Safety
Hydrogeochemical Modeling to Identify Potential Risks of Underground Hydrogen Storage in Depleted Gas Fields
Nov 2018
Publication
Underground hydrogen storage is a potential way to balance seasonal fluctuations in energy production from renewable energies. The risks of hydrogen storage in depleted gas fields include the conversion of hydrogen to CH4(g) and H2S(g) due to microbial activity gas–water–rock interactions in the reservoir and cap rock which are connected with porosity changes and the loss of aqueous hydrogen by diffusion through the cap rock brine. These risks lead to loss of hydrogen and thus to a loss of energy. A hydrogeochemical modeling approach is developed to analyze these risks and to understand the basic hydrogeochemical mechanisms of hydrogen storage over storage times at the reservoir scale. The one-dimensional diffusive mass transport model is based on equilibrium reactions for gas–water–rock interactions and kinetic reactions for sulfate reduction and methanogenesis. The modeling code is PHREEQC (pH-REdox-EQuilibrium written in the C programming language). The parameters that influence the hydrogen loss are identified. Crucial parameters are the amount of available electron acceptors the storage time and the kinetic rate constants. Hydrogen storage causes a slight decrease in porosity of the reservoir rock. Loss of aqueous hydrogen by diffusion is minimal. A wide range of conditions for optimized hydrogen storage in depleted gas fields is identified.
Modelling of Ventilated Hydrogen Dispersion in Presence of Co-flow and Counter-flow
Sep 2021
Publication
In the framework of the EU-funded project HyTunnel-CS an inter-comparison among partners CFD simulations has been carried out. The simulations are based on experiments conducted within the project by Pro-Science and involve hydrogen release inside a safety vessel testing different ventilation configurations. The different ventilation configurations that were tested are co-flow counter-flow and cross-flow. In the current study co-flow and counter-flow tests along with the no ventilation test (m' = S g/s d = 4 mm ) are simulated with the aim to validate available and well-known CFD codes against such applications and to provide recommendations on modeling strategies. Special focus is given on modeling the velocity field produced by the fan during the experiments. The computational results are compared with the experimental results and a discussion follows regarding the efficiency of each ventilation configuration.
Velocity Measurements of Hydrogen Jets Using the Optical Flow Method
Sep 2021
Publication
Concentration and velocity measurements are crucial for developing and validating hydrogen jet models which provide scientific bases for hydrogen safety analyses. The concentration fields have been visualized and accurately measured using laser diagnostic methods based on lase Rayleigh and Raman scattering techniques. However the velocity measurements are more challenging. Particle image velocimetry (PIV) has been commonly used for measuring velocities in turbulent flows by seeding tracer particles into the flow and assuming the particles intimately following the flow. However sometimes the particle seeding is difficult or disturbs the flow. Moreover simultaneously concentration and velocity measurements are very difficult when using PIV systems to measure the velocities. Therefore the optical flow velocimetry (OFV) method was used to resolve the velocity fields from the scalar fields or particle images of hydrogen jets. In the present work the velocity field and particle images of hydrogen jets were simulated using FLUENT with the large eddy simulation (LES) model and the particle images were then used to resolve the velocity field by the OFV method. The OFV results were compared with the CFD simulations to verify their accuracy. The results show that the OFC method was an efficient low-cost way to extract the velocity fields from particle images. The OFV method accurately located the large vortices in the flow and the velocity distribution of the high-velocity gradients regions was consistent with the CFD results. The present study lays a foundation for using the OFV method to directly resolve the velocity fields from the concentration fields of hydrogen jets measured by laser diagnostics.
An Investigation into the Volumetric Flow Rate Requirement of Hydrogen Transportation in Existing Natural Gas Pipelines and Its Safety Implications
Oct 2021
Publication
As an alternative to the construction of new infrastructure repurposing existing natural gas pipelines for hydrogen transportation has been identified as a low-cost strategy for substituting natural gas with hydrogen in the wake of the energy transition. In line with that a 342 km 3600 natural gas pipeline was used in this study to simulate some technical implications of delivering the same amount of energy with different blends of natural gas and hydrogen and with 100% hydrogen. Preliminary findings from the study confirmed that a three-fold increase in volumetric flow rate would be required of hydrogen to deliver an equivalent amount of energy as natural gas. The effects of flowing hydrogen at this rate in an existing natural gas pipeline on two flow parameters (the compressibility factor and the velocity gradient) which are crucial to the safety of the pipeline were investigated. The compressibility factor behaviour revealed the presence of a wide range of values as the proportions of hydrogen and natural gas in the blends changed signifying disparate flow behaviours and consequent varying flow challenges. The velocity profiles showed that hydrogen can be transported in natural gas pipelines via blending with natural gas by up to 40% of hydrogen in the blend without exceeding the erosional velocity limits of the pipeline. However when the proportion of hydrogen reached 60% the erosional velocity limit was reached at 290 km so that beyond this distance the pipeline would be subject to internal erosion. The use of compressor stations was shown to be effective in remedying this challenge. This study provides more insights into the volumetric and safety considerations of adopting existing natural gas pipelines for the transportation of hydrogen and blends of hydrogen and natural gas.
Risk Assessment Method Combining Independent Protection Layers (IPL) of Layer of Protection Analysis (LOPA) and RISKCURVES Software: Case Study of Hydrogen Refueling Stations in Urban Areas
Jul 2021
Publication
The commercialization of eco-friendly hydrogen vehicles has elicited attempts to expand hydrogen refueling stations in urban areas; however safety measures to reduce the risk of jet fires have not been established. The RISKCURVES software was used to evaluate the individual and societal risks of hydrogen refueling stations in urban areas and the F–N (Frequency–Number of fatalities) curve was used to compare whether the safety measures satisfied international standards. From the results of the analysis it was found that there is a risk of explosion in the expansion of hydrogen refueling stations in urban areas and safety measures should be considered. To lower the risk of hydrogen refueling stations this study applied the passive and active independent protection layers (IPLs) of LOPA (Layer of Protection Analysis) and confirmed that these measures significantly reduced societal risk as well as individual risk and met international standards. In particular such measures could effectively reduce the impact of jet fire in dispensers and tube trailers that had a high risk. Measures employing both IPL types were efficient in meeting international standard criteria; however passive IPLs were found to have a greater risk reduction effect than active IPLs. The combination of RISKCURVES and LOPA is an appropriate risk assessment method that can reduce work time and mitigate risks through protective measures compared to existing risk assessment methods. This method can be applied to risk assessment and risk mitigation not only for hydrogen facilities but also for hazardous materials with high fire or explosion risk.
Liquid Organic Hydrogen Carriers - A Technology to Overcome Common Risks of Hydrogen Storage
Sep 2021
Publication
In transport and storage of hydrogen the risks are mainly seen in its volatile nature its ability to form explosive mixtures with air and the harsh conditions (high pressure or low temperature) for efficient storage. The concept of Liquid Organic Hydrogen Carriers (LOHC) offers a technology to overcome the above mentioned threats. The present submission describes the basics of the LOHC technology. It contains a comparison of a selection of common LOHC materials with a view on physical properties. The advantages of a low viscosity at low temperatures and a high flash point are expressed. LOHCs are also discussed as a concept to import large amounts of energy/hydrogen. A closer look is taken on the environmental and safety aspects of hydrogen storage in LOHCs since here the main differences to pressurized and cryo-storage of hydrogen can be found. The aim of this paper is to provide an overview of the principles of the LOHC technology the different LOHC materials and their risks and opportunities and an impression of a large scale scenario on the basis of the LOHC technology.
Hydrogen as a Maritime Fuel–Can Experiences with LNG Be Transferred to Hydrogen Systems?
Jul 2021
Publication
As the use of fossil fuels becomes more and more restricted there is a need for alternative fuels also at sea. For short sea distance travel purposes batteries may be a solution. However for longer distances when there is no possibility of recharging at sea batteries do not have sufficient capacity yet. Several projects have demonstrated the use of compressed hydrogen (CH2) as a fuel for road transport. The experience with hydrogen as a maritime fuel is very limited. In this paper the similarities and differences between liquefied hydrogen (LH2) and liquefied natural gas (LNG) as a maritime fuel will be discussed based on literature data of their properties and our system knowledge. The advantages and disadvantages of the two fuels will be examined with respect to use as a maritime fuel. Our objective is to discuss if and how hydrogen could replace fossil fuels on long distance sea voyages. Due to the low temperature of LH2 and wide flammability range in air these systems have more challenges related to storage and processing onboard than LNG. These factors result in higher investment costs. All this may also imply challenges for the LH2 supply chain.
Flammability Reduction in a Pressurised Water Electrolyser Based on a Thin Polymer Electrolyte Membrane through a Pt-alloy Catalytic Approach
Jan 2019
Publication
Various Pt-based materials (unsupported Pt PtRu PtCo) were investigated as catalysts for recombining hydrogen and oxygen back into water. The recombination performance correlated well with the surface Pt metallic state. Alloying cobalt to platinum was observed to produce an electron transfer favouring the occurrence of a large fraction of the Pt metallic state on the catalyst surface. Unsupported PtCo showed both excellent recombination performance and dynamic behaviour. In a packed bed catalytic reactor when hydrogen was fed at 4% vol. in the oxygen stream (flammability limit) 99.5% of the total H2 content was immediately converted to water in the presence of PtCo thus avoiding safety issues. The PtCo catalyst was thus integrated in the anode of the membrane-electrode assembly of a polymer electrolyte membrane electrolysis cell. This catalyst showed good capability to reduce the concentration of hydrogen in the oxygen stream under differential pressure operation (1–20 bar) in the presence of a thin (90 μm) Aquivion® membrane. The modified system showed lower hydrogen concentration in the oxygen flow than electrolysis cells based on state-of-the-art thick polymer electrolyte membranes and allowed to expand the minimum current density load down to 0.15 A cm−2 . This was mainly due to the electrochemical oxidation of permeated H2 to protons that were transported back to the cathode. The electrolysis cell equipped with a dual layer PtCo/IrRuOx oxidation catalyst achieved a high operating current density (3 A cm−2 ) as requested to decrease the system capital costs under high efficiency conditions (about 77% efficiency at 55 °C and 20 bar). Moreover the electrolysis system showed reduced probability to reach the flammability limit under both high differential pressure (20 bar) and partial load operation (5%) as needed to properly address grid-balancing service
Safety Standard for Hydrogen and Hydrogen Systems Guidelines for Hydrogen System Design, Materials Selection, Operations, Storage and Transportation
Jan 1997
Publication
The NASA Safety Standard which establishes a uniform process for hydrogen system design materials selection operation storage and transportation is presented. The guidelines include suggestions for safely storing handling and using hydrogen in gaseous (GH2) liquid (LH2) or slush (SLH2) form whether used as a propellant or non-propellant. The handbook contains 9 chapters detailing properties and hazards facility design design of components materials compatibility detection and transportation. Chapter 10 serves as a reference and the appendices contained therein include: assessment examples; scaling laws explosions blast effects and fragmentation; codes standards and NASA directives; and relief devices along with a list of tables and figures abbreviations a glossary and an index for ease of use. The intent of the handbook is to provide enough information that it can be used alone but at the same time reference data sources that can provide much more detail if required.
CFD Simulations of Large Scale LH2 Dispersion in Open Environment
Sep 2021
Publication
An inter-comparison among partners’ CFD simulations has been carried out within the EU-funded project PRESLHY to investigate the dispersion of the mixture cloud formed from large scale liquid hydrogen release. Rainout experiments performed by Health and Safety Executive (HSE) have been chosen for the work. From the HSE experimental series trial-11 was selected forsimulation due to its conditions where only liquid flow at the nozzle was achieved. During trial-11 liquid hydrogen is spilled horizontally 0.5 m above a concrete pad from a 5 barg tank pressure through a 12 mm (1/2 inch) nozzle. The dispersion takes place outdoors and thus it is imposed to variant wind conditions. Comparison of the CFD results with the measurements at several sensors is presented and useful conclusions are drawn.
Advanced Polymeric/inorganic Nanohybrids: An Integrated Platform for Gas Sensing Applications
Jan 2022
Publication
Rapid industrial development vehicles domestic activities and mishandling of garbage are the main sources of pollutants which are destroying the atmosphere. There is a need to continuously monitor these pollutants for the safety of the environment and human beings. Conventional instruments for monitoring of toxic gases are expensive bigger in size and time-consuming. Hybrid materials containing organic and inorganic components are considered potential candidates for diverse applications including gas sensing. Gas sensors convert the information regarding the analyte into signals. Various polymeric/inorganic nanohybrids have been used for the sensing of toxic gases. Composites of different polymeric materials like polyaniline (PANI) poly (4-styrene sulfonate) (PSS) poly (34-ethylene dioxythiophene) (PEDOT) etc. with various metal/metal oxide nanoparticles have been reported as sensing materials for gas sensors because of their unique redox features conductivity and facile operation at room temperature. Polymeric nanohybrids showed better performance because of the larger surface area of nanohybrids and the synergistic effect between polymeric and inorganic materials. This review article focuses on the recent developments of emerging polymeric/inorganic nanohybrids for sensing various toxic gases including ammonia hydrogen nitrogen dioxide carbon oxides and liquefied petroleum gas. Advantages disadvantages operating conditions and prospects of hybrid composites have also been discussed.
Hy4Heat Annex To Site Specific Safety Case for Hydrogen Community Demonstration - Work Package 7
May 2021
Publication
The Hy4Heat Safety Assessment has focused on assessing the safe use of hydrogen gas in certain types of domestic properties and buildings. The summary reports (the Precis and the Safety Assessment Conclusions Report) bring together all the findings of the work and should be looked to for context by all readers. The technical reports should be read in conjunction with the summary reports. While the summary reports are made as accessible as possible for general readers the technical reports may be most accessible for readers with a degree of technical subject matter understanding. All of the safety assessment reports have now been reviewed by the HSE<br/>Annex prepared to support Site Specific Safety Cases for hydrogen gas community demonstrations based on work undertaken by the Hy4Heat programme. It covers a collection of recommended risk reduction measures for application downstream of the Emergency Control Valve (ECV)
Fundamentals and Principles of Solid-State Electrochemical Sensors for High Temperature Gas Detection
Dec 2021
Publication
The rapid development of science technology and engineering in the 21st century has offered a remarkable rise in our living standards. However at the same time serious environmental issues have emerged such as acid rain and the greenhouse effect which are associated with the ever-increasing need for energy consumption 85% of which comes from fossil fuels combustion. From this combustion process except for energy the main greenhouse gases-carbon dioxide and steam-are produced. Moreover during industrial processes many hazardous gases are emitted. For this reason gas-detecting devices such as electrochemical gas sensors able to analyze the composition of a target atmosphere in real time are important for further improving our living quality. Such devices can help address environmental issues and inform us about the presence of dangerous gases. Furthermore as non-renewable energy sources run out there is a need for energy saving. By analyzing the composition of combustion emissions of automobiles or industries combustion processes can be optimized. This review deals with electrochemical gas sensors based on solid oxide electrolytes which are employed for the detection of hazardous gasses at high temperatures and aggressive environments. The fundamentals the principle of operation and the configuration of potentiometric amperometric combined (amperometric-potentiometric) and mixed-potential gas sensors are presented. Moreover the results of previous studies on carbon oxides (COx) nitrogen oxides (NOx) hydrogen (H2 ) oxygen (O2 ) ammonia (NH3 ) and humidity (steam) electrochemical sensors are reported and discussed. Emphasis is given to sensors based on oxygen ion and proton-conducting electrolytes.
ZnO@ZIF-8 Core-Shell Structure Gas Sensors with Excellent Selectivity to H2
Jun 2021
Publication
As the energy crisis becomes worse hydrogen as a clean energy source is more and more widely used in industrial production and people’s daily life. However there are hidden dangers in hydrogen storage and transportation because of its flammable and explosive features. Gas detection is the key to solving this problem. High quality sensors with more practical and commercial value must be able to accurately detect target gases in the environment. Emerging porous metal-organic framework (MOF) materials can effectively improve the selectivity of sensors as a result of high surface area and coordinated pore structure. The application of MOFs for surface modification to improve the selectivity and sensitivity of metal oxides sensors to hydrogen has been widely investigated. However the influence of MOF modified film thickness on the selectivity of hydrogen sensors is seldom studied. Moreover the mechanism of the selectivity improvement of the sensors with MOF modified film is still unclear. In this paper we prepared nano-sized ZnO particles by a homogeneous precipitation method. ZnO nanoparticle (NP) gas sensors were prepared by screen printing technology. Then a dense ZIF-8 film was grown on the surface of the gas sensor by hydrothermal synthesis. The morphology the composition of the elements and the characters of the product were analyzed by X-ray diffraction analysis (XRD) transmission electron microscope (TEM) scanning electron microscope (SEM) energy dispersive spectrometer (EDS) Brunauer-Emmett-Teller (BET) and differential scanning calorimetry (DSC). It is found that the ZIF-8 film grown for 4 h cannot form a dense core-shell structure. The thickness of ZIF-8 reaches 130 nm at 20 h. Through the detection and analysis of hydrogen (1000 ppm) ethanol (100 ppm) and acetone (50 ppm) from 150 °C to 290 °C it is found that the response of the ZnO@ZIF-8 sensors to hydrogen has been significantly improved while the response to ethanol and acetone was decreased. By comparing the change of the response coefficient when the thickness of ZIF-8 is 130 nm the gas sensor has a significantly improved selectivity to hydrogen at 230 °C. The continuous increase of the thickness tends to inhibit selectivity. The mechanism of selectivity improvement of the sensors with different thickness of the ZIF-8 films is discussed.
CFD Model Based Ann Prediction of Flammable Vapor Colour Formed by Liquid Hydrogen Spill
Sep 2021
Publication
Unintended releases can occur during the production storage transportation and filling of liquid hydrogen which may cause devastating consequences. In the present work liquid hydrogen leak is modeled in ANSYS Fluent with the numerical model validated using the liquid hydrogen spill test data. A three-layer artificial neural network (ANN) model is built in which the wind speed ground temperature leakage time and leakage rate are taken as the inputs the horizontal diffusion distance and vertical diffusion distance of combustible gas as the outputs of the ANN. The representative sample data derived from the detailed calculation results of the numerical model are selected via the orthogonal experiment method to train and verify the back propagation (BP) neural network. Comparing the calculation results of the formula fitting with the sample data the results show that the established ANN model can quickly and accurately predict the horizontal and vertical diffusion distance of flammable vapor cloud relatively. The influences of four parameters on the horizontal hazard distance as well as vertical hazard height are predicted and analyzed in the case of continuous overflow of liquid hydrogen using the ANN model.
Hydrogen Tank Rupture in Fire in the Open Atmosphere: Hazard Distance Defined by Fireball
Feb 2021
Publication
The engineering correlations for assessment of hazard distance defined by a size of fireball after either liquid hydrogen spill combustion or high-pressure hydrogen tank rupture in a fire in the open atmosphere (both for stand-alone and under-vehicle tanks) are presented. The term “fireball size” is used for the maximum horizontal size of a fireball that is different from the term “fireball diameter” applied to spherical or semi-spherical shape fireballs. There are different reasons for a fireball to deviate from a spherical shape e.g. in case of tank rupture under a vehicle the non-instantaneous opening of tank walls etc. Two conservative correlations are built using theoretical analysis numerical simulations and experimental data available in the literature. The theoretical model for hydrogen fireball size assumes complete isobaric combustion of hydrogen in air and presumes its hemispherical shape as observed in the experiments and the simulations for tank rupturing at the ground level. The dependence of the fireball size on hydrogen mass and fireball’s diameter-to-height ratio is discussed. The correlation for liquid hydrogen release fireball is based on the experiments by Zabetakis (1964). The correlations can be applied as engineering tools to access hazard distances for scenarios of liquid or gaseous hydrogen storage tank rupture in a fire in the open atmosphere
The Effect of Hydrogen Enrichment, Flame-flame Interaction, Confinement, and Asymmetry on the Acoustic Response of a Model Can Combustor
Apr 2022
Publication
To maximise power density practical gas turbine combustion systems have several injectors which can lead to complex interactions between flames. However our knowledge about the effect of flame-flame interactions on the flame response the essential element to predict the stability of a combustor is still limited. The present study investigates the effect of hydrogen enrichment flame-flame interaction confinement and asymmetries on the linear and non-linear acoustic response of three premixed flames in a simple can combustor. A parametric study of the linear response characterised by the flame transfer function (FTF) is performed for swirling and non-swirling flames. Flame-flame interactions were achieved by changing the injector spacing and the level of hydrogen enrichment by power from 10 to 50%. It was found that the latter had the most significant effect on the flame response. Asymmetry effects were investigated by changing one of the flames by using a different bluff-body to alter both the flame shape and flow field. The global flame response showed that the asymmetric cases can be reconstructed using a superposition of the two symmetric cases where all three bluff-bodies and flames are the same. Overall the linear response characterised by the flame transfer function (FTF) showed that the effect of increasing the level of hydrogen enrichment is more pronounced than the effect of the injector spacing. Increasing hydrogen enrichment results in more compact flames which minimises flame-flame interactions. More compact flames increase the cut-off frequency which can lead to self-excited modes at higher frequencies. Finally the non-linear response was characterised by measuring the flame describing function (FDF) at a frequency close to a self-excited mode of the combustor for different injector spacings and levels of hydrogen enrichment. It is shown that increasing the hydrogen enrichment leads to higher saturation amplitude whereas the effect of injector spacing has a comparably smaller effect.
Recent Progress in Hydrogen Flammability Prediction for the Safe Energy Systems
Nov 2020
Publication
Many countries consider hydrogen as a promising energy source to resolve the energy challenges over the global climate change. However the potential of hydrogen explosions remains a technical issue to embrace hydrogen as an alternate solution since the Hindenburg disaster occurred in 1937. To ascertain safe hydrogen energy systems including production storage and transportation securing the knowledge concerning hydrogen flammability is essential. In this paper we addressed a comprehensive review of the studies related to predicting hydrogen flammability by dividing them into three types: experimental numerical and analytical. While the earlier experimental studies had focused only on measuring limit concentration recent studies clarified the extinction mechanism of a hydrogen flame. In numerical studies the continued advances in computer performance enabled even multi-dimensional stretched flame analysis following one-dimensional planar flame analysis. The different extinction mechanisms depending on the Lewis number of each fuel type could be observed by these advanced simulations. Finally historical attempts to predict the limit concentration by analytical modelling of flammability characteristics were discussed. Developing an accurate model to predict the flammability limit of various hydrogen mixtures is our remaining issue.
Hy4Heat Safety Assessment: Precis - Work Package 7
May 2021
Publication
The Hy4Heat Safety Assessment has focused on assessing the safe use of hydrogen gas in certain types of domestic properties and buildings. The summary reports (the Precis and the Safety Assessment Conclusions Report) bring together all the findings of the work and should be looked to for context by all readers. The technical reports should be read in conjunction with the summary reports. While the summary reports are made as accessible as possible for general readers the technical reports may be most accessible for readers with a degree of technical subject matter understanding. All of the safety assessment reports have now been reviewed by the HSE.<br/><br/>This document is an overview of the Safety Assessment work undertaken as part of the Hy4Heat programme
Effect of Deformation Microstructures on Hydrogen Embrittlement Sensitivity and Failure Mechanism of 304 Austenitic Stainless Steel: The Significant Role of Rolling Temperature
Feb 2022
Publication
Metastable austenitic stainless steels (ASSs) have excellent ductility but low strength so that their usage as load-bearing components is significantly limited. Rolling is an effective method of increasing strength whereas the effect of rolling temperature on microstructural evolution the hydrogen embrittlement (HE) sensitivity and fracture mechanisms is still unclear. In present study the effect of cold/warm rolling on detailed microstructural characteristics of 304 ASS was quantitatively investigated and the corresponding HE sensitivity was evaluated via slow strain rate test. The results suggest that cold-rolling led to high strength but poor plasticity and deteriorated HE sensitivity while warm-rolled samples provided combination of high strength and ductility and also superior HE resistance. Compared with 18% α′-martensite in cold -rolled steel warm-rolled specimens consisted of complete austenite less twins and lower dislocation density,moreover the favorable {112} ND and {110} ND textures replaced the harmful {001} ND texture. Based on in-situ EBSD observation during SSRT the HE sensitivity was governed by the combined effect of pre-deformation microstructures and the dynamic microstructural evolution. Advanced method of time-of-flight secondary ion mass spectrometry was used to observe the distribution of hydrogen and the hydrogen content of specimens was determined by the gas chromatograph thermal desorption analysis method. An exceedingly small amount of hydrogen entered the warm-rolled samples while a large amount of hydrogen was trapped at grain boundaries of cold-rolled sample leading to complete intergranular fracture. Therefore warm rolling is an effective pathway for obtaining high combination of strength and ductility together with excellent HE sensitivity.
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