Italy
Innovative Passive Protection Systems For Hydrogen Production Plants
Sep 2005
Publication
As a part of a broader project on hydrogen production by reforming of methane in a membrane catalytic reactor this paper outlines the research activity performed at the University of Pisa Department of Chemical Engineering aimed at developing and testing composite panels that can operate as thermal protective shields against hydrogen jet fires. The shield design criterion that appears to give a more practical and convenient solution for the type of installation to be protected is the one that suggest to realize composite panels. Composite material are made of two elements fiber and matrix. In this study composite panels will be realized with basalt fabric as fiber and epoxy-phenolic resins as matrix. Therefore following the indications given by norms as UNI 9174 and ASTM E 1321-93 a test method has been studied to obtain temperature data from a specimen impinged by an hydrogen flame. Thanks to thermocouples applied on backside of the sample and an infrared video camera to realize thermal images of specimen surface impinged by flame this type of test try to characterize the behaviour of composite materials under the action of hydrogen flame simulating in a simple way the action of hydrogen jet fires.
Consequence Assessment of the BBC Hydrogen Refuelling Station, Using The Adrea-Hf Code
Sep 2009
Publication
Within the framework of the internal project HyQRA of the HYSAFE Network of Excellence (NoE) funded by the European Commission (EC) the participating partners were requested to apply their Quantitative Risk Assessment (QRA) methodologies on a predefined hypothetical gaseous H2 refuelling station named BBC (Benchmark Base Case). The overall aim of the HyQRA project was to perform an inter-comparison of the various QRA approaches and to identify the knowledge gaps on data and information needed in the QRA steps specifically related to H2. Partners NCSRD and UNIPI collaborated on a common QRA. UNIPI identified the hazards on site selected the most critical ones defined the events that could be the primary cause of an accident and provided to NCSRD the scenarios listed in risk order for the evaluation of the consequences. NCSRD performed the quantitative analysis using the ADREA-HF CFD code. The predicted risk assessment parameters (flammable H2 mass and volume time histories and maximum horizontal and vertical distances of the LFL from the source) were provided to UNIPI to analyze the consequences and to evaluate the risk and distances of damage. In total 15 scenarios were simulated. Five of them were H2 releases in confined ventilated spaces (inside the compression and the purification/drying buildings). The remaining 10 scenarios were releases in open/semi-confined spaces (in the storage cabinet storage bank and refuelling hose of one dispenser). This paper presents the CFD methodology applied for the quantitative analysis of the common UNIPI/NCSRD QRA and discusses the results obtained from the performed calculations.
Safety Distances: Comparison of the Methodologies for Their Determination
Sep 2011
Publication
In this paper a study on the comparison between the different methodologies for the determination of the safety distances proposed by Standard Organizations and national Regulations is presented. The application of the risk-informed approach is one of the methodologies used for the determination of safety distances together with the risk-based approach. One of the main differences between the various methodologies is the risk criterion chosen. In fact a critical point is which level of risk should be used and then which are the harm events that must be considered. The harm distances are evaluated for a specified leak diameter that is a consequence of some parameters used in the various methodologies. The values of the safety distances proposed by Standard Organizations and national Regulations are a demonstration of the different approaches of the various methodologies especially in the choice of the leak diameter considered.
Thermal Efficiency of On-site, Small-scale Hydrogen Production Technologies using Liquid Hydrocarbon Fuels in Comparison to Electrolysis a Case Study in Norway
Oct 2018
Publication
The main goal of this study was to assess the energy efficiency of a small-scale on-site hydrogen production and dispensing plant for transport applications. The selected location was the city of Narvik in northern Norway where the hydrogen demand is expected to be 100 kg/day. The investigated technologies for on-site hydrogen generation starting from common liquid fossil fuels such as heavy naphtha and diesel were based on steam reforming and partial oxidation. Water electrolysis derived by renewable energy was also included in the comparison. The overall thermal efficiency of the hydrogen station was computed including compression and miscellaneous power consumption.
Hydrogen and Fuel Cell Stationary Applications: Key Findings of Modelling and Experimental Work in the Hyper Project
Sep 2009
Publication
Síle Brennan,
A. Bengaouer,
Marco Carcassi,
Gennaro M. Cerchiara,
Andreas Friedrich,
O. Gentilhomme,
William G. Houf,
N. Kotchourko,
Alexei Kotchourko,
Sergey Kudriakov,
Dmitry Makarov,
Vladimir V. Molkov,
Efthymia A. Papanikolaou,
C. Pitre,
Mark Royle,
R. W. Schefer,
G. Stern,
Alexandros G. Venetsanos,
Anke Veser,
Deborah Willoughby,
Jorge Yanez and
Greg H. Evans
"This paper summarises the modelling and experimental programme in the EC FP6 project HYPER. A number of key results are presented and the relevance of these findings to installation permitting guidelines (IPG) for small stationary hydrogen and fuel cell systems is discussed. A key aim of the activities was to generate new scientific data and knowledge in the field of hydrogen safety and where possible use this data as a basis to support the recommendations in the IPG. The structure of the paper mirrors that of the work programme within HYPER in that the work is described in terms of a number of relevant scenarios as follows: 1. high pressure releases 2. small foreseeable releases 3. catastrophic releases and 4. the effects of walls and barriers. Within each scenario the key objectives activities and results are discussed.<br/>The work on high pressure releases sought to provide information for informing safety distances for high-pressure components and associated fuel storage activities on both ignited and unignited jets are reported. A study on small foreseeable releases which could potentially be controlled through forced or natural ventilation is described. The aim of the study was to determine the ventilation requirements in enclosures containing fuel cells such that in the event of a foreseeable leak the concentration of hydrogen in air for zone 2 ATEX is not exceeded. The hazard potential of a possibly catastrophic hydrogen leakage inside a fuel cell cabinet was investigated using a generic fuel cell enclosure model. The rupture of the hydrogen feed line inside the enclosure was considered and both dispersion and combustion of the resulting hydrogen air mixture were examined for a range of leak rates and blockage ratios. Key findings of this study are presented. Finally the scenario on walls and barriers is discussed; a mitigation strategy to potentially reduce the exposure to jet flames is to incorporate barriers around hydrogen storage equipment. Conclusions of experimental and modelling work which aim to provide guidance on configuration and placement of these walls to minimise overall hazards is presented. "
Quantification of the Uncertainty of the Peak Pressure Value in the Vented Deflagrations of Air-Hydrogen Mixtures
Sep 2007
Publication
In the problem of the protection by the consequences of an explosion is actual for many industrial application involving storage of gas like methane or hydrogen refuelling stations and so on. A simple and economic way to reduce the peak pressure associated to a deflagration is to supply to the confined environment an opportune surface substantially less resistant then the protected structure typically in stoichiometric conditions the peak pressure reduction is around the 8 bars for a generic hydrocarbon combustion in an adiabatic system lacking of whichever mitigation system. In general the problem is the forecast of the peak pressure value (PMAX) of the explosion. This problem is faced using CFD codes modelling the structure in which the explosion is located and setting the main parameters like concentration of the gas in the mixture the volume available the size of vent area and obstacles (if included) and so on. In this work the idea is to start from empirical data to train a Neural Network (NN) in order to find the correlation among the parameters regulating the phenomenon. Associated to this prediction a fuzzy model will provide to quantify the uncertainty of the predicted value.
Integration of Experimental Facilities: A Joint Effort for Establishing a Common Knowledge Base in Experimental Work on Hydrogen Safety
Sep 2009
Publication
With regard to the goals of the European HySafe Network research facilities are essential for the experimental investigation of relevant phenomena for testing devices and safety concepts as well as for the generation of validation data for the various numerical codes and models. The integrating activity ‘Integration of Experimental Facilities (IEF)’ has provided basic support for jointly performed experimental work within HySafe. Even beyond the funding period of the NoE HySafe in the 6th Framework Programme IEF represents a long lasting effort for reaching sustainable integration of the experimental research capacities and expertise of the partners from different research fields. In order to achieve a high standard in the quality of experimental data provided by the partners emphasis was put on the know-how transfer between the partners. The strategy for reaching the objectives consisted of two parts. On the one hand a documentation of the experimental capacities has been prepared and analysed. On the other hand a communication base has been established by means of biannual workshops on experimental issues. A total of 8 well received workshops has been organised covering topics from measurement technologies to safety issues. Based on the information presented by the partners a working document on best practice including the joint experimental knowledge of all partners with regard to experiments and instrumentation was created. Preserving the character of a working document it was implemented in the IEF wiki website which was set up in order to provide a central communication platform. The paper gives an overview of the IEF network activities over the last 5 years.
Trends in Gas Sensor Development for Hydrogen Safety
Sep 2013
Publication
Gas sensors are applied for facilitating the safe use of hydrogen in for example fuel cell and hydrogen fuelled vehicles. New sensor developments aimed at meeting the increasingly stringent performance requirements in emerging applications are presented based on in-house technical developments and a literature study. The strategy of combining different detection principles i.e. sensors based on electrochemical cells semiconductors or field effects in combination with thermal conductivity sensor or catalytic combustion elements in one new measuring system is reported. This extends the dynamic measuring range of the sensor while improving sensor reliability to achieve higher safety integrity through diverse redundancy. The application of new nanoscaled materials nano wires carbon tubes and graphene as well as the improvements in electronic components of field-effect resistive-type and optical systems are evaluated in view of key operating parameters such as sensor response time low energy consumption and low working temperature.
Helios- A New Method for Hydrogen Permeation Test
Sep 2013
Publication
Hydrogen induced cracking is still a severe and current threat for several industrial applications. With the aim of providing a simple and versatile device for hydrogen detection a new instrument was designed based on solid state sensor technology. New detection technique allows to execute hydrogen permeation measurement in short time and without material surface preparation. Thanks to this innovation HELIOS offers a concrete alternative to traditional experimental methods for laboratory permeability tests. In addition it is proposed as a new system for Non Destructive Testing of components in service in hydrogenating environment. Hydrogen flux monitoring is particularly relevant for risk mitigation of elements involved in hydrogen storage and transportation. Hydrogen permeation tests were performed by means of HELIOS instruments both on a plane membrane and on the wall of a gas cylinder. Results confirmed the extreme sensitivity of the detection system and its suitability to perform measurements even on non metallic materials by means of an easy-to-handle instrument.
Non-stoichiometric Methanation as Strategy to Overcome the Limitations of Green Hydrogen Injection into the Natural Gas Grid
Jan 2022
Publication
The utilization of power to gas technologies to store renewable electricity surpluses in the form of hydrogen enables the integration of the gas and electricity sectors allowing the decarbonization of the natural gas network through green hydrogen injection. Nevertheless the injection of significant amounts of hydrogen may lead to high local concentrations that may degrade materials (e.g. hydrogen embrittlement of pipelines) and in general be not acceptable for the correct and safe operation of appliances. Most countries have specific regulations to limit hydrogen concentration in the gas network. The methanation of hydrogen represents a potential option to facilitate its injection into the grid. However stoichiometric methanation will lead to a significant presence of carbon dioxide limited in gas networks and requires an accurate design of several reactors in series to achieve relevant concentrations of methane. These requirements are smoothed when the methanation is undertaken under non-stoichiometric conditions (high H/C ratio). This study aims to assess to influence of nonstoichiometric methanation under different H/C ratios on the limitations presented by the pure hydrogen injection. The impact of this injection on the operation of the gas network at local level has been investigated and the fluid-dynamics and the quality of gas blends have been evaluated. Results show that non-stoichiometric methanation could be an alternative to increase the hydrogen injection in the gas network and facilitates the gas and electricity sector coupling.
Micro-wrinkled Pd Surface for Hydrogen Sensing and Switched Detection of Lower Explosive Limit
Sep 2011
Publication
We report the development and testing of a novel hydrogen sensor that shows a very peculiar response to hydrogen exposure due to its micro-structured palladium surface. The fabrication of the wrinkled Pd surface is obtained using an innovative fast and cheap technique based on the deposition of a thin Pd film on to a thermo-retractable polystyrene sheet that shrinks to 40% of its original size when heated. The buckling of the Pd surface induced by shrinking of the substrate produces nano and micro-wrinkles on the sensor surface. The micro-structured sensor surface is very stable even after repeated hydrogen sorption/desorption cycles. The hydrogen sensing mechanism is based on the transitory absorption of hydrogen atoms into the Pd layer leading to the reversible change of its electrical resistance. Interestingly depending on hydrogen concentration the proposed sensor shows the concurrent effect of both the usually described behaviors of increase or decrease of resistance related to different phenomena occurring upon hydrogen exposure and formation of palladium hydride. The study reports and discusses evidences for an activation threshold of hydrogen concentration in air switching the behavior of sensor performances from e.g. poor negative to large positive sensitivity and from slow to fast detection.
Design and Costs Analysis of Hydrogen Refuelling Stations Based on Different Hydrogen Sources and Plant Configurations
Jan 2022
Publication
In this study the authors present a techno-economic assessment of on-site hydrogen refuelling stations (450 kg/day of H2 ) based on different hydrogen sources and production technologies. Green ammonia biogas and water have been considered as hydrogen sources while cracking autothermal reforming and electrolysis have been selected as the hydrogen production technologies. The electric energy requirements of the hydrogen refuelling stations (HRSs) are internally satisfied using the fuel cell technology as power units for ammonia and biogas-based configurations and the PV grid-connected power plant for the water-based one. The hydrogen purification where necessary is performed by means of a Palladium-based membrane unit. Finally the same hydrogen compression storage and distribution section are considered for all configurations. The sizing and the energy analysis of the proposed configurations have been carried out by simulation models adequately developed. Moreover the economic feasibility has been performed by applying the life cycle cost analysis. The ammonia-based configurations are the best solutions in terms of hydrogen production energy efficiency (>71% LHV) as well as from the economic point of view showing a levelized cost of hydrogen (LCOH) in the range of 6.28 EUR/kg to 6.89 EUR/kg a profitability index greater than 3.5 and a Discounted Pay Back Time less than five years.
Material Testing and Design Recommendations for Components Exposed to Hydrogen Enhanced Fatigue – the Mathryce Project
Sep 2013
Publication
The three years European MATHRYCE project dedicated to material testing and design recommendations for components exposed to hydrogen enhanced fatigue started in October 2012. Its main goal is to provide an “easy” to implement methodology based on lab-scale experimental tests under hydrogen gas to assess the service life of a real scale component taking into account fatigue loading under hydrogen gas. Dedicated experimental tests will be developed for this purpose. In the present paper the proposed approach is presented and compared to the methodologies currently developed elsewhere in the world.
Benchmark Exercise on Risk Assessment Methods Applied to a Virtual Hydrogen Refuelling Station
Sep 2009
Publication
A benchmarking exercise on quantitative risk assessment (QRA) methodologies has been conducted within the project HyQRA under the framework of the European Network of Excellence (NoE) HySafe. The aim of the exercise was basically twofold: (i) to identify the differences and similarities in approaches in a QRA and their results for a hydrogen installation between nine participating partners representing a broad spectrum of background in QRA culture and history and (ii) to identify knowledge gaps in the various steps and parameters underlying the risk quantification. In the first step a reference case was defined: a virtual hydrogen refuelling station (HRS) in virtual surroundings comprising housing school shops and other vulnerable objects. All partners were requested to conduct a QRA according to their usual approach and experience. Basically participants were free to define representative release cases to apply models and frequency assessments according their own methodology and to present risk according to their usual format. To enable inter-comparison a required set of results data was prescribed like distances to specific thermal radiation levels from fires and distances to specific overpressure levels. Moreover complete documentation of assumptions base data and references was to be reported. It was not surprising that a wide range of results was obtained both in the applied approaches as well as in the quantitative outcomes and conclusions. This made it difficult to identify exactly which assumptions and parameters were responsible for the differences in results as the paper will show. A second phase was defined in which the QRA was determined by a more limited number of release cases (scenarios). The partners in the project agreed to assess specific scenarios in order to identify the differences in consequence assessment approaches. The results of this phase provide a better understanding of the influence of modelling assumptions and limitations on the eventual conclusions with regard to risk to on-site people and to the off-site public. This paper presents the results and conclusions of both stages of the exercise.
Integration of Open Slag Bath Furnace with Direct Reduction Reactors for New‐Generation Steelmaking
Jan 2022
Publication
The present paper illustrates an innovative steel processing route developed by employing hydrogen direct reduced pellets and an open slag bath furnace. The paper illustrates the direct reduction reactor employing hydrogen as reductant on an industrial scale. The solution allows for the production of steel from blast furnace pellets transformed in the direct reduction reactor. The reduced pellets are then melted in open slag bath furnaces allowing carburization for further refining. The proposed solution is clean for the decarbonization of the steel industry. The kinetic chemical and thermodynamic issues are detailed with particular attention paid to the slag conditions. The proposed solution is also supported by the economic evaluation compared to traditional routes.
Risk Analysis of Complex Hydrogen Infrastructures
Oct 2015
Publication
Building a network of hydrogen refuelling stations is essential to develop the hydrogen economy within transport. Additional hydrogen is regarded a likely key component to store and convert back excess electrical power to secure future energy supply and to improve the quality of biomass-based fuels. Therefore future hydrogen supply and distribution chains will have to address several objectives. Such a complexity is a challenge for risk assessment and risk management of these chains because of the increasing interactions. Improved methods are needed to assess the supply chain as a whole. The method of “Functional modelling” is discussed in this paper. It will be shown how it could be a basis for other decision support methods for comprehensive risk and sustainability assessments.
Cylinders and Tubes Used as Buffers in Filling Stations
Oct 2015
Publication
Buffers are key components for hydrogen filling stations that are currently being developed. Type 1 or composite cylinders are used for this application. The type used depends on many parameters including pressure level cost and space available for the filling station. No international standards exist for such high pressure vessels whereas many standards exist covering Types 123 and 4 used for transport of gas or on-board fuel tanks. It is suggested to use the cylinders approved for transport or on-board applications as buffers. This solution appears to be safe if at least one issue is solved. The main difference is that transport or on-board cylinders are cycled from a low pressure to a high pressure during service whereas buffers are cycled from a relatively high pressure (corresponding to the vehicle’s filling pressure) to the MAWP. Another difference is that buffers are cycled many times per day. For standards developers requesting to systematically verify that buffers pass millions of cycles at low pressure amplitude would be impractical. Several standards and codes give formulae to estimate the number of shallow cycles when number of deep cycles are known. In this paper we describe tests performed on all types of composite cylinders to verify or determine the appropriate formulae.
Hydrogen Permeation in X65 Steel under Cyclic Loading
May 2020
Publication
This experimental work analyzes the hydrogen embrittlement mechanism in quenched and tempered low-alloyed steels. Experimental tests were performed to study hydrogen diffusion under applied cyclic loading. The permeation curves were fitted by considering literature models in order to evaluate the role of trapping—both reversible and irreversible—on the diffusion mechanism. Under loading conditions a marked shift to the right of the permeation curves was noticed mainly at values exceeding the tensile yield stress. In the presence of a relevant plastic strain the curve changes due to the presence of irreversible traps which efficiently subtract diffusible atomic hydrogen. A significant reduction in the apparent diffusion coefficient and a considerable increase in the number of traps were noticed as the maximum load exceeded the yield strength. Cyclic loading at a tensile stress slightly higher than the yield strength of the material increases the hydrogen entrapment phenomena. The tensile stress causes a marked and instant reduction in the concentration of mobile hydrogen within the metal lattice from 55% of the yield strength and it increases significantly in the plastic field.
Lock-In Effects on the Energy Sector: Evidence from Hydrogen Patenting Activities
Apr 2022
Publication
The aim of the paper is to analyze how regulatory design and its framework’s topics other than macroeconomic factors might impact green innovation by taking into consideration a brand-new renewable source of energy that is becoming more and more important in recent years: hydrogen and fuel cell patenting activities. Such activities have been used as a proxy for green technological change in a panel data of 52 countries over a 6-year period. A series of sectorial energy regulation and macroeconomic variables were tested to assess their impact on that technological frontier of green energy transition policy. As might have been expected the empirical analysis carried out with the model that was prefigured confirms significant evidence of lock-in effects on fossil fuel policies. The model confirms however another evidence: countries already investing in renewables might be willing to invest in hydrogen projects. A sort of reinforcement to the further development of green sustainable strategies seems to derive from having already concretely undertaken this direction. Future research should exploit different approaches to the research question and address the econometric criticalities mentioned in the paper along with exploiting results of the paper with further investigations.
How Far Away is Hydrogen? Its Role in the Medium and Long-term Decarbonisation of the European Energy System
Nov 2015
Publication
Hydrogen is a promising avenue for decarbonising energy systems and providing flexibility. In this paper the JRC-EU-TIMES model – a bottom-up technology-rich model of the EU28 energy system – is used to assess the role of hydrogen in a future decarbonised Europe under two climate scenarios current policy initiative (CPI) and long-term decarbonisation (CAP). Our results indicate that hydrogen could become a viable option already in 2030 – however a long-term CO2 cap is needed to sustain the transition. In the CAP scenario the share of hydrogen in the final energy consumption of the transport and industry sectors reaches 5% and 6% by 2050. Low-carbon hydrogen production technologies dominate and electrolysers provide flexibility by absorbing electricity at times of high availability of intermittent sources. Hydrogen could also play a significant role in the industrial and transport sectors while the emergence of stationary hydrogen fuel cells for hydrogen-to-power would require significant cost improvements over and above those projected by the experts.
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