Transmission, Distribution & Storage
Injecting Hydrogen into the Gas Network- A Literature Search
Jan 2015
Publication
Hydrogen injection into the GB gas network is a likely consequence of using excess offshore wind generated electricity to power large-scale onshore electrolysis plants. Government and DECC in particular now have a keen interest in supporting technologies that can take advantage of the continued use of the gas networks. HSE can contribute to the government’s Growth and Green agendas by effectively regulating and safely enabling this technology.
This report will allow HSE to regulate effectively by pulling together scientific and engineering knowledge regarding the hazards of conveying hydrogen/methane mixtures in network pipes and its use in consumer appliances into a single ‘state-of-play’ report. It enables Energy Division to consider and assess submissions for ‘gas quality’ exemptions to the Gas Safety (Management) Regulations 1996 (GSMR).
In particular the report has examined the following hazards:
This report will allow HSE to regulate effectively by pulling together scientific and engineering knowledge regarding the hazards of conveying hydrogen/methane mixtures in network pipes and its use in consumer appliances into a single ‘state-of-play’ report. It enables Energy Division to consider and assess submissions for ‘gas quality’ exemptions to the Gas Safety (Management) Regulations 1996 (GSMR).
In particular the report has examined the following hazards:
- conveyance of H2/CH4 mixtures in network pipes
- use of H2/CH4 mixtures in consumer appliances (domestic/commercial/industrial)
- explosion and damage characteristics (and ignition likelihood) of H2/CH4 mixtures
- effects on odourisation
Seasonal Energy Storage for Zero-emissions Multi-energy Systems Via Underground Hydrogen Storage
Jan 2020
Publication
The deployment of diverse energy storage technologies with the combination of daily weekly and seasonal storage dynamics allows for the reduction of carbon dioxide (CO2) emissions per unit energy provided. In particular the production storage and re-utilization of hydrogen starting from renewable energy has proven to be one of the most promising solutions for offsetting seasonal mismatch between energy generation and consumption. A realistic possibility for large-scale hydrogen storage suitable for long-term storage dynamics is presented by salt caverns. In this contribution we provide a framework for modelling underground hydrogen storage with a focus on salt caverns and we evaluate its potential for reducing the CO2 emissions within an integrated energy systems context. To this end we develop a first-principle model which accounts for the transport phenomena within the rock and describes the dynamics of the stored energy when injecting and withdrawing hydrogen. Then we derive a linear reduced order model that can be used for mixed-integer linear program optimization while retaining an accurate description of the storage dynamics under a variety of operating conditions. Using this new framework we determine the minimum-emissions design and operation of a multi-energy system with H2 storage. Ultimately we assess the potential of hydrogen storage for reducing CO2 emissions when different capacities for renewable energy production and energy storage are available mapping emissions regions on a plane defined by storage capacity and renewable generation. We extend the analysis for solar- and wind-based energy generation and for different energy demands representing typical profiles of electrical and thermal demands and different CO2 emissions associated with the electric grid.
Fast Synthesis of TiNi by Mechanical Alloying and its Hydrogenation Properties
Mar 2019
Publication
Mechanical alloying is widely used for the synthesis of hydrogen storage materials. However amorphization and contamination triggered by long-time milling are serious drawbacks for obtaining efficient hydrogen storage. In this work short-time ball milling synthesis is explored for a representative hydride forming compound: TiNi. Through structural morphological and chemical characterizations we evidence that formation of TiNi is complete in only 20 min with minor Fe contamination (0.2 wt%). Cross-sectional analysis of powder stuck on milling balls reveals that alloy formation occurs through the interdiffusion between thin layers of co-laminated pure elements. Hydrogenation thermodynamics and kinetics of short-time mechanically alloyed TiNi are similar to those of coarse-grained compounds obtained by classical high-temperature melting. Mechanical alloying is a suitable method for fast and energy-efficient synthesis of intermetallic compounds such as TiNi.
Isotopic Tracing of Hydrogen Transport and Trapping in Nuclear Materials
Jun 2017
Publication
Some illustrations of the use of deuterium or tritium for isotopic tracing of hydrogen absorption transport and trapping in nuclear materials are presented. Isotopic tracing of hydrogen has been shown to be successful for the determination of the boundaries conditions for hydrogen desorption or absorption in a material exposed to a hydrogen source. Also the unique capabilities of isotopic tracing and related techniques to characterize H interactions with point defects and dislocations acting as moving traps has been demonstrated. Such transport mechanisms are considered to play a major role in some stress corrosion cracking and hydrogen embrittlement mechanisms.
Link to document download on Royal Society Website
Link to document download on Royal Society Website
Concepts for Improving Hydrogen Storage in Nanoporous Materials
Feb 2019
Publication
Hydrogen storage in nanoporous materials has been attracting a great deal of attention in recent years as high gravimetric H2 capacities exceeding 10 wt% in some cases can be achieved at 77 K using materials with particularly high surface areas. However volumetric capacities at low temperatures and both gravimetric and volumetric capacities at ambient temperature need to be improved before such adsorbents become practically viable. This article therefore discusses approaches to increasing the gravimetric and volumetric hydrogen storage capacities of nanoporous materials and maximizing the usable capacity of a material between the upper storage and delivery pressures. In addition recent advances in machine learning and data science provide an opportunity to apply this technology to the search for new materials for hydrogen storage. The large number of possible component combinations and substitutions in various porous materials including Metal-Organic Frameworks (MOFs) is ideally suited to a machine learning approach; so this is also discussed together with some new material types that could prove useful in the future for hydrogen storage applications.
Stress Corrosion Cracking of Gas Pipeline Steels of Different Strength
Jul 2016
Publication
With the development of the natural gas industry gas transmission pipelines have been developed rapidly in terms of safety economy and efficiency. Our recent studies have shown that an important factor of main pipelines serviceability loss under their long-term service is the in-bulk metal degradation of the pipe wall. This leads to the loss of the initial mechanical properties primarily resistance to brittle fracture which were set in engineering calculations at the pipeline design stage. At the same time stress corrosion cracking has been identified as one of the predominant failures in pipeline steels in humid environments which causes rupture of high-pressure gas transmission pipes as well as serious economic losses and disasters.
In the present work the low-carbon pipeline steels with different strength levels from the point of view of their susceptibility to stress corrosion cracking in the as-received state and after in-laboratory accelerated degradation under environmental conditions similar to those of an acidic soil were investigated. The main objectives of this study were to determine whether the development of higher strength materials led to greater susceptibility to stress corrosion cracking and whether degraded pipeline steels became more susceptible to stress corrosion cracking than in the as-received state. The procedure of accelerated degradation of pipeline steels was developed and introduced in laboratory under the combined action of axial loading and hydrogen charging. It proved to be reliable and useful to performed laboratory simulation of in-service degradation of pipeline steels with different strength. The in-laboratory degraded 17H1S and X60 pipeline steels tested in the NS4 solution saturated with CO2 under open circuit potential revealed the susceptibility to stress corrosion cracking reflected in the degradation of mechanical properties and at the same time the degraded X60 steel showed higher resistance to stress corrosion cracking than the degraded 17H1S steel. Fractographic observation confirmed the pipeline steels hydrogen embrittlement caused by the permeated hydrogen.
In the present work the low-carbon pipeline steels with different strength levels from the point of view of their susceptibility to stress corrosion cracking in the as-received state and after in-laboratory accelerated degradation under environmental conditions similar to those of an acidic soil were investigated. The main objectives of this study were to determine whether the development of higher strength materials led to greater susceptibility to stress corrosion cracking and whether degraded pipeline steels became more susceptible to stress corrosion cracking than in the as-received state. The procedure of accelerated degradation of pipeline steels was developed and introduced in laboratory under the combined action of axial loading and hydrogen charging. It proved to be reliable and useful to performed laboratory simulation of in-service degradation of pipeline steels with different strength. The in-laboratory degraded 17H1S and X60 pipeline steels tested in the NS4 solution saturated with CO2 under open circuit potential revealed the susceptibility to stress corrosion cracking reflected in the degradation of mechanical properties and at the same time the degraded X60 steel showed higher resistance to stress corrosion cracking than the degraded 17H1S steel. Fractographic observation confirmed the pipeline steels hydrogen embrittlement caused by the permeated hydrogen.
In Situ Formed Ultrafine Metallic Ni from Nickel (II) Acetylacetonate Precursor to Realize an Exceptional Hydrogen Storage Performance of MgH2–Ni-EG Nanocomposite
Dec 2021
Publication
It has been well known that doping nano-scale catalysts can significantly improve both the kinetics and reversible hydrogen storage capacity of MgH2. However so far it is still a challenge to directly synthesize ultrafine catalysts (e.g. < 5 nm) mainly because of the complicated chemical reaction processes. Here a facile one-step high-energy ball milling process is developed to in situ form ultrafine Ni nanoparticles from the nickel acetylacetonate precursor in the MgH2 matrix. With the combined action of ultrafine metallic Ni and expanded graphite (EG) the formed MgH2–Ni-EG nanocomposite with the optimized doping amounts of Ni and EG can still release 7.03 wt.% H2 within 8.5 min at 300 °C after 10 cycles. At a temperature close to room temperature (50 °C) it can also absorb 2.42 wt.% H2 within 1 h It can be confirmed from the microstructural characterization analysis that the in situ formed ultrafine metallic Ni is transformed into Mg2Ni/Mg2NiH4 in the subsequent hydrogen absorption and desorption cycles. It is calculated that the dehydrogenation activation energy of the MgH2–Ni-EG nanocomposite is also reduced obviously in comparison with the pure MgH2. Our work provides a methodology to significantly improve the hydrogen storage performance of MgH2 by combining the in situ formed and uniformly dispersed ultrafine metallic catalyst from the precursor and EG.
Model of Local Hydrogen Permeability in Stainless Steel with Two Coexisting Structures
Apr 2021
Publication
The dynamics of hydrogen in metals with mixed grain structure is not well understood at a microscopic scale. One of the biggest issues facing the hydrogen economy is “hydrogen embrittlement” of metal induced by hydrogen entering and diffusing into the material. Hydrogen diffusion in metallic materials is difficult to grasp owing to the non-uniform compositions and structures of metal. Here a time-resolved “operando hydrogen microscope” was used to interpret local diffusion behaviour of hydrogen in the microstructure of a stainless steel with austenite and martensite structures. The martensite/austenite ratios differed in each local region of the sample. The path of hydrogen permeation was inferred from the time evolution of hydrogen permeation in several regions. We proposed a model of hydrogen diffusion in a dual-structure material and verified the validity of the model by simulations that took into account the transfer of hydrogen at the interfaces.
Unconventional Pearlitic Pseudocolonies Affecting Macro-, Micro- and Nano-structural Integrity of Cold-drawn Pearlitic Steel Wires: Resembling van Gogh, Bernini, Mantegna and Picasso
Dec 2020
Publication
Prestressing steel wires are manufactured by cold drawing during which a preferential orientation is achieved in the matter of pearlitic colonies and lamellae. In addition to this general trend special (unconventional) pearlitic pseudocolonies evolve during the heavy-drawing manufacture process affecting the posterior macro- micro- and nano-structural integrity of the material. This paper discusses the important role of such a special microstructural unit (the pearlitic pseudocolony) in the fracture process in air (inert) environment in the presence of crack-like defects as well as in the case of environmentally assisted cracking (stress corrosion cracking by localized anodic dissolution) or hydrogen embrittlement. Results clearly demonstrate the key role of pearlitic pseudocolonies in promoting crack deflection (and thus mixed-mode propagation) after a global mode I cracking especially in the case of fracture in air and stress corrosion cracking.
Fractographic Features of Long Term Operated Gas Pipeline Steels Fracture Under Impact Loading
Jan 2020
Publication
Pipelines during their service life subjected to operational degradation i.e. their mechanical characteristics worsened with time. Pronounced texture of pipe steels associated with their manufacturing process revealed itself in an essential difference in impact toughness determined for specimens cut in mutually perpendicular directions with respect to the pipe axis. Higher KCV values for longitudinal specimens as compared with transverse ones were explained by the difference in a length of perlite grain strips separated by ferrite grains in specimens of different orientation. A role of hydrogen absorbed my metal during its operation in steel degradation was discussed.<br/>The main fractographic peculiarity for the operated steels comparing to the steels in the initial state is the appearance of delamination on the fracture surfaces which are oriented in the rolling direction. Correlation was found for the tested steels between fractographic sings of their embrittlement due to operational degradation and their loss of brittle fracture resistance. It is concluded that a decrease of impact toughness caused by long term operation of pipeline steels is definitely concerned with the amount of delamination on the fracture surfaces.
Stress Corrosion Behavior of AM50Gd Magnesium Alloy in Different Environments
May 2019
Publication
A new type of high strength corrosion-resistant magnesium alloy was prepared by adding 1% rare earth Gd to AM50 and then treated with hot extrusion method. The stress corrosion properties of the new materials in air pure water 0.5 mol/L NaCl and 0.5 mol/L Na2SO4 solution were studied by the slow strain rate tensile (SSRT) test in situ open circuit potential test Tafel curve test stereomicroscope SEM and EDS. The results showed the following. The stress corrosion sensitivity of the material in different environments was Na2SO4> NaCl > distilled water > air. According to the Tafel curves measured at 0 and 100 MPa the corrosion voltage decreased little and the corrosion current density increased rapidly under 100 Pa. This was because the film of the corrosion product ruptured to form a large cathode and a small anode which resulted in a large instantaneous corrosion current. The mechanism of hydrogen embrittlement and anodic dissolution together affected the stress corrosion behavior of the alloy. In distilled water hydrogen embrittlement played a major role while in NaCl and Na2SO4solution hydrogen embrittlement and anodic dissolution were both affected. The direct reason of the stress corrosion crack (SCC) samples’ failure was the cracks expanding rapidly at the bottom of pit which was caused by corrosion.
Blue Hydrogen as an Enabler of Green Hydrogen: The Case of Germany
Jun 2020
Publication
In Germany decarbonization of the electricity sector by fostering renewables and now phasing out coal-fired power is on track to reach the 2050 de-carbonisation targets while decarbonising non-electric energy consumption is proving to be more difficult. The present discussion of a national hydrogen strategy has run into strong political opposition against carbon sequestration as a necessary element in the use of decarbonized natural gas (blue hydrogen) and is aiming at the use of green hydrogen only (from renewable electricity and electrolysis). This paper shows that as long as the power sector is not decarbonized – not likely before 2040 – only marginal volumes of renewable electricity will be available to produce green hydrogen. To meet the decarbonization target by 2050 blue hydrogen has to fill that gap paving the way for green hydrogen at a later stage. The paper discusses the elements needed for an expedient development of blue hydrogen. It also points at the need and instruments to decarbonize core industries like the steel and chemical industry so that they can become future proof in competition with the US which is more advanced with a decarbonization strategy for its industry based on carbon sequestration.
Absence of Spillover of Hydrogen Adsorbed on Small Palladium Clusters Anchored to Graphene Vacancies
May 2021
Publication
Experimental evidence exists for the enhancement of the hydrogen storage capacity of porous carbons when these materials are doped with metal nanoparticles. One of the most studied dopants is palladium. Dissociation of the hydrogen molecules and spillover of the H atoms towards the carbon substrate has been advocated as the reason for the enhancement of the storage capacity. We have investigated this mechanism by performing ab initio density functional molecular dynamics (AIMD) simulations of the deposition of molecular hydrogen on Pd6 clusters anchored on graphene vacancies. The clusters are initially near-saturated with atomic and molecular hydrogen. This condition would facilitate the occurrence of spillover since our energy calculations based on density functional theory indicate that migration of preadsorbed H atoms towards the graphene substrate becomes exothermic on Pd clusters with high hydrogen coverages. However AIMD simulations show that the H atoms prefer to intercalate and absorb within the Pd cluster rather than migrate to the carbon substrate. These results reveal that high activation barriers exist preventing the spillover of hydrogen from the anchored Pd clusters to the carbon substrate.
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.
Green Synthesis of Olefin-linked Covalent Organic Frameworks for Hydrogen Fuel Cell Applications
Mar 2021
Publication
Green synthesis of crystalline porous materials for energy-related applications is of great significance but very challenging. Here we create a green strategy to fabricate a highly crystalline olefin-linked pyrazine-based covalent organic framework (COF) with high robustness and porosity under solvent-free conditions. The abundant nitrogen sites high hydrophilicity and well-defined one-dimensional nanochannels make the resulting COF an ideal platform to confine and stabilize the H3PO4 network in the pores through hydrogen-bonding interactions. The resulting material exhibits low activation energy (Ea) of 0.06 eV and ultrahigh proton conductivity across a wide relative humidity (10–90 %) and temperature range (25–80 °C). A realistic proton exchange membrane fuel cell using the olefin-linked COF as the solid electrolyte achieve a maximum power of 135 mW cm−2 and a current density of 676 mA cm−2 which exceeds all reported COF materials.
Optimisation-based System Designs for Deep Offshore Wind Farms including Power to Gas Technologies
Feb 2022
Publication
A large deployment of energy storage solutions will be required by the stochastic and non-controllable nature of most renewable energy sources when planning for higher penetration of renewable electricity into the energy mix. Various solutions have been suggested for dealing with medium- and long-term energy storage. Hydrogen and ammonia are two of the most frequently discussed as they are both carbon-free fuels. In this paper the authors analyse the energy and cost efficiency of hydrogen and ammonia-based pathways for the storage transportation and final use of excess electricity from an offshore wind farm. The problem is solved as a linear programming problem simultaneously optimising the size of each problem unit and the respective time-dependent operational conditions. As a case study we consider an offshore wind farm of 1.5 GW size located in a reference location North of Scotland. The energy efficiency and cost of the whole chain are evaluated and compared with competitive alternatives namely batteries and liquid hydrogen storage. The results show that hydrogen and ammonia storage can be part of the optimal solution. Moreover their use for long-term energy storage can provide a significant cost-effective contribution to an extensive penetration of renewable energy sources in national energy systems.
Analysis of Stress Corrosion Cracking in X80 Pipeline Steel: An Approach from the Theory of Critical Distances
Dec 2018
Publication
This paper presents an analysis of Stress Corrosion Cracking (SCC) based on the Theory of Critical Distances (TCD). The research is based on an experimental program composed of fracture specimens with notch radius varying from 0 mm (crack-like defect) up to 1 mm and tensile specimens. A pipeline steel was used in this work (X80). It has been analysed in one hydrogen embrittlement situation. The study has been completed with Finite Elements Simulation analysis. The capacity of the TCD to analyse SCC processes has been proven.
Failure Analysis of Cooling Duct of Top Engine Cowl Panel of Fighter Aircraft
Jun 2019
Publication
Present work describes the failure analysis of cooling duct of a fighter aircraft. The analyzed chemical composition of cooling duct indicates that it is manufactured from Al-based alloy (AA 3003 or its equivalent). Microstructure of cooling duct displays the presence of two phases namely matrix and insoluble particles. The hardness values at different locations within damaged area of cooling duct reflect nearly same and consistent. The fracture surface of the cooling duct exhibits transgranular features and cracks with little branching. The analyzed hydrogen content in cooling duct is significantly higher (∼ 12 ppm) than the specified one (< 1 ppm). However the alloy used to fabricate cooling duct is not susceptible to typical hydrogen embrittlement. This shows hydrogen pick up during operation. The presence of cracks with branching does reflect features of hydrogen embrittlement. In addition striations indicative of fatigue features are also observed. It thus appears that the cooling duct has failed due to pick up of large amount of hydrogen as well as vibrational fatigue.
On the Concept of Micro-fracture Map (MFM) and its Role in Structural Integrity Evaluations in Materials Science and Engineering: A Tribute to Jorge Manrique
Dec 2020
Publication
This paper deals with the concept of micro-fracture map (MFM) and its role in structural integrity evaluations in materials science and engineering on the basis of previous research by the author on notch-induced fracture and hydrogen embrittlement of progressively cold drawn pearlitic steels and 316L austenitic stainless steel. With regard to this some examples are provided of assembly of MFMs in particular situations.
Nonlinear Model Predictive Control of an Autonomous Power System Based on Hydrocarbon Reforming and High Temperature Fuel Cell
Mar 2021
Publication
The integration and control of energy systems for power generation consists of multiple heterogeneous subsystems such as chemical electrochemical and thermal and contains challenges that arise from the multi-way interactions due to complex dynamic responses among the involved subsystems. The main motivation of this work is to design the control system for an autonomous automated and sustainable system that meets a certain power demand profile. A systematic methodology for the integration and control of a hybrid system that converts liquefied petroleum gas (LPG) to hydrogen which is subsequently used to generate electrical power in a high-temperature fuel cell that charges a Li-Ion battery unit is presented. An advanced nonlinear model predictive control (NMPC) framework is implemented to achieve this goal. The operational objective is the satisfaction of power demand while maintaining operation within a safe region and ensuring thermal and chemical balance. The proposed NMPC framework based on experimentally validated models is evaluated through simulation for realistic operation scenarios that involve static and dynamic variations of the power load.
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