Publications
A Dual Zone Thermodynamic Model for Refueling Hydrogen Vehicles
Sep 2017
Publication
With the simple structure and quick refuelling process the compressed hydrogen storage system is currently widely used. However thermal effects during charging-discharging cycle may induce temperature change in storage tank which has significant impact on the performance of hydrogen storage and the safety of hydrogen storage tank. To address this issue we once propose a single zone lumped parameter model to obtain the analytical solution of hydrogen temperature and use the analytical solution to estimate the hydrogen temperature but the effect of the tank wall is ignored. For better description of the heat transfer characteristics of the tank wall a dual zone (hydrogen gas and tank wall) lumped parameter model will be considered for widely representation of the reference (experimental or simulated) data. Now we extend the single zone model to the dual zone model which uses two different temperatures for gas zone and wall zone. The dual zone model contains two coupled differential equations. To solve them and obtain the solution we use the method of decoupling the coupled differential equations and coupling the solutions of the decoupled differential equations. The steps of the method include: (1) Decoupling of coupled differential equations; (2) Solving decoupled differential equations; (3) Coupling of solutions of differential equations; (4) Solving coupled algebraic equations. Herein three cases are taken into consideration: constant inflow/outflow temperature variable inflow/outflow temperature and constant inflow temperature and variable outflow temperature. The corresponding approximate analytical solutions of hydrogen temperature and wall temperature can be obtained. The hydrogen pressure can be calculated from the hydrogen temperature and the hydrogen mass using the equation of state for ideal gas. Besides the two coupled differential equations can also be solved numerically and the simulated solution can also be obtained. This study will help to set up a formula based approach of refuelling protocol for gaseous hydrogen vehicles.
Hydrogen Storage Mechanism in Sodium-Based Graphene Nanoflakes: A Density Functional Theory Study
Jan 2022
Publication
Carbon materials such as graphene nanoflakes carbon nanotubes and fullerene can be widely used to store hydrogen and doping these materials with lithium (Li) generally increases their H2 -storage densities. Unfortunately Li is expensive; therefore alternative metals are required to realize a hydrogen-based society. Sodium (Na) is an inexpensive element with chemical properties that are similar to those of lithium. In this study we used density functional theory to systematically investigate how hydrogen molecules interact with Na-doped graphene nanoflakes. A graphene nanoflake (GR) was modeled by a large polycyclic aromatic hydrocarbon composed of 37 benzene rings with GR-Na-(H2 )n and GR-Na+ -(H2 )n (n = 0–12) clusters used as hydrogen storage systems. Data obtained for the Na system were compared with those of the Li system. The single-H2 GR-Li and GR-Na systems (n = 1) exhibited binding energies (per H2 molecule) of 3.83 and 2.72 kcal/mol respectively revealing that the Li system has a high hydrogen-storage ability. This relationship is reversed from n = 4 onwards; the Na systems exhibited larger or similar binding energies for n = 4–12 than the Li-systems. The present study strongly suggests that Na can be used as an alternative metal to Li in H2 -storage applications. The H2 -storage mechanism in the Na system is also discussed based on the calculated results.
Optimizing Mixture Properties for Accurate Laminar Flame Speed Measurement from Spherically Expanding Flame: Application to H2/O2/N2/He Mixtures
Sep 2019
Publication
The uncertainty on the laminar flame speed extracted from spherically expanding flames can be minimized by using large flame radius data for the extrapolation to zero stretch-rate. However at large radii the hydrodynamic and thermo-diffusive instabilities induce the formation of a complex cellular flame front and limit the range of usable data. In the present study we have employed the flame stability theory of Matalon to optimize the properties of the initial mixture so that transition to cellularity may occur at a pre-determined large radius. This approach was employed to measure the laminar flame speeds of H2/O2/N2/He mixtures with equivalence ratios from 0.6 to 2.0 at pressures of 50/80/100 kPa and a temperature of 300 K. For all the performed experiments the uncertainty related to the extrapolation to zero stretch-rate (performed with the linear curvature model) was below 2% as shown by the position of the data points in the (Lb/Rf;U Lb/Rf;L) plan where Lb is the burned Markstein length; and Rf;L and Rf;U are the flame radii at the lower and upper bounds of the extrapolation range. Comparison of the predictions of four chemical mechanisms with the present unstretched laminar flame speed data indicated an error below 10% for most conditions. In addition unsteady 1-D simulations performed with A-SURF demonstrated that the flame dynamical response to stretch rate could not be captured by the mechanisms. The present work indicates that although the stability theory of Matalon provides a well defined framework to optimize the mixture properties for improved flame speed measurement the uncertainty of some of the required parameters can result in largely over-estimated critical radius for cellularity onset which compromise the accuracy of the optimization procedure.
Development and Functionalization of Visible-Light-Driven Water-Splitting Photocatalysts
Jan 2022
Publication
With global warming and the depletion of fossil resources our fossil fuel-dependent society is expected to shift to one that instead uses hydrogen (H2) as a clean and renewable energy. To realize this the photocatalytic water-splitting reaction which produces H2 from water and solar energy through photocatalysis has attracted much attention. However for practical use the functionality of water-splitting photocatalysts must be further improved to efficiently absorb visible (Vis) light which accounts for the majority of sunlight. Considering the mechanism of water-splitting photocatalysis researchers in the various fields must be employed in this type of study to achieve this. However for researchers in fields other than catalytic chemistry ceramic (semiconductor) materials chemistry and electrochemistry to participate in this field new reviews that summarize previous reports on water-splitting photocatalysis seem to be needed. Therefore in this review we summarize recent studies on the development and functionalization of Vis-light-driven water-splitting photocatalysts. Through this summary we aim to share current technology and future challenges with readers in the various fields and help expedite the practical application of Vis-light-driven water-splitting photocatalysts.
Annual Science Review 2019
Mar 2019
Publication
Having a robust evidence base enables us to tackle real issues causing pain and suffering in the workplace. Critically it enables us to better understand developing issues and ways of working to ensure that we support innovation rather than stifle it through lack of knowledge. For example the work on the use of 3D printers in schools demonstrates HSE’s bility to engage and understand the risks to encourage safe innovation in a developing area (see p47).<br/>Other examples in this report show just a selection of the excellent work carried out by our staff often collaborating with others which contributes to improving how we regulate health and safety risks proportionately and effectively.<br/>One of HSEs key priorities is to prevent future cases of occupational lung disease by improving the management and control of hazardous substances. The case study on measuring Respirable Crystalline Silica exposure contributes to this and to recognise developing and future issues such as the work on diacetyl in the coffee industry (see p24 and p39). This type of scientific investigation gives our regulators good trusted information enabling critical decisions on the actions needed to protect workers.<br/>The case study on publishing new guidance on the use of Metalworking Fluids (MWF) demonstrates the important contribution of collaborative science to improving regulation. If used inappropriately exposure to MWF mist can cause serious long-term lung disease and it was recognised that users needed help to control this risk. HSE scientists and regulators worked with industry stakeholders to produce new free guidance which reflects changes in scientific understanding in a practical easy to use guide. As well as enabling users to better manage the risks and as a bonus likely save money it has assisted regulation by providing clear benchmarks for all to judge control against. An excellent example of science contributing to controlling serious health risks (see p22).<br/>These case studies are excellent examples of how science contributes to reducing risk. Hopefully they will inspire you to think about how risk in your workplace could be improved and where further work might be needed.
Improving Hydrogen Embrittlement Resistance of Hot-Stamped 1500 MPa Steel Parts That Have Undergone a Q&P Treatment by the Design of Retained Austenite and Martensite Matrix
Nov 2020
Publication
Hydrogen embrittlement is one of the largest obstacles against the commercialisation of ultra-high strength quenching and partitioning (Q&P) steels with ultimate tensile strength over 1500 MPa including the hot stamped steel parts that have undergone a Q&P treatment. In this work the influence of partitioning temperature on hydrogen embrittlement of ultra-high strength Q&P steels is studied by pre-charged tensile tests with both dog-bone and notched samples. It is found that hydrogen embrittlement resistance is enhanced by the higher partitioning temperature. Then the hydrogen embrittlement mechanism is analysed in terms of hydrogen retained austenite and martensite matrix. Thermal desorption analysis (TDA) shows that the hydrogen trapping properties are similar in the Q&P steels which cannot explain the enhancement of hydrogen embrittlement resistance. On the contrary it is found that the relatively low retained austenite stability after the higher temperature partitioning ensures more sufficient TRIP effect before hydrogen-induced fracture. Additionally dislocation recovery and solute carbon depletion at the higher partitioning temperature can reduce the flow stress of the martensite matrix improving its intrinsic toughness and reducing its hydrogen sensitivity both of which result in the higher hydrogen embrittlement resistance.
Inhibition of Hydrogen-yielding Dark Fermentation by Ascomycetous Yeasts
May 2018
Publication
Hydrogen-yielding fermentation conducted in bioreactors is an alternative method of hydrogen production. However unfavourable processes can seriously inhibit bio-hydrogen generation during the acidogenic step of anaerobic digestion. Here ascomycetous yeasts were identified as a major factor inhibiting the production of bio-hydrogen by fermentation. Changes in the performance of hydrogen-producing bioreactors including metabolic shift quantitative changes in the fermentation products decreased pH instability of the microbial community and consequently a dramatic drop in bio-hydrogen yield were observed following yeast infection. Ascomycetous yeasts from the genera Candida Kazachstania and Geotrichum were isolated from hydrogen-producing bioreactors. Yeast metabolites secreted into the growth medium showed antibacterial activity. Our studies indicate that yeast infection of hydrogen-producing microbial communities is one of the serious obstacles to use dark fermentation as an alternative method of bio-hydrogen production. It also explains why studies on hydrogen fermentation are still limited to the laboratory or pilot-scale systems.
Potential Development of Renewable Hydrogen Imports to European Markets until 2030
Mar 2022
Publication
This paper considers potential import routes for low-carbon and renewable hydrogen (H2) to main European markets like Germany. In particular it analyses claims made by Hydrogen Europe and subsequently picked up by the European Commission in its Hydrogen Strategy that there will be 40GW of electrolyser capacity in nearby countries providing hydrogen imports to Europe by 2030. The analysis shows that by 2030 potential demand for H2 could be high enough to initiate some limited international hydrogen trade most likely between European countries initially rather than from outside Europe. Geographically a northern hydrogen cluster around Netherlands and NW Germany will be more significant for hydrogen demand while southern Europe is more likely to have surplus low cost renewable power generation. The paper considers potential H2 exporters to Europe including Ukraine and North African countries (in line with the proposal from Hydrogen Europe) as well as Norway and Russia. (The research pre-dates recent political and military tensions between Russia and Ukraine which are likely to influence future development pathways). The supply cost of hydrogen in 2030 is predicted to be in a reasonably (and perhaps surprisingly) narrow band around €3/kg from various sources and supply chains. The paper concludes that overall while imports of hydrogen to Europe are certainly possible in the longer term there are many challenges to be addressed. This conclusion supports the growing consensus that development of low carbon hydrogen certainly within Europe is likely to start within relatively local hydrogen clusters with some limited bilateral trade.
The research paper can be found on their website
The research paper can be found on their website
H2FC SUPERGEN- The Role of Hydrogen and Fuel Cells in Delivering Energy Security for the UK
Mar 2017
Publication
This White Paper has been commissioned by the UK Hydrogen and Fuel Cell (H2FC) SUPERGEN Hub to examine the roles and potential benefits of hydrogen and fuel cell technologies within each sector of future energy systems and the transition infrastructure that is required to achieve these roles. The H2FC SUPERGEN Hub is an inclusive network encompassing the entire UK hydrogen and fuel cells research community with around 100 UK-based academics supported by key stakeholders from industry and government. It is funded by the UK EPSRC research council as part of the RCUK Energy Programme. This paper is the third of four that were published over the lifetime of the Hub with the others examining: (i) low-carbon heat; (ii) energy security; and (iv) economic impacts.
- Hydrogen and fuel cells are now being deployed commercially for mainstream applications.
- Hydrogen can play a major role alongside electricity in the low-carbon economy.
- Hydrogen technologies can support low-carbon electricity systems dominated by intermittent renewables and/or electric heating demand.
- The hydrogen economy is not necessary for hydrogen and fuel cells to flourish.
Open-source Simulation of the Long-term Diffusion of Alternative Passenger Cars on the Basis of Investment Decisions of Private Persons
Feb 2021
Publication
Numerous studies have shown that a full electrification of passenger cars is needed to stay within the 1.5° C temperature rise. This article deals with the question of how the required shares of alternative vehicles can be achieved by the year 2050. In literature the preferred technology are battery electric vehicles as these are more energy efficient than hydrogen vehicles. To be able to demonstrate how alternative vehicles diffuse into the German market the passenger car investment behavior of private persons was investigated. For this purpose a discrete choice experiment (DCE) with 1921 participants was carried out empirically. The results of the DCE show that the investment costs in particular are important when choosing a vehicle. This is followed by the driving range fuel costs and vehicle type. Less important are the charging infrastructure and CO2 emissions of the vehicle. A CO2 tax is of least importance. The utility values of the DCE were used to simulate future market shares. For this purpose the open-source software Invest was developed and different scenarios were defined and calculated. This paper shows that conservative assumptions on attribute development leave a large gap until full electrification as conventional vehicles still account for around 62% of market shares in 2050. In order to achieve full electrification extreme efforts must be made targeting the technical and economic characteristics of the vehicles but also addressing person-related characteristics such as level of information the subjective norm or the technological risk attitude. A ban on new registrations of combustion engines from 2030 could also lead to a full electrification by 2050. An average annual increase in the market share of alternative vehicles of 2.4 percentage points is needed to achieve full electrification. Other important factors are measures that address the modal shift to other modes of transport (rail public transport car-sharing).
Risk Informed Separation Distances For Hydrogen Refuelling Stations
Sep 2011
Publication
The lay-out requirements developed for hydrogen systems operated in industrial environment are not suitable for the operating conditions specific to hydrogen refuelling stations (service pressure of up to 95 MPa facility for public use). A risk informed rationale has been developed to define and substantiate separation distance requirements in ISO 20100 Gaseous hydrogen – refuelling stations [1]. In this approach priority is given to preventing escalation of small incidents into majors ones with a focus on critical exposures such as places of occupancy (fuelling station retail shop) while optimizing use of the available space from a risk perspective a key objective for being able to retrofit hydrogen refuelling in existing stations.
Cell Failure Mechanisms in PEM Water Electrolyzers
Sep 2011
Publication
PEM water electrolysis offers an efficient and flexible way to produce “green-hydrogen” from renewable (intermittent) energy sources. Most research papers published in the open literature on the subject are addressing performances issues and to date very few information is available concerning the mechanisms of performance degradation and the associated consequences. Results reported in this communication have been used to analyze the failure mechanisms of PEM water electrolysis cells which can ultimately lead to the destruction of the electrolyzer. A two-step process involving firstly the local perforation of the solid polymer electrolyte followed secondly by the catalytic recombination of hydrogen and oxygen stored in the electrolysis compartments has been evidenced. The conditions leading to the onset of such mechanism are discussed and some preventive measures are proposed to avoid accidents.
Regulations, Codes, and Standards (RCS) for Multi-fuel Motor Vehicle Dispensing Station
Sep 2017
Publication
In the United States requirements for liquid motor vehicle fuelling stations have been in place for many years. Requirements for motor vehicle fuelling stations for gaseous fuels including hydrogen are relatively new. These requirements have in the United States been developed along different code and standards paths. The liquid fuels have been addressed in a single document and the gaseous fuels have been addressed in documents specific to an individual gas. The result of these parallel processes is that multi-fuel stations are subject to requirements in several fuelling regulations codes and standards (RCS). This paper describes a configuration of a multi-fuel motor vehicle fuelling station and provides a detailed breakdown of the codes and standards requirements. The multi-fuel station would dispense what the U.S. Department of Energy defines as the six key alternative fuels: biodiesel electricity ethanol hydrogen natural gas and propane. The paper will also identify any apparent gaps in RCS and potential research projects that could help fill these gaps.
Assessment of Safety for Hydrogen Fuel Cell Vehicle
Sep 2011
Publication
A prospective global market share of Electric vehicle (EV) Hybrid electric vehicle (HEV) and Hydrogen Fuel Cell Vehicle (HFCV) is expected to grow due to stringent emission regulation and oil depletion. However it is essential to secure protection against high-pressure hydrogen gas and high-voltage in fuel cell vehicles and thus needs to develop a technique for safety assessment of HFCV. In this experiment 8 research institutes including the Korea Automobile Testing and Research Institute Hyundai Motor Company took part in. This project was supported by the Ministry of Land Transportation and Maritime Affairs of the Republic of Korea.
Effect of Rotation on Ignition Thresholds of Stoichiometric Hydrogen Mixtures
Sep 2017
Publication
Successful transition to a hydrogen economy calls for a deep understanding of the risks associated with its widespread use. Accidental ignition of hydrogen by hot surfaces is one of such risks. In the present study we investigated the effect that rotation has on the reported ignition thresholds by numerically determining the minimum surface temperature required to ignite stoichiometric hydrogen-air using a hot horizontal cylinder rotating at various angular velocities ω. Numerical experiments showed a weak but interesting dependence of the ignition thresholds on rotation: the ignition thresholds increased by 8 K from 931 K to 939 K with increasing angular velocity (0 ≤ ω ≤ 240 rad/s). A further increase to ω = 480 rad/s resulted in a decrease in ignition surface temperature to 935 K. Detailed analysis of the flow patterns inside the vessel and in close proximity to the hot surface brought about by the combined effect of buoyancy and rotation as well as of the distribution of the wall heat flux along the circumference of the cylinder support our previous findings in which regions where temperature gradients are small were found to be prone to ignition.
The Residual Strength of Automotive Hydrogen Cylinders After Exposure to Flames
Sep 2017
Publication
Fuel cell vehicles and some compressed natural gas vehicles are equipped with carbon fiber reinforced plastic (CFRP) composite cylinders. Each of the cylinders has a pressure relief device designed to detect heat and release the internal gas to prevent the cylinder from bursting in a vehicle fire accident. Yet in some accident situations the fire may be extinguished before the pressure relief device is activated leaving the high-pressure fuel gas inside the fire-damaged cylinder. To handle such a cylinder safely after an accident it is necessary that the cylinder keeps a sufficient post-fire strength against its internal gas pressure but in most cases it is difficult to accurately determine cylinder strength at the accident site. One way of solving this problem is to predetermine the post-fire burst strengths of cylinders by experiments. In this study automotive CFRP cylinders having no pressure relief device were exposed to a fire to the verge of bursting; then after the fire was extinguished the residual burst strengths and the overall physical state of the test cylinders were examined. The results indicated that the test cylinders all recorded a residual burst strength at least twice greater than their internal gas pressure for tested cylinders with new cylinder burst to nominal working pressure in the range 2.67–4.92 above the regulated ratio of 2.25.
Experiments on the Combustion Behaviour of Hydrogen-Carbon Monoxide-Air Mixtures
Sep 2019
Publication
As a part of a German nuclear safety project on the combustion behaviour of hydrogen-carbon monoxide-air mixtures small scale experiments were performed to determine the lower flammability limit and the laminar burning velocity of such mixtures. The experiments were performed in a spherical explosion bomb with a free volume of 8.2 litre. The experimental set-up is equipped with a central spark ignition and quartz glass windows for optical access. Further instrumentation included pressure and temperature sensors as well as high-speed shadow-videography. A wide concentration range for both fuel gases was investigated in numerous experiments from the lower flammability limits up to the stoichiometric composition of hydrogen carbon monoxide and air (H2-CO-air) mixtures. The laminar burning velocities were determined from the initial pressure increase after the ignition and by using high-speed videos taken during the experiments.
Data for the Evaluation of Hydrogen Risks Onboard Vehicles: Outcomes from the French Project Drive
Sep 2011
Publication
From 2006 to 2009 INERIS alongside with CEA PSA PEUGEOT CITROËN and IRPHE were involved in a project called DRIVE. Its objective was to provide data on the whole reaction chain leading to a hydrogen hazard onboard a vehicle. Out of the three types of leakage identified by the consortium (permeation chronic and accidental) the chronic leakage taking place within the engine was judged to be more problematic since it can feature a high probability of occurrence and a significant release flow rate (up to 100 NL/min). Ignition tests carried out within a real and dummy engine compartment showed that pressure effects due to an explosion will be relatively modest provided that the averaged hydrogen concentration in this area is limited to 10% vol/vol which would correspond to a maximum release flow of 10 NL/min. This maximum concentration could be used as a threshold value for detection or as a target while designing the vehicle. Jet fire experiments were also conducted in the frame of the DRIVE project. It was found that pressure-relief devices (PRDs) might be unsuited to protect humans from the explosion of a tank caused by a bonfire. Other solutions are proposed in this paper.
Spontaneous Ignition Processes Due To High-Pressure Hydrogen Release in Air
Sep 2011
Publication
Spontaneous ignition processes due to the high-pressure hydrogen releases into air were investigated both experimentally and theoretically. Such processes reproduce accident scenarios of sudden expansion of pressurized hydrogen into the ambient atmosphere in cases of tube or valve rupture. High-pressure hydrogen releases in the range of initial pressures from 20 to 275 bar and with nozzle diameters of 0.5 – 4 mm have been investigated. Glass tubes and high-speed CCD camera were used for experimental study of self-ignition process. The problem was theoretically considered in terms of contact discontinuity for the case when spontaneous ignition of pressurized hydrogen due to the contact with hot pressurized air occurs. The effects of boundary layer and material properties are discussed in order to explain the minimum initial pressure of 25 bar leading to the self-ignition of hydrogen with air.
Experimental Study of Ignited Unsteady Hydrogen Jets into Air
Sep 2009
Publication
In order to simulate an accidental hydrogen release from the low pressure pipe system of a hydrogen vehicle a systematic study on the nature of transient hydrogen jets into air and their combustion behaviour was performed at the FZK hydrogen test site HYKA. Horizontal unsteady hydrogen jets with an amount of hydrogen up to 60 STP dm3 and initial pressures of 5 and 16 bar have been investigated. The hydrogen jets were ignited with different ignition times and positions. The experiments provide new experimental data on pressure loads and heat releases resulting from the deflagration of hydrogen-air clouds formed by unsteady turbulent hydrogen jets released into a free environment. It is shown that the maximum pressure loads occur for ignition in a narrow position and time window. The possible hazard potential arising from an ignited free transient hydrogen jet is described.
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