing the recent high oil price and its adverse impact on the global economy it is time to accelerate our efforts towards this change.
Industries are tackling global energy issues such as oil and CO2 as well as local environmental problems such as NOx and particulate matter. Hydrogen is the most promising candidate to provide carbon-free emission-free and oil-free mobility. As such engineers are working very hard to bring this technology into the real society. This paper describes recent progress of vehicle technologies as well as hydrogen-storage technologies to extend the cruise range and ensure the easiness of refuelling and requesting material scientists to collaborate with industry to fight against global warming.
Link to document download on Royal Society Website
Industries are tackling global energy issues such as oil and CO2 as well as local environmental problems such as NOx and particulate matter. Hydrogen is the most promising candidate to provide carbon-free emission-free and oil-free mobility. As such engineers are working very hard to bring this technology into the real society. This paper describes recent progress of vehicle technologies as well as hydrogen-storage technologies to extend the cruise range and ensure the easiness of refuelling and requesting material scientists to collaborate with industry to fight against global warming.
Link to document download on Royal Society Website
Rock Mass Response for Lined Rock Caverns Subjected to High Internal Gas Pressure
Mar 2022
Publication
The storage of hydrogen gas in underground lined rock caverns (LRCs) enables the implementation of the first fossil-free steelmaking process to meet the large demand for crude steel. Predicting the response of rock mass is important to ensure that gas leakage due to rupture of the steel lining does not occur. Analytical and numerical models can be used to estimate the rock mass response to high internal pressure; however the fitness of these models under different in situ stress conditions and cavern shapes has not been studied. In this paper the suitability of analytical and numerical models to estimate the maximum cavern wall tangential strain under high internal pressure is studied. The analytical model is derived in detail and finite element (FE) models considering both two-dimensional (2D) and three-dimensional (3D) geometries are presented. These models are verified with field measurements from the LRC in Skallen southwestern Sweden. The analytical model is inexpensive to implement and gives good results for isotropic in situ stress conditions and large cavern heights. For the case of anisotropic horizontal in situ stresses as the conditions in Skallen the 3D FE model is the best approach
Investigation of Hydrogen Embrittlement Susceptibility and Fracture Toughness Drop after in situ Hydrogen Cathodic Charging for an X65 Pipeline Steel
Apr 2020
Publication
The present research focuses on the investigation of an in situ hydrogen charging effect during Crack Tip Opening Displacement testing (CTOD) on the fracture toughness properties of X65 pipeline steel. This grade of steel belongs to the broader category of High Strength Low Alloy Steels (HSLA) and its microstructure consists of equiaxed ferritic and bainitic grains with a low volume fraction of degenerated pearlite islands. The studied X65 steel specimens were extracted from pipes with 19.15 mm wall thickness. The fracture toughness parameters were determined after imposing the fatigue pre-cracked specimens on air on a specific electrolytic cell under a slow strain rate bending loading (according to ASTM G147-98 BS7448 and ISO12135 standards). Concerning the results of this study in the first phase the hydrogen cations’ penetration depth the diffusion coefficient of molecular and atomic hydrogen and the surficial density of blisters were determined. Next the characteristic parameters related to fracture toughness (such as J KQ CTODel CTODpl) were calculated by the aid of the Force-Crack Mouth Open Displacement curves and the relevant analytical equations.
The Influence of Refractory Metals on the Hydrogen Storage Characteristics of FeTi-based Alloys Prepared by Suspended Droplet Alloying
Jun 2020
Publication
The influence of the addition of refractory metals (molybdenum and tantalum) on the hydrogenation properties of FeTi intermetallic phase-based alloys was investigated. The suspended droplet alloying technique was applied to fabricate FeTiTa-based and FeTiMo-based alloys. The phase composition and hydrogen storage properties of the samples were investigated. The samples modified with the refractory metals exhibited lower plateau pressures and lower hydrogen storage capacities than those of the FeTi reference sample due to solid solution formation. It was observed that the equilibrium pressures decreased with the amount of molybdenum which is in good agreement with the increase in the cell parameters of the TiFe phase. Suspended droplet alloying was found to be a practical method to fabricate alloys with refractory metal additions; however it is appropriate for screening samples with desired chemical and phase compositions rather than for manufacturing purposes.
Seasonal and Multi-Seasonal Energy Storage by Power-to-Methane Technology
Jun 2021
Publication
The time-range of applicability of various energy-storage technologies are limited by self-discharge and other inevitable losses. While batteries and hydrogen are useful for storage in a time-span ranging from hours to several days or even weeks for seasonal or multi-seasonal storage only some traditional and quite costly methods can be used (like pumped-storage plants Compressed Air Energy Storage or energy tower). In this paper we aim to show that while the efficiency of energy recovery of Power-to-Methane technology is lower than for several other methods due to the low self-discharge and negligible standby losses it can be a suitable and cost-effective solution for seasonal and multi-seasonal energy storage.
The Effect of Graphite Size on Hydrogen Absorption and Tensile Properties of Ferritic Ductile Cast Iron
Jun 2019
Publication
Ductile cast iron (DCI) is one of prospective materials used for the hydrogen equipment because of low-cost good workability and formability. The wide range of mechanical properties of DCI is obtained by controlling microstructural factors such as graphite size volume fraction of graphite matrix structure and so on. Therefore it is important to find out an optimal microstructural condition that is less susceptible to hydrogen embrittlement. In this study the effects of graphite size on the hydrogen absorption capability and the hydrogen-induced ductility loss of ferritic DCI were investigated.<br/>Several kinds of ferritic DCIs with a different graphite diameter of about 10 µm - 30 µm were used for the tensile test and the hydrogen content measurement. Hydrogen charging was performed prior to the tensile test by exposing a specimen to high-pressure hydrogen gas. Then the tensile test was performed in air at room temperature. The hydrogen content of a specimen was measured by a thermal desorption analyzer.<br/>It was found that the amount of hydrogen stored in DCI was dependent on the graphite size. As the graphite diameter increased the hydrogen content sharply increased at a certain graphite diameter and then it became nearly constant irrespective of increase in graphite diameter. In other words there was the critical graphite diameter that significantly changed the hydrogen absorption capability. The ductility was decreased by hydrogen and the hydrogen-induced ductility loss was dependent on the hydrogen content. Therefore the hydrogen embrittlement of DCI became remarkable when the graphite size was larger than the critical value.
Complex Methods of Estimation Technological Strength of Welded Joints in Welding at Low Temperatures
Feb 2021
Publication
A comprehensive methodology for estimating the technological strength of welded joints are developed based on parameters reflecting the welding technology weldability hydrogen force and deformation conditions for welding and other informative parameters that correlate with the characteristics of the welded joint as well as improving existing methods for estimating the technological strength of welded joints connections through the introduction of modern equipment and non-destructive testing systems. It has been established that the proposed comprehensive estimation methodology will allow reaching a new qualitative level in assessing the technological strength of a welded joint using modern equipment and measuring instruments. According to the results of the experimental work it was found that when welding at low temperatures the increase in the probability of the formation and development of cold cracks is mainly determined by the critical content of diffusible hydrogen in the weld metal depending on the structural and force parameters of the welded joints.
Unusual Hydrogen Implanted Gold with Lattice Contraction at Increased Hydrogen Content
Mar 2021
Publication
The experimental evidence for the contraction of volume of gold implanted with hydrogen at low doses is presented. The contraction of lattice upon the addition of other elements is very rare and extraordinary in the solid-state not only for gold but also for many other solids. To explain the underlying physics the pure kinetic theory of absorption is not adequate and the detailed interaction of hydrogen in the lattice needs to be clarified. Our analysis points to the importance of the formation of hydride bonds in a dynamic manner and explains why these bonds become weak at higher doses leading to the inverse process of volume expansion frequently seen in metallic hydrogen containers.
Hydrogen Embrittlement of Steel Pipelines During Transients
May 2021
Publication
Blending hydrogen into natural gas pipelines is a recent alternative adopted for hydrogen transportation as a mixture with natural gas. In this paper hydrogen embrittlement of steel pipelines originally designed for natural gas transportation is investigated. Solubility permeation and diffusion phenomena of hydrogen molecules into the crystalline lattice structure of the pipeline material are followed up based on transient evolution of internal pressure applied on the pipeline wall. The transient regime is created through changes of gas demand depending on daily consumptions. As a result the pressure may reach excessive values that lead to the acceleration of hydrogen solubility and its diffusion through the pipeline wall. Furthermore permeation is an important parameter to determine the diffusion amount of hydrogen inside the pipeline wall resulting in the embrittlement of the material. The numerical obtained results have shown that using pipelines designed for natural gas conduction to transport hydrogen is a risky choice. Actually added to overpressure and great fluctuations during transients that may cause fatigue and damage the structure also the latter pressure evolution is likely to induce the diffusion phenomena of hydrogen molecules into the lattice of the structure leading to brittle the pipe material. The numerical simulation reposes on solving partial differential equations describing transient gas flow in pipelines coupled with the diffusion equation for mass transfer. The model is built using the finite elements based software COMSOL Multiphysics considering different cases of pipe material; API X52 (base metal and nutrided) and API X80 steels. Obtained results allowed tracking the evolution with time of hydrogen concentration through the pipeline internal wall based on the pressure variation due to transient gas flow. Such observation permits to estimate the amount of hydrogen diffused in the metal to avoid leakage of this flammable gas. Thus precautions may be taken to prevent explosive risks due to hydrogen embrittlement of steel pipelines among other effects that can lead to alter safe conditions of gas conduction.
A Review of Recent Advances on the Effects of Microstructural Refinement and Nano-Catalytic Additives on the Hydrogen Storage Properties of Metal and Complex Hydrides
Dec 2010
Publication
The recent advances on the effects of microstructural refinement and various nano-catalytic additives on the hydrogen storage properties of metal and complex hydrides obtained in the last few years in the allied laboratories at the University of Waterloo (Canada) and Military University of Technology (Warsaw Poland) are critically reviewed in this paper. The research results indicate that microstructural refinement (particle and grain size) induced by ball milling influences quite modestly the hydrogen storage properties of simple metal and complex metal hydrides. On the other hand the addition of nanometric elemental metals acting as potent catalysts and/or metal halide catalytic precursors brings about profound improvements in the hydrogen absorption/desorption kinetics for simple metal and complex metal hydrides alike. In general catalytic precursors react with the hydride matrix forming a metal salt and free nanometric or amorphous elemental metals/intermetallics which in turn act catalytically. However these catalysts change only kinetic properties i.e. the hydrogen absorption/desorption rate but they do not change thermodynamics (e.g. enthalpy change of hydrogen sorption reactions). It is shown that a complex metal hydride LiAlH4 after high energy ball milling with a nanometric Ni metal catalyst and/or MnCl2 catalytic precursor is able to desorb relatively large quantities of hydrogen at RT 40 and 80 °C. This kind of behavior is very encouraging for the future development of solid state hydrogen systems.
Charpy Impact Properties of Hydrogen-Exposed 316L Stainless Steel at Ambient and Cryogenic Temperatures
May 2019
Publication
316L stainless steel is a promising material candidate for a hydrogen containment system. However when in contact with hydrogen the material could be degraded by hydrogen embrittlement (HE). Moreover the mechanism and the effect of HE on 316L stainless steel have not been clearly studied. This study investigated the effect of hydrogen exposure on the impact toughness of 316L stainless steel to understand the relation between hydrogen charging time and fracture toughness at ambient and cryogenic temperatures. In this study 316L stainless steel specimens were exposed to hydrogen in different durations. Charpy V-notch (CVN) impact tests were conducted at ambient and low temperatures to study the effect of HE on the impact properties and fracture toughness of 316L stainless steel under the tested temperatures. Hydrogen analysis and scanning electron microscopy (SEM) were conducted to find the effect of charging time on the hydrogen concentration and surface morphology respectively. The result indicated that exposure to hydrogen decreased the absorbed energy and ductility of 316L stainless steel at all tested temperatures but not much difference was found among the pre-charging times. Another academic insight is that low temperatures diminished the absorbed energy by lowering the ductility of 316L stainless steel
Large-scale Storage of Hydrogen
Mar 2019
Publication
The large-scale storage of hydrogen plays a fundamental role in a potential future hydrogen economy. Although the storage of gaseous hydrogen in salt caverns already is used on a full industrial scale the approach is not applicable in all regions due to varying geological conditions. Therefore other storage methods are necessary. In this article options for the large-scale storage of hydrogen are reviewed and compared based on fundamental thermodynamic and engineering aspects. The application of certain storage technologies such as liquid hydrogen methanol ammonia and dibenzyltoluene is found to be advantageous in terms of storage density cost of storage and safety. The variable costs for these high-density storage technologies are largely associated with a high electricity demand for the storage process or with a high heat demand for the hydrogen release process. If hydrogen is produced via electrolysis and stored during times of low electricity prices in an industrial setting these variable costs may be tolerable.
Modifications in the Composition of CuO/ZnO/Al2O3 Catalyst for the Synthesis of Methanol by CO2 Hydrogenation
Jun 2021
Publication
Renewable methanol obtained from CO2 and hydrogen provided from renewable energy was proposed to close the CO2 loop. In industry methanol synthesis using the catalyst CuO/ZnO/Al2O3 occurs at a high pressure. We intend to make certain modification on the traditional catalyst to work at lower pressure maintaining high selectivity. Therefore three heterogeneous catalysts were synthesized by coprecipitation to improve the activity and the selectivity to methanol under mild conditions of temperature and pressure. Certain modifications on the traditional catalyst Cu/Zn/Al2O3 were employed such as the modification of the synthesis time and the addition of Pd as a dopant agent. The most efficient catalyst among those tested was a palladium-doped catalyst 5% Pd/Cu/Zn/Al2O3. This had a selectivity of 64% at 210 °C and 5 bar.
Research Progress of Cryogenic Materials for Storage and Transportation of Liquid Hydrogen
Jul 2021
Publication
Liquid hydrogen is the main fuel of large-scale low-temperature heavy-duty rockets and has become the key direction of energy development in China in recent years. As an important application carrier in the large-scale storage and transportation of liquid hydrogen liquid hydrogen cryogenic storage and transportation containers are the key equipment related to the national defense security of China’s aerospace and energy fields. Due to the low temperature of liquid hydrogen (20 K) special requirements have been put forward for the selection of materials for storage and transportation containers including the adaptability of materials in a liquid hydrogen environment hydrogen embrittlement characteristics mechanical properties and thermophysical properties of liquid hydrogen temperature which can all affect the safe and reliable design of storage and transportation containers. Therefore it is of great practical significance to systematically master the types and properties of cryogenic materials for the development of liquid hydrogen storage and transportation containers. With the wide application of liquid hydrogen in different occasions the requirements for storage and transportation container materials are not the same. In this paper the types and applications of cryogenic materials commonly used in liquid hydrogen storage and transportation containers are reviewed. The effects of low-temperature on the mechanical properties of different materials are introduced. The research progress of cryogenic materials and low-temperature performance data of materials is introduced. The shortcomings in the research and application of cryogenic materials for liquid hydrogen storage and transportation containers are summarized to provide guidance for the future development of container materials. Among them stainless steel is the most widely used cryogenic material for liquid hydrogen storage and transportation vessel but different grades of stainless steel also have different applications which usually need to be comprehensively considered in combination with its low temperature performance corrosion resistance welding performance and other aspects. However with the increasing demand for space liquid hydrogen storage and transportation the research on high specific strength cryogenic materials such as aluminum alloy titanium alloy or composite materials is also developing. Aluminum alloy liquid hydrogen storage and transportation containers are widely used in the space field while composite materials have significant advantages in being lightweight. Hydrogen permeation is the key bottleneck of composite storage and transportation containers. At present there are still many technical problems that have not been solved.
Micro and Macro Mechanical Analysis of Gas Pipeline Steels
Sep 2017
Publication
The actual safety margins of gas pipelines depend on a number of factors that include the mechanical characteristics of the material. The evolution with time of the metal properties can be evaluated by mechanical tests performed at different scales seeking for the best compromise between the simplicity of the experimental setup to be potentially employed in situ and the reliability of the results. Possible alternatives are comparatively assessed on pipeline steels of different compositions and in different states.
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