纳米储氢材料贮存使用安全评估方法研究

储氢材料贮存使用的安全可靠性是安全工程和可靠性领域中的特殊问题 ,纳米储氢材料的使用 ,其安全性和贮存可靠性同时占有重要地位。笔者依据纳米储氢材料使用和在正常贮存状态下的失效特点 ,应用Poisson过程理论建立纳米储氢材料使用和贮存安全性评估数学模型和统计分析方法 ,给出了在一定置信度下纳米储氢材料贮存寿命与可靠度之间的关系表达式。为纳米储氢材料和新型能源材料研究和使用等提供了理论基础和应用控制的方法。     

Process safety aspects in water-gas-shift (WGS) membrane reactors used for pure hydrogen production

The syngas produced by coal gasification processes can be utilized in Pd-based water-gas-shift membrane reactors for the production of pure H₂. Pd/alloy composite membrane reactors exhibit comparative advantages over traditional packed bed reactors such as simultaneous reaction/separation in one compact unit and increased reaction yields. Furthermore, the development of comprehensive process intensification strategies could further enhance membrane reactor performance resulting in a substantially smaller and functional, inherently safer, environmentally friendlier and more energy efficient process.A systematic non-isothermal modeling framework under both steady state and dynamic/transient conditions for a catalytic high temperature water-gas shift reaction in a Pd-based membrane reactor has been developed to characterize the dynamic behavior of the process system at various operating conditions from a process safety standpoint. In particular, various reaction conditions as well as key process variables such as feed temperature and flow rate, catalyst loading, driving force for H₂ permeation are considered as they are critically related to various safety aspects in the operation of a Pd-based membrane reactor. Within the proposed framework, process parameters and operating conditions which may induce hazards and compromise process safety are identified, analyzed and characterized. Finally, the proposed approach is evaluated through detailed simulation studies in an illustrative case study involving a real Pd-based membrane reactor used for pure hydrogen production and separation that exhibits complex behavior over a wide operating regime.     

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。     

Application of human factors evaluation in engineering design and safe operation of dense phase ethylene treaters

Ethylene treaters are widely used in the petrochemical industry to remove impurities from ethylene feedstock imported from pipeline networks or storage caverns. The safety concerns of dense phase ethylene treaters due to the reactive and highly flammable nature of ethylene are well known and studied. Under certain conditions, ethylene may self-polymerize and decompose violently with heat release. Under other conditions, ethylene will auto-refrigerate, generating cold liquids that may cause potential brittle fracture hazards. Therefore, dense phase ethylene treaters present design challenges with the unique combination of high temperature decomposition and cold temperature brittle fracture hazards.Due to these safety concerns, it is important to select the appropriate engineering design options for dense phase ethylene treaters and the associated regeneration facilities. Totally automated treater regeneration systems add complexity and instrument maintenance requirements while manually operated systems rely heavily on operator training and procedures. Unfortunately, little or no information or design guidance is available from published research findings in the literature on the evaluation and risk assessment of current industrial design options and practices for dense phase ethylene treaters.This paper presents a systematic risk assessment method to evaluate the engineering design and safe operation options for dense phase ethylene treaters. The proposed risk assessment method integrates human factors task analysis into the traditional HAZOP, LOPA and fault tree analysis to allow evaluation of automated, manual and hybrid approaches with a goal of selecting and optimizing design options to ensure plant safety. This approach provides a realistic assessment of the operational risk and allows identification of fit-for-purpose risk reduction. Applying this systematic risk assessment approach, a simpler and more cost effective design solution can be justified, thereby avoiding the need for a high integrity protective system.     

Study on the effect of explosion suppression equipment on hydrogen explosions

Hydrogen safety is a critical component of modern industrial safety production. In this study, a set of hydrogen explosion suppression equipment is designed independently. The suppression effects of the equipment on hydrogen explosions are studied at normal room temperature and pressure. The experimental results show that the actuation time of the equipment and the spraying mode of the suppressant are the main factors leading to the failure of the hydrogen explosion suppression equipment. The flame, with a hydrogen equivalence ratio of 0.7 and 1.0, spreads out of control when the suppressant touches the flame front. At this time, the addition of the suppressant enhances flame propagation and increases pressure. In addition, because the suppressant does not fully cover the developing flame, the hydrogen flame with the equivalence ratio of 0.5 eventually breaks through the suppressant cloud, and the explosion happens. However, when the initial flame is completely covered by the suppressant, the hydrogen explosion is suppressed by hydrogen explosion suppression equipment. This research provides a solid and reliable foundation for hydrogen explosion suppression equipment in industrial safety and production protection.     

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.     

An innovative and comprehensive approach for the consequence analysis of liquid hydrogen vessel explosions

Hydrogen is one of the most suitable solutions to replace hydrocarbons in the future. Hydrogen consumption is expected to grow in the next years. Hydrogen liquefaction is one of the processes that allows for increase of hydrogen density and it is suggested when a large amount of substance must be stored or transported. Despite being a clean fuel, its chemical and physical properties often arise concerns about the safety of the hydrogen technologies. A potentially critical scenario for the liquid hydrogen (LH₂) tanks is the catastrophic rupture causing a consequent boiling liquid expanding vapour explosion (BLEVE), with consequent overpressure, fragments projection and eventually a fireball. In this work, all the BLEVE consequence typologies are evaluated through theoretical and analytical models. These models are validated with the experimental results provided by the BMW care manufacturer safety tests conducted during the 1990's. After the validation, the most suitable methods are selected to perform a blind prediction study of the forthcoming LH₂ BLEVE experiments of the Safe Hydrogen fuel handling and Use for Efficient Implementation (SH₂IFT) project. The models drawbacks together with the uncertainties and the knowledge gap in LH₂ physical explosions are highlighted. Finally, future works on the modelling activity of the LH₂ BLEVE are suggested.     

基于氢气充放试验及数值模拟的储氢气瓶安全评价

储氢气瓶是新能源汽车的重要储能设备,其可靠性直接关系到汽车的安全性。研究了不同环境温度下,35 MPa铝合金内胆车用储氢III型气瓶在充放气时的最终温度和应力分布情况,并对其安全性进行了评价。借助试验测试平台,在不同温度下进行了实际充放试验。试验过程中无漏气现象,且最终温度符合要求,表明储氢气瓶在试验条件下是安全的。由此,在获得了储氢气瓶充放时热响应规律的基础上,对不同温度下的氢气充放过程进行了数值模拟,得到其应力分布情况。结果表明,储氢气瓶复合层的应力远小于其材料抗拉强度,即内胆和复合层的强度均可视为满足要求。研究结果可为储氢气瓶的试验开展、安全评价、寿命预测提供依据。     

室内氢气泄漏扩散的数值模拟

氢能是有发展前景的新型能源之一,氢气的安全储存是氢能应用必须解决的问题。本文建立了基于大容量金属储氢装置的室内氢气泄漏扩散模型,利用计算流体力学软件FLUENT,对室内储氢罐的泄漏扩散过程进行数值模拟,得到了氢气泄漏扩散的速度分布、浓度分布。分析数值模拟结果,得出在该模拟条件下,氢气泄漏时的流动状态为射流湍流;泄漏后上浮扩散,空间密闭时积累于室顶;通风条件下大部分区域的氢气浓度仍然高于安全限值。通过数值模拟,总结出氢气在室内环境下的泄漏扩散规律,可为氢气泄漏事故的处理消防安全设置提供依据。     

A review on hybrid mixture explosions: Safety parameters,explosion regimes and criteria,flame characteristics

The hybrid mixture of combustible dusts and flammable gases/vapours widely exist in various industries, including mining, petrochemical, metallurgical, textile and pharmaceutical. It may pose a higher explosion risk than gas/vapor or dust/mist explosions since the hybrid explosions can still be initiated even though both the gas and the dust concentration are lower than their lower explosion limit (LEL) values. Understanding the explosion threat of hybrid mixtures not only contributes to the inherent safety and sustainability of industrial process design, but promotes the efficiency of loss prevention and mitigation. To date, however, there is no test standard with reliable explosion criteria available to determine the safety parameters of all types of hybrid mixture explosions, nor the flame propagation and quenching mechanism or theoretical explanation behind these parameters. This review presents a state-of-the-art overview of the comprehensive understanding of hybrid mixture explosions mainly in an experimental study level; thereby, the main limitations and challenges to be faced are explored. The discussed main contents include the experimental measurement for the safety parameters of hybrid mixtures (i.e., explosion sensitivity and severity parameters) via typical test apparatuses, explosion regime and criterion of hybrid mixtures, the detailed flame propagation/quenching characteristics behind the explosion severities/sensitivities of hybrid mixtures. This work aims to summarize the essential basics of experimental studies, and to provide the perspectives based on the current research gaps to understand the explosion hazards of hybrid mixtures in-depth.     

Explosion hazards related to hydrogen releases in nuclear facilities

Hydrogen explosion risk needs to be carefully assessed and evaluated in nuclear facilities because of the potential catastrophic consequences: breakdown of safety equipments, failure of containment, dissemination of radioactive materials in the environment.When studying an indoor release, one possible simplification is to assume a perfect gas mixing inside the room. This assumption is effectively often used to evaluate toxic risks in the environment outside a building (Mastellone, Ponte, & Arena, 2003). However, perfect gas mixing assumption is only a rough approximation, as indoor concentrations can largely differ from mean values, due to buoyancy, recirculation zones or obstacles for example.In order to better evaluate the risk of explosion in case of an accidental release of hydrogen, IRSN conducted a numerical study using FLACS CFD software. Several parameters have been studied to identify dangerous situations and draw a representative picture of the risk: room size, position and direction of hydrogen leak, ventilation characteristics. Hydrogen release flow rates used for numerical simulations have been chosen as the highest leak rate which, by applying the assumption of perfect mixing, produces an average concentration in the room equal to hydrogen lower flammability limit (LFL).Simulation results indicate that in some particular configurations, especially for impinging hydrogen jets, hydrogen concentrations can locally be above LFL and then create explosive atmospheres with significant volumes.     

普光天然气净化厂投料试车H2S泄漏安全管理

普光气田天然气净化厂是中国石化集团公司"川气东送工程"的关键组成部分,在投料试车期间,富含高浓度H2S的原料气决定了净化过程中的泄漏中毒高风险,尤其在投料试车过程中,实时监测现场H2S气体浓度是试车安全管理的关键。介绍了天然气净化厂净化工艺,分析了试车安全风险;利用安全监测系统、GasFindIR红外成像仪、有毒挥发气体分析仪等先进仪器设备建立了实时安全管理监测方法,实时监测现场H2S气体浓度。结果表明,该方法在天然气净化厂投料试车阶段发现H2S气体泄漏及时,泄漏点定位准确,泄漏量检测精确,保证了普光气田天然气净化厂投料试车作业安全的顺利进行,为高含H2S气田投料试车作业的安全管理提供了参考。     

The legacy of Bhopal: The impact over the last 20 years and future direction

Chemical process safety was not a major public concern prior to 1984. As far as chemical hazards were concerned, public fears focused on disease (cancer) and environmental degradation. Even a series of major process incident tragedies did not translate into widespread public concerns about major incidents in chemical plants that might disastrously affect the public. This situation changed completely after the December 1984 disaster at the Union Carbide plant in Bhopal. Not only was the public's confidence in the chemical industry shaken, the chemical industry itself questioned whether its provisions for protection against major incidents were adequate.

The recognition of the need for technical advances and implementation of management systems led to a number of initiatives by various stakeholders throughout the world. Governments and local authorities throughout the world initiated regulatory regimes. Has all that has resulted from the legacy of Bhopal reduced the frequency and severity of incidents? How can we answer this question? As we move into more and more globalization and other complexities what are the challenges we must address? According to the authors, some of these challenges are widespread dissemination and sharing of lessons learned, risk migration because of globalization, changing workforce, and breakthroughs in emerging areas in process safety.     

Assessment of hazardous material risks for rail yard safety

This paper illustrates the application of quantitative risk assessment in a rail yard where tank cars of hazardous materials are received and stored. The assessment was conducted in response to community concerns about the safety of a proposed yard expansion. Six different chemicals are involved. For each one, the average monthly volume and the hazard of most concern are specified. We use an event tree populated with empirical data to compute the probability of a major spill in each case and we estimate the corresponding critical impact distances using available modeling tools. We find that for some of the chemicals, the relative increases in risk are appreciable, but that in all cases, the absolute levels of risk remain low. Then we identify some ways in which such an analysis can be extended and discuss the potential difficulties associated with these extensions.     

Identification of accident scenarios caused by internal factors using HAZOP to assess an organic hydride hydrogen refueling station involving methylcyclohexane

Organic hydride hydrogen refueling stations have been remarked as stations that can employ a practicable method based on the organic chemical hydride system involving methylcyclohexane (MCH) for the transport of hydrogen. This station has advantages in that the storage and transportation of MCH does not require a large amount of energy compared to compressed and liquefied hydrogen, and the system can use existing infrastructure. This type of station involves some hazardous materials, and thus, scenario identifications and risk assessments have been performed by researchers. However, the sample of studies available have employed a conceptual design model, and they did not identify concrete scenarios triggered by internal factors. Therefore, the purpose of this study is to identify accidental scenarios caused by internal factors that can affect an organic hydride hydrogen refueling station. In this study, we used Hazard and Operability study (HAZOP) and examined safety measures for the scenarios. As a result of the HAZOP, 105 accidental scenarios were identified and classified into the two following groups; (i) the scenarios assumed that the substances were ignited after they were released to the atmosphere, and (ii) the scenarios assumed that the substances were ignited in the process before they were released. Significant scenarios in group (i) were MCH or toluene pool fires, hydrogen jet fires, vapor gas explosions, or flash fires. The significant scenarios classified in (ii) were newly identified in this study. The scenarios include the explosion of the explosive mixture formed by the gaseous phase of toluene and oxygen from the vent line connected to the tank due to the static electric charge in the tank. For each scenario, safety measures to prevent the progression of the accident scenario were examined with reference to the current laws and regulations in Japan.     

Using soybean isoflavone to prevent hydrogen production reaction of aluminium dust and water in wet dust removal systems

Using a dry dust removal system used for aluminium dust collection presents a dust explosion risk, whereas a wet dust removal system presents a risk of hydrogen fire and explosion. Neither system can attain a sufficient level of safety for use at aluminium processing sites. In this paper, soybean isoflavone, a non-toxic and environmentally sustainable flavonoid, was investigated to inhibit hydrogen production from aluminium dust and water. Scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and Fourier transform infrared spectroscopy (FTIR) were used to characterize aluminium particles before and after the reaction. Soybean isoflavone was found to inhibit hydrogen production from aluminium dust and water. At a soybean isoflavone solution concentration of 2.1 g L⁻¹, a dense protective film resulting from chemical adsorption on the surfaces of the aluminium particles isolated the aluminium particles from water molecules. This film blocked the reaction pathway between the aluminium particles and water to suppress hydrogen generation. This fundamental study addresses the problems of hydrogen fires and explosions in wet dust removal systems for aluminium dust collection and provides a novel, safe and effective method for aluminium dust removal.     

Detailed and reduced chemistry for hydrogen autoignition

Reaction-rate parameters are given for the detailed chemistry of gas-phase hydrogen combustion, involving 21 reversible elementary steps. It is indicated that, when attention is restricted to specific combustion processes and particular conditions of interest, fewer elementary steps are needed. In particular, for calculating autoignition times over a wide range of pressures for temperatures between about 1000 and 2000 K, five irreversible elementary steps suffice, yielding a remarkable reduction in complexity. It is explained that, from a mathematical viewpoint, in terms of global reaction-kinetic mechanisms, the hydrogen–oxygen system in principle comprises only six overall steps. Rational reduced chemical mechanisms for hydrogen combustion therefore necessarily must have fewer than six overall steps. For autoignition over the range of conditions specified above, ignition times can be determined accurately by considering, in addition to an elementary initiation step and an elementary termination step, at most three overall steps for reaction intermediaries, which reduce to two for very fuel-lean conditions and to one for stoichiometric or fuel-rich conditions. The resulting reductions can simplify computations that need to be performed in risk analyses for hydrogen storage and utilization.     

An improved methodology for assessing risk in aircraft operations at airports, applied to runway overruns

The paper addresses the need for models to assess risk at any particular airport, based on risk management principles used by the present risk management process, that use all available data on previous accidents. The case of runway overruns is taken as an example application, because new regulations require the provision of much longer Runway End Safety Areas than had previously been the norm. The paper presents models for overruns arising from both landings and aborted takeoffs. In each case models of overrun risk, of wreckage location and of the consequences are detailed. An example application of the models is then given in a hypothetical risk assessment.The models, though adding value to existing methods of assessing risk, are not as good as they could be, due to the lack of data on normal operations. It was therefore possible only to relate the rate of overruns to the rate of occurrence of the possible driving factors for a few factors where such comparable data on normal operations existed. It is recommended that effort be put into the collection of data to allow a more comprehensive analysis.     

A pattern of contractor selection for oil and gas industries in a safety approach using ANP-DEMATEL in a Grey environment

Contractor selection is one of the major concerns of industry managers such as those in the oil industry. The objective of this study was to determine a contractor selection pattern for oil and gas industries in a safety approach. Assessment of contractors based on specific criteria and ultimately selecting an eligible contractor preserves the organizational resources. Due to the safety risks involved in the oil industry, one of the major criteria of contractor selection considered by managers today is safety. The results indicated that the most important safety criterion of contractor selection was safety records and safety investments. This represented the industry’s risks and the impact of safety training and investment on the performance of other sectors and the overall organization. The output of this model could be useful in the safety risk assessment process in the oil industry and other industries.     

Competency requirements for process hazard analysis (PHA) teams

Process hazard analysis (PHA) is a cornerstone of process safety management programs. The quality of the PHA performed directly affects the level of risk tolerated for a process. The lower the quality of a PHA, the more likely higher risk will be tolerated. There are few requirements for PHA team members in the U.S. Occupational Safety and Health Administration's process safety management regulations. More detailed requirements for participation in a PHA are desirable.A competency management program should be used to ensure PHA practitioners and teams are appropriately qualified. Criteria for selecting PHA team leaders, or facilitators, and other team members are key to such a program and are described in this paper. The criteria cover both technical and personal attributes. Application of the criteria is described and team performance metrics, which can be used to correlate performance with the assessment of competency to validate the criteria and methods used, are discussed.Owing to the importance of the role played by team leaders, certification of their competency is desirable. Criteria for certification are described and their application is discussed.