Review of hydrogen safety during storage,transmission, and applications processes

Hydrogen is considered an excellent clean fuel with potential applications in several fields. There are serious safety concerns associated with the hydrogen process. These concerns need to be thoroughly understood and addressed to ensure its safe operation. To better understand the safety challenges of hydrogen use, application, and process, it is essential to undertake a detailed risk analysis. This can be achieved by performing detailed consequence modellings and assessing risk using the computational fluid dynamics (CFD) approach. This study comprehensively reviews and analyses safety challenges related to hydrogen, focusing on hydrogen storage, transmission, and application processes. Range of release and dispersion scenarios are investigated to analyse associated hazards. Approaches to quantitative risk assessment are also briefly discussed.     

锂电池在特种设备行业中梯次利用的前景展望

特种设备行业对动力电池的要求不仅局限于功率性能,同时由于特种设备的应用场景特殊性,其环保要求和性价比同样重要。梯次利用作为应对电动汽车退役电池处理的重要手段,在电池余能利用方面发挥重要作用。现有特种设备动力来源正从燃油向电能转化,而且还有一大批鉛酸动力电池需要更新换代,梯次利用锂电池在机电类特种设备行业中的应用符合节能减排的政策导向,具有市场前景。     

阻燃电解液改善钛酸锂电池体系热稳定性研究

为了提高锂离子电池安全性,将碳酸亚乙烯酯、亚硫酸丙烯酯与二甲基乙酰胺加入到1.0mol/L LiPF_6/碳酸乙烯酯+碳酸二乙酯(1∶1wt%)的基准电解液中,配制成阻燃电解液。运用C80微量量热仪对钛酸锂负极(放电至1.0V)与基准电解液共存体系、钛酸锂负极(放电至1.0V)与阻燃电解液共存体系进行热稳定性测试,并计算得到热力学参数。对Li/基准电解液/Li_4Ti_5O_(12)和Li/阻燃电解液/Li_4Ti_5O_(12)半电池进行充放电循环测试、循环伏安测试与SEM扫描电镜测试。实验结果表明,钛酸锂负极与阻燃电解液体系反应放出的热量较钛酸锂负极与基准电解液体系减少了35.4%,且具有更高的活化能,提高了钛酸锂电池体系的热稳定性;同时电化学测试结果表明,阻燃电解液与钛酸锂负极有良好的相容性,可以应用到钛酸锂电池体系。     

Semi-quantitative risk assessment of commercial scale supply chain of hydrogen fuel and implications for industry and society

This paper is derived from a study on the safety of bulk transport and storage of hydrogen as a fuel, carried out by the Health and Safety Laboratory (HSL) for the Department for Transport (DfT). The aim of the study was to identify the knowledge and data required to develop fully a risk assessment for a hydrogen delivery and storage infrastructure. The methodology used was to begin to carry out a risk assessment for a representative delivery and storage supply chain, using a risk assessment methodology commensurate with the availability of necessary data. Semi-quantitative risk assessment was carried out through top-down HAZID brainstorming, consequence modelling using commercially available software, and use of a risk matrix.Finally through the risk assessment carried out and relevant literature review, the gaps in hazard identification, consequence modelling and frequency assessment, which should be filled to develop a quantified methodology, were compiled.Using data for current UK LPG consumption, comparisons were made between hydrogen and LPG for mode of failures and number of trips required to supply equivalent energy demand. The implications of using ammonia as a hydrogen carrier (hydrogen is within the ammonia molecule) and regulatory implications on hydrogen fuelling or storage sites are also discussed.     

The hazards and risks of hydrogen

An analysis was completed of the hazards and risks of hydrogen, compared to the traditional fuel sources of gasoline and natural gas (methane). The study was based entirely on the physical properties of these fuels, and not on any process used to store and extract the energy. The study was motivated by the increased interest in hydrogen as a fuel source for automobiles.The results show that, for flammability hazards, hydrogen has an increased flammability range, a lower ignition energy and a higher deflagration index. For both gasoline and natural gas (methane) the heat of combustion is higher (on a mole basis). Thus, hydrogen has a somewhat higher flammability hazard.The risk is based on probability and consequence. The probability of a fire or explosion is based on the flammability range, the auto-ignition temperature and the minimum ignition energy. In this case, hydrogen has a larger flammability zone and a lower minimum ignition energy—thus the probability of a fire or explosion is higher. The consequence of a fire or explosion is based on the heat of combustion, the maximum pressure during combustion, and the deflagration index. Hydrogen has an increased consequence due to the large value of the deflagration index while gasoline and natural gas (methane) have a higher heat of combustion. Thus, based on physical properties alone, hydrogen poses an increase risk, primarily due to the increased probability of ignition.This study was unable to assess the effects of the increased buoyancy of hydrogen—which might change the probability depending on the actual physical situation.A complete hazard and risk analysis must be completed once the actual equipment for hydrogen storage and energy extraction is specified. This paper discusses the required procedure.     

Explosibility of hydrogen–graphite dust hybrid mixtures

To evaluate the hazard of combined hydrogen/dust explosions under severe accident conditions in International Thermonuclear Experimental Reactor (ITER), standard method of 20-L-sphere was used to measure the explosion indices of 4-μm fine graphite dust in lean hydrogen/air mixtures. The mixtures were ignited by a weak electric spark. The tested fuel concentrations were 8–18 vol% H₂ and 25–250 g/m³ dust. If the hydrogen content is higher than 10 vol%, the dust constituent can be induced to explode by the hydrogen explosion initiated by a weak electric spark. Depending on the fuel component concentrations, the explosions proceed in either one or two stages. In two-stage explosions occurring at low hydrogen and dust concentrations, the mixture ignition initiates first a fast hydrogen explosion followed by a slower phase of the dust explosion. With increasing dust concentration, the dust explodes faster and can overlap the hydrogen-explosion stage. At higher hydrogen concentrations, the hybrid mixtures explode in one stage, with hydrogen and dust reacting at the same time scale. Maximum overpressures of hybrid explosions are higher than those observed with hydrogen alone; maximum rates of pressure rise are lower in two-phase explosions and, generally, higher in one-stage explosions, than those characteristic of the corresponding H₂/air mixtures.     

Thermal hazard evaluation for γ-valerolactone production by using formic acid as hydrogen donor

Aiming at the green and sustainable energy substitution and supply, biomass valorization has become a potential strategy to face the energy crisis and increasing demand all over the world from long-term perspectives. Among the bio-based chemicals, γ-valerolactone (GVL) production from hydrogenation of levulinic acid (LA) and its esters has attracted great interests due to its wide applications, such as fuel, solvent, and additives. However, the safety evaluation for this hydrogenation reaction has received few attentions. To fill this gap, thermal hazard evaluation for GVL production from LA hydrogenation by using formic acid (FA) as hydrogen donor was first performed. The process conditions were optimized by using orthogonal experimental method for further calorimetry study. Thermal stability of chemicals and thermal risk of reaction process under adiabatic conditions were investigated by applying differential scanning calorimetry and accelerating rate calorimeter Phi-Tec II, respectively. The results revealed that the chemicals were stable in temperature range from 30 to 250 °C except FA due to its evaporation and decomposition with endothermic behaviors. The reaction process under isothermal and adiabatic conditions demonstrates that the decomposition of FA was rapid and followed by the hydrogenation of LA to GVL. Based on kinetic model under adiabatic conditions and risk matrix, the thermal runaway risk was found to be medium, indicating that certain safety measures should be properly designed and taken for loss prevention. This work could benefit the safety design and thermal risk prevention for GVL production by using FA as hydrogen donor.     

Fatal crashes involving large numbers of vehicles and weather

IntroductionAdverse weather has been recognized as a significant threat to traffic safety. However, relationships between fatal crashes involving large numbers of vehicles and weather are rarely studied according to the low occurrence of crashes involving large numbers of vehicles.MethodBy using all 1,513,792 fatal crashes in the Fatality Analysis Reporting System (FARS) data, 1975–2014, we successfully described these relationships.ResultsWe found: (a) fatal crashes involving more than 35 vehicles are most likely to occur in snow or fog; (b) fatal crashes in rain are three times as likely to involve 10 or more vehicles as fatal crashes in good weather; (c) fatal crashes in snow [or fog] are 24 times [35 times] as likely to involve 10 or more vehicles as fatal crashes in good weather. If the example had used 20 vehicles, the risk ratios would be 6 for rain, 158 for snow, and 171 for fog.ConclusionsTo reduce the risk of involvement in fatal crashes with large numbers of vehicles, drivers should slow down more than they currently do under adverse weather conditions. Driver deaths per fatal crash increase slowly with increasing numbers of involved vehicles when it is snowing or raining, but more steeply when clear or foggy.Practical applicationsWe conclude that in order to reduce risk of involvement in crashes involving large numbers of vehicles, drivers must reduce speed in fog, and in snow or rain, reduce speed by even more than they already do.     

Fire Tests on E-vehicle Battery Cells and Packs

Objective: The purpose of this study was to investigate the effects of abuse conditions, including realistic crash scenarios, on Li ion battery systems in E-vehicles in order to develop safe practices and priorities when responding to accidents involving E-vehicles.

Method: External fire tests using a single burning item equipment were performed on commercial Li ion battery cells and battery packs for electric vehicle (E-vehicle) application. The 2 most common battery cell technologies were tested: Lithium iron phosphate (LFP) and mixed transition metal oxide (lithium nickel manganese cobalt oxide, NMC) cathodes against graphite anodes, respectively. The cell types investigated were “pouch” cells, with similar physical dimensions, but the NMC cells have double the electric capacity of the LFP cells due to the higher energy density of the NMC chemistry, 7 and 14 Ah, respectively.

Heat release rate (HRR) data and concentrations of toxic gases were acquired by oxygen consumption calorimetry and Fourier transform infrared spectroscopy (FTIR), respectively.

Results: The test results indicate that the state of charge (SOC) affects the HRR as well as the amount of toxic hydrogen fluoride (HF) gas formed during combustion. A larger number of cells increases the amount of HF formed per cell. There are significant differences in response to the fire exposure between the NMC and LFP cells in this study. The LFP cells generate a lot more HF per cell, but the overall reactivity of the NMC cells is higher. However, the total energy released by both batteries during combustion was independent of SOC, which indicates that the electric energy content of the test object contributes to the activation energy of the thermal and heat release process, whereas the chemical energy stored in the materials is the main source of thermal energy in the batteries.

Conclusions: The results imply that it is difficult to draw conclusions about higher order system behavior with respect to HF emissions based on data from tests on single cells or small assemblies of cells. This applies to energy release rates as well. The present data show that mass and shielding effects between cells in multicell assemblies affect the propagation of a thermal event.     

氢安全研究现状及面临的挑战

氢能具有储运便捷、来源多样、洁净环保等突出优点,许多国家把发展氢能作为重要的能源战略。氢安全是氢能大规模商业化应用的重要保障。在分析国内外氢安全领域近年来最新研究进展的基础上,依次从氢泄漏与扩散、氢燃烧与爆炸、氢与金属材料相容性及氢风险评价等方面,系统总结了国内外氢安全研究面临的挑战,并对我国氢安全的发展提出了建议。     

热污染及其防治

对热污染状况进行了介绍.概括了热污染的危害,包括危害人体健康、影响全球气候变化、污染大气、污染水体、加快水分蒸发、增加能量消耗等.分析了热污染的原因,自然气候的异常变化和人为因素是热污染产生的两大原因.最后提出了几点防治热污染的措施.     

CFD modelling of hydrogen release, dispersion and combustion for automotive scenarios

The paper describes the analysis of the potential effects of releases from compressed gaseous hydrogen systems on commercial vehicles in urban and tunnel environments using computational fluid dynamics (CFD). Comparative releases from compressed natural gas systems are also included in the analysis.

This study is restricted to typical non-articulated single deck city buses. Hydrogen releases are considered from storage systems with nominal working pressures of 20, 35 and 70 MPa, and a comparative natural gas release (20 MPa). The cases investigated are based on the assumptions that either fire causes a release via a thermally activated pressure relief device(s) (PRD) and that the released gas vents without immediately igniting, or that a PRD fails. Various release strategies were taken into account. For each configuration some worst-case scenarios are considered.

By far the most critical case investigated in the urban environment, is a rapid release of the entire hydrogen or natural gas storage system such as the simultaneous opening of all PRDs. If ignition occurs, the effects could be expected to be similar to the 1983 Stockholm hydrogen accident [Venetsanos, A. G., Huld, T., Adams, P., & Bartzis, J. G. (2003). Source, dispersion and combustion modelling of an accidental release of hydrogen in an urban environment. Journal of Hazardous Materials, A105, 1–25]. In the cases where the hydrogen release is restricted, for example, by venting through a single PRD, the effects are relatively minor and localised close to the area of the flammable cloud. With increasing hydrogen storage pressure, the maximum energy available in a flammable cloud after a release increases, as do the predicted overpressures resulting from combustion. Even in the relatively confined environment considered, the effects on the combustion regime are closer to what would be expected in a more open environment, i.e. a slow deflagration should be expected.

Among the cases studied the most severe one was a rapid release of the entire hydrogen (40 kg) or natural gas (168 kg) storage system within the confines of a tunnel. In this case there was minimal difference between a release from a 20 MPa natural gas system or a 20 MPa hydrogen system, however, a similar release from a 35 MPa hydrogen system was significantly more severe and particularly in terms of predicted overpressures. The present study has also highlighted that the ignition point significantly affects the combustion regime in confined environments. The results have indicated that critical cases in tunnels may tend towards a fast deflagration, or where there are turbulence generating features, e.g. multiple obstacles, there is the possibility that the combustion regime could progress to a detonation.

When comparing the urban and tunnel environments, a similar release of hydrogen is significantly more severe in a tunnel, and the energy available in the flammable cloud is greater and remains for a longer period in tunnels. When comparing hydrogen and natural gas releases, for the cases and environments investigated and within the limits of the assumptions, it appears that hydrogen requires different mitigation measures in order that the potential effects are similar to those of natural gas in case of an accident. With respect to a PRD opening strategy, hydrogen storage systems should be designed to avoid simultaneous opening of all PRD, and that for the consequences of the released energy to be mitigated, either the number of PRDs opening should be limited or their vents to atmosphere should be restricted (the latter point would require validation by a comprehensive risk assessment).     

车载储氢瓶泄漏及车库内通风方式研究

为研究车库内燃料电池汽车氢气意外泄漏后的浓度分布情况,采用ANSYS软件,通过分析可燃性气体体积、水平方向和垂直方向氢气的扩散分布、不同泄漏位置氢气的扩散情况,研究6种不同通风方式对氢气意外泄漏扩散分布的影响,针对车库内氢气泄漏的特性,在通风方式上引入侧墙底部送风和侧墙顶部送风方式。研究结果表明：底部送风能显著加快氢气的扩散和排出。垂直高度上氢气浓度分布不均,侧墙顶部送风能使顶部堆积的氢气向下扩散,降低最大气体浓度;在墙角泄漏会由于墙壁的影响导致氢气堆积,对墙角局部通风尤为重要。研究结果可为氢燃料电池汽车专用车库的通风设计提供重要参考。     

Risk quantification framework of hydride-based hydrogen storage systems for light-duty vehicles

This study aims to develop a quantitative risk assessment (QRA) framework for on-board hydrogen storage systems in light-duty fuel cell vehicles, with focus on hazards from potential vehicular collision affecting hydride-based hydrogen storage vessels. Sodium aluminum hydride (NaAlH₄) has been selected as a representative reversible hydride for hydrogen storage. Functionality of QRA framework is demonstrated by presenting a case study of a postulated vehicle collision (VC) involving the onboard hydrogen storage system. An event tree (ET) model is developed for VC as the accident initiating event. For illustrative purposes, a detailed FT model is developed for hydride dust cloud explosion as part of the accident progress. Phenomenologically-driven ET branch probabilities are estimated based on an experimental program performed for this purpose. Safety-critical basic events (BE) in the FT model are determined using conventional risk importance measures. The Latin Hypercube sampling (LHS) technique has been employed to propagate the aleatory (i.e., stochastic) and epistemic (i.e., phenomenological) uncertainties associated with the probabilistic ET and FT models. Extrapolation of the proposed QRA framework and its core risk-informed insights to other candidate on-board reversible and off-board regenerable hydrogen storage systems could provide better understanding of risk consequences and mitigation options associated with employing this hydrogen-based technology in the transportation sector.     

过氧化氢热爆炸研究进展

过氧化氢作为绿色环保的氧化剂,广泛应用于工业的各个领域,同时也因其热分解爆炸危险性导致了一系列严重的火灾爆炸事故。过氧化氢在高温或与一些不兼容化学物质作用下,将会激发其热危险性,进而引发热失控反应,最终导致爆炸事故的发生。结合近年来国内发生的过氧化氢热爆炸事故,简要概述了其热爆炸事故历程,并从理论研究和实验研究两个方面综述了过氧化氢热爆炸的研究进展。理论研究方面,主要介绍了化学反应失控模型和基于热动力学的研究方法,尤其对基于热失控模型的热风险评估进行了详细的阐述。实验研究方面,分析了高温条件下与杂质催化作用下过氧化氢的热危险性,包括无机杂质和有机杂质。最后就过氧化氢热爆炸的研究提出了进一步的研究方向。     

炼厂液化石油气(高含烯烃LPG)作为车用燃料的试验研究

炼厂液化石油气成分复杂,主体成分包含大量的烯烃,且含有硫、水及其他杂质.将其直接作为汽车燃料,对车辆以及燃料供给系统均存在不同程度的危害.通过试验研究除杂等精制工艺过程,得到了高含烯烃精制液化石油气,消除了杂质对燃料供给系统和发动机的影响.并研究了高含烯烃液化石油气在车辆上的使用性能.试验表明,高含烯烃液化石油气可使车辆的动力性有所提高,排放性能与标准车用液化石油气接近.由于炼厂液化石油气价格相对较低,因此车辆燃料费用大大降低,得到了包括出租车辆在内的广大用户的认可,具有良好的推广应用前景.     

Analyzing effective factors on leakage-induced hydrogen fires

Currently, novel energy resources are receiving increasing attention as a response to the limitation in fossil fuels as well as their adverse effects on human health. Hydrogen, one of the most abundant elements on the earth, can be regarded as a new energy source to replace fossil fuels. Therefore, safety assessment of the relating processes is very crucial by increasing use of hydrogen as a fuel source. In this regard, consequence analysis for risk assessment and power reduction is very important. The present study aims at modeling hydrogen dispersion along with consequence analyses for such events as jet fire and flash fire. The model was validated by using the data derived from a study on hydrogen leakage in supply pipelines in the laboratory of the University of Pisa. Modeling results reveal that ambient conditions will impose a milder impact on leakage consequences if internal pressure is high in release source. The safe distance was also estimated to be 14 m. Dispersion consequence modeling was performed, followed by the evaluation of the effect of environmental (i.e., stability, ambient temperature, surface roughness, wind speed, and humidity) and process (i.e., vessel temperature and pressure, leakage diameter, and releasing point height) parameters on maximum size flammable vapor cloud and maximum level jet fire radiation on the ground. The size of flammable vapor cloud (consequence dispersion index) and the maximum flux of radiation were affected by process parameters more than ambient parameters. Leakage diameter and the vessel pressure were found to have the highest impact on the operational parameters.     

Characterization of Ti powders mixed with TiO2 powders: Thermal and kinetic studies

The fire and explosion risks of metal powders admixed with solid inertants have been extensively investigated for many years. However, it remains unclear why such solid mixtures have high potential fire and explosion risk even when mixed with high percentages of non-combustible solids. This paper investigates how to interpret these risks, from a microscopic perspective, with thermal and kinetic parameters including initial ignition temperature, mass unit exothermic energy, activation energy and risk index of spontaneous combustion. The results show that the initial ignition temperature based on TG (Thermogravimetry) analysis is related to ignition sensitivity, and increased with percentage of admixed solid inertant. The unit mass exothermic energy based on DSC (Differential scanning calorimetry) analysis is related to flame spread velocity. Activation energy and the risk index of spontaneous combustion can be used to explain the reactivity and spontaneous combustion hazard, respectively, of metal powders. We conclude that thermal and kinetic parameters may provide another way to describe the fire and explosion risk of combustible powders, especially for nano metal powders due to the laboratory safety in the normative tests for explosion parameter determination.     

铂载钴钼二元硫化物对H_2S电催化活性研究

为考察溶胶凝胶法制备的Co-Mo二元硫化物对H_2S气体的电催化活性,通过循环伏安法和Tafel曲线分析对铂载不同Co、Mo掺杂比的电催化剂进行表征.结果表明,不同阳极电催化剂交换电流密度J_0由大到小依次为,铂载n(Co):n(Mo)=2:3、铂载n(Co):n(Mo)=2:1、铂载n(Co):n(Mo)=1:1和铂,即铂载n(Co):n(Mo)=2:3阳极电催化剂具有较好的活性,这与循环伏安曲线测试结果一致.电解质溶液pH值为6～7时,随着温度的升高铂载n(co):n(Mo)=2:3阳极电催化剂活性呈现上升的趋势.优化后的Co、Mo掺杂原子比约为0.66,此类电催化剂在操作温度80℃下,交换电流密度为1.318mA/cm~2,表观活化焙值为616.6 kJ/mol .研究表明,铂载钴钼二元硫化物适合作为低温H_2S燃料电池阳极电催化剂,其中Co、Mo掺杂比对电催化活性影响较大.     

Lithium ion battery energy storage systems (BESS) hazards

There has been an increase in the development and deployment of battery energy storage systems (BESS) in recent years. In particular, BESS using lithium-ion batteries have been prevalent, which is mainly due to their power density, performance, and economical aspects. BESS have been increasingly used in residential, commercial, industrial, and utility applications for peak shaving or grid support. As the number of installed systems is increasing, the industry has also been observing more field failures that resulted in fires and explosions. Lithium-ion batteries contain flammable electrolytes, which can create unique hazards when the battery cell becomes compromised and enters thermal runaway. The initiating event is frequently a short circuit which may be a result of overcharging, overheating, or mechanical abuse. During the exothermic reaction process (i.e., thermal runaway), large amounts of flammable and potentially toxic battery gas will be generated. The released gas largely contains hydrogen, which is highly flammable under a wide range of conditions. This may create an explosive atmosphere in the battery room or storage container. As a result, a number of the recent incidents resulted in significant consequences highlighting the difficulties on how to safely deal with the hazard. This paper identifies fire and explosion hazards that exist in commercial/industrial BESS applications and presents mitigation measures. Common threats, barriers, and consequences are conceptually shown and how they would be identified in a hazard mitigation analysis (HMA). Mitigation measures that can be implemented to reduce the risk of a fire or an explosion are discussed. The presented information is intended to provide practical information to professionals and authorities in this fairly new industry to assure that prevention and mitigation strategies can be effectively implemented and that the regulatory requirement of the HMA can be met.