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Major accidents in the process industry often lead to the release of light or dense gases, which can mean a thread to employees, local residents or to the environment. Possible scenarios are therefore analyzed and evaluated in advance for approval issues. There is a trend, where simple empirical models are being replaced with more complex numerical models. Gaussian dispersion models or models based on dimensional analysis approaches are for example, increasingly replaced by CFD simulations. The main reason for this is the potentially higher accuracy. However, usually scenarios using sharp parameter values are calculated, since comprehensive consideration of parameter distributions via Monte Carlo or Latin Hypercube Sampling fails due to the numerical effort. This includes the risk that the influence of uncertainties on the simulation results is not taken into account. Response surface methods offer an alternative, with which the CFD problem can be mapped onto an algebraic surrogate model. If this is sufficiently precise, parameter sampling can also be carried out with the surrogate as well, as shown in some publications. Previous investigations only demonstrated the basic principle using trivial dispersion models. In this paper two realistic CFD simulations from the plant safety area are considered: VOC emissions from a storage tank and near-ground dense gas emissions. The entire procedure of response surface determination and parameter studies was automated and parallelized for high-performance-computing, and is carried out on the underlying CFD grids. For the CFD simulations as well as for all visualizations, the commercial software ANSYS CFX and the open source software OpenFOAM were used. The aim of this paper is to demonstrate the method using industry-relevant applications as well as to show how this can be used in practical engineering applications. The quality of surrogate modeling, the numerical effort and advantages that can result from the procedure are discussed as well as advantages which may result from taking parameter uncertainties into account in safety studies.
In this paper, we investigate the evaporation mass flow originating from spills of gas-oline. Large spills of gasoline may form during partial or complete roof sinkings or inthe case of perforations at various deck fittings at external floating roof tanks usedfor the storage. Additionally, spills may form in the retention area in the case of leak-ages at pipes or at the hull. The aim is to predict the order of magnitude of real-scaleevaporation mass flow. The determined evaporation mass flows will be used in arelated project as input values for subsequent dispersion modeling in the vicinity ofthe tanks. This is relevant for questions of fire and explosion protection as well as forenvironmental protection aspects in tank farms or refineries, which use externalfloating roof tanks. The measurements presented in this paper were compared withpredictions by empirical models and investigations of evaporations from small floorspills, round-bottom flask, or from Petri dishes published in the literature. The maingoal of this paper is to test the applicability of empirical models to provide reasonableevaporation mass flows as input for CFD dispersion simulations.
The explosion characteristics of anthracite coal dust with/without small amount of CH4 (1.14 vol %) were investigated by using a 20 L spherical explosion apparatus with an emphasis on the roles of oxygen mole fraction and inert gas. Two methods based on overpressure and combustion duration time were used to determine the minimum explosion concentration (MEC) or the lower explosion limit (LEL) of the pure anthracite coal dust and the hybrid coal-methane mixtures, respectively. The experiment results showed that increasing oxygen mole fraction increases the explosion risk of coal dust: with increasing oxygen mole fraction, the explosion pressure (Pex) and the rate of explosion pressure rise ((dp/dt)ex)) increase, while MEC decreases. The explosion risk of anthracite dust was found to be lower after replacing N2 with CO2, suggesting that CO2 has a better inhibition effect on explosion mainly due to its higher specific heat. However, the addition of 1.14% CH4 moderates the inhibition effect of CO2 and the promotion effect of O2 on anthracite dust explosion for some extent, increasing explosion severity and reducing the MEC of anthracite dust. For hybrid anthracite/CH4 mixture explosions, Barknecht’s curve was found to be more accurate and conservative than Chatelier’s line, but neither are sufficient from the safety considerations. The experimental results provide a certain help for the explosion prevention and suppression in carbonaceous dust industries.
The semi-batch reactors (SBRs) system, which is widely used in industrial processes, possesses an intrinsic parametric sensitivity, in which infinitesimal disturbances of input parameters can result in large variations in output variables. In this work, local parametric sensitivity analysis (PSA) was used to understand parameter variations and global PSA was conducted to examine the interaction of input parameters. The effects of these parameters on the output of the system model were analyzed based on the Monte Carlo method with Latin hypercube sampling and the extended Fourier amplitude sensitivity test model. The results showed that the evolution of thermal behaviors in SBRs were observed: marginal ignition; thermal runaway; and the quick onset, fair conversion, and smooth temperature profile. The threshold point of transition from marginal ignition to thermal runaway was at the maximal value of local sensitivity, for which the slope with respect to cooling temperature equaled zero. Moreover, the sequence of the global sensitivity of six common input parameters was computed and evaluated. The reliability of the numerical models was verified by using our previous experimental results of cyclohexanone peroxide reaction. This comprehensive sensitivity analysis could provide valuable operating information to improve chemical process safety.
The safety characteristics of flammable gases and liquids are required when identifying potentially explosive mixtures and taking appropriate actions concerning explosion protection. Examples are given in this review of the safe handling and evaluation of hazards during the processing, storage, transport, and disposal of flammable liquids and gases. The CHEMSAFE database is presented as a reliable source of safety characteristic data, and ist new open-access version is introduced. CHEMSAFE currently contains assessed properties for about 3000 flammable liquids, gases and mixtures. The lack of a broad experimental foundation in the extensive field of non-atmospheric conditions shows the need for further investigation and standardization. This review summarizes experimental evidence and estimation methods for safety characteristic data under non-atmospheric conditions pointing out current limitations. Suggestions for pre-normative research on safety data under nonatmospheric conditions are given.
In this joint project, standardized measurement methods for hybrid
mixtures are developed, which serve to determine safety
characteristics for explosion protection.
A hybrid mixture is a multi-phase System consisting of fuel gas or
vapor, as well as air and flammable dust. This combination can occur
for instance in drying processes or during heterogenous reaction
processes.
The safety characteristics of flammable gases and liquids are required when identifying potentially explosive mixtures and taking appropriate actions concerning explosion protection. Examples are given in this review of the safe handling and evaluation of hazards during the processing, storage, transport, and disposal of flammable liquids and gases. The CHEMSAFE database is presented as a reliable source of safety characteristic data, and ist new open-access version is introduced. CHEMSAFE currently contains assessed properties for about 3000 flammable liquids, gases and mixtures. The lack of a broad experimental foundation in the extensive field of non-atmospheric conditions shows the need for further investigation and standardization. This review summarizes experimental evidence and estimation methods for safety characteristic data under non-atmospheric conditions pointing out current limitations. Suggestions for pre-normative research on safety data under nonatmospheric conditions are given.
Hydrogen leakage of vehicles in the tunnel is a great threat to the safety operation of the tunnel and longitudinal ventilation strategies have always been utilized to control the fire and smoke movement of rail transit, electric and fossil-fueled vehicles in the engineering field. It is in doubt whether the longitudinal ventilation strategy could still help to reduce the jet fire hazard of transportation with H2 power in the tunnel, considering the rapid development of the hydrogen energy. In present work, a numerical research on effects of longitudinal ventilation strategies on hydrogen jet flames in the tunnel is conducted. The results illustrate that longitudinal ventilation could affect the flame characteristics of jet flames greatly in the tunnel. The critical ventilation velocity increases firstly with the increase of hydrogen leakage rates and then changes little after a critical value. The predicted theoretical model of pool fires could well predict the critical ventilation velocity for hydrogen jet fires. With the increase of longitudinal ventilation velocity, maximum ceiling temperatures are decreased greatly. According to the heat releases, jet speeds and ventilation velocities, three kinds of flame bending characteristics of hydrogen jet fire could be observed due to different effects of the inertial force. At last, the stable thermal stratification could also be destroyed by large ventilation velocities but the corresponding ventilation velocity is far larger than the critical ventilation one. With the increase of longitudinal ventilation velocities, the height of thermal layer is reduced firstly and then maintained at a constant value.
The data center needs more and more electricity due to the explosive growth of IT servers and it could cause electricity power shortage and huge carbon emission. It is an attractive and promising solution to power the data center with hydrogen energy source. The present work aims to conduct an economic analysis on the hydrogen-powered data center. Configurations of hydrogen-powered and traditional data centers are compared and the differences focus on backup power system, converter/inverter, fuel cell subsystem, carbon emission, hydrogen and electricity consumptions. Economic analysis is conducted to evaluate the feasibility to power the data center with hydrogen energy source. Results show that electricity price increasing rate and hydrogen cost are the main factors to influence economic feasibility of hydrogen-powered data center. When the electricity price keeps constant in the coming two decades, the critical hydrogen price is about 2.8 U.S. dollar per kilogram. If the electricity price could increase 5% annually due to explosive growth of electric vehicles and economy, critical hydrogen price will become 6.4 U.S. dollar per kilogram. Hydrogen sources and transportation determine the hydrogen price together. Hydrogen production cost varies greatly with hydrogen sources and production technologies. Hydrogen transport cost is greatly influenced by distances and H2 consumptions to consumers. It could be summarized that the hydrogen-powered data center is economic if hydrogen could be produced from natural gas or H2-rich industrial waste streams in chemical plant and data center could not be built too far away from hydrogen sources. In addition, large-scale hydrogen-powered data center is more likely to be economic. Solar hydrogen powered data center has entered into a critical stage in the economic feasibility. Solar hydrogen production cost has restrained the H2 utilization in data center power systems now, since it could be competitive only when more strict carbon emission regulation is employed, hydrogen production cost reduces greatly and electricity price is increasing greatly in the future. However, it could be expected solar hydrogen-powered system will be adopted as the power source of data centers in the next few years.
Thermoelectric generator (TEG) has been proved as a promising technology for directly converting heat into electricity based on Seebeck effect. On the contrary, this electricity can trigger a solid-state cooling based on conventional Peltier effect. However, these two effects induce a coupling between heat and electric flux, especially for the quantitative relationship still remaining a mystery. Here, we show experimental evidence and theoretical calculation for the coupling by monitoring transient response of fluid temperature and output power. The experimental maximum heat flow in open circuit is 1162 W at cold fluid flow rate = 0.3 m3/h and fluid temperature difference ΔTf = 70 °C, enhanced by 13% owing to heat compensation from intrinsic coupling in closed-loop circuit. Meanwhile, the measured maximum output power of TEG is 18.2 W, and subsequently decreases to 15.4 W due to the objective existence of coupling. This double-edged sword in coupling vigorously inspires the potential applications in heat-dissipation situation such as spacecraft, electronic components, photovoltaic, refrigerator and etc. Present findings open a novel avenue for manipulating heat-electricity conversion in practical engineering.
Gaseous inhibitors are used in many industries for the explosion prevention of combustible dusts, mitigating the potential hazard to humans, properties and environments. This work experimentally and theoretically studied the inerting effect of gaseous inhibitors on the ignition process of dust clouds in O2/N2/CO2 atmospheres, with an emphasis on the role of the CO2/N2 ratio. 10 different combustible carbonaceous dusts were selected, including grain dust, biomass dust and coal dust. Experimental results showed that the inhibition effect of CO2/N2 is closely related to the ignition mechanism of dust clouds. Specifically, a higher ratio of CO2/N2 yields a stronger inhibition effect on the ignition process of dust samples with relatively low volatile matter contents predominated by heterogeneous ignition. In addition, two novel steady-state ignition mechanism models were developed to interpret the experimental observations. Maxwell-Stefan equations were used to describe the diffusivity in the ternary O2/N2/CO2 gas mixtures. The analytical results were in good agreement with the experimental data of the minimum ignition temperature of dust cloud (MITC) in oxygen-lean atmospheres. The mechanism modelling can be used to estimate the critical ignition temperature of all carbonaceous dust clouds with a wide range of volatile matter content under different inert atmospheres, which will provide a reference for the explosion hazard assessment of dust posed by a hot surface in the process industries.
The poor thermal conductivity of MH beds limits hydrogen absorption in metal hydride (MH) reactors for thermochemical heat storage. The compaction of MH powder with expanded natural graphite (ENG) is an efficient and cost-effective approach for the heat transfer enhancement of MH beds. However, the addition of ENG reduces the hydrogen storage density of the compacted composites. How to optimize the allocation of a limited amount of ENG in the MH bed has not been studied. In this study, a multilayer MH bed configuration with an ENG grade content was adopted to improve the heat transfer performance of an MH reactor for thermochemical heat storage. The effect of the ENG content gradient on the performance of the MH reactor was investigated using a mathematical model of the MH reactor. Furthermore, an optimization method based on the entransy dissipation extremum principle (EDEP) was proposed to optimize the ENG distribution in magnesium hydride (MgH2)-ENG compacts. The results showed that a larger ENG content gradient resulted in faster hydrogen absorption and better heat-discharge performance. Compared with a configuration with a uniform ENG content, the optimized configuration based on the EDEP exhibited a shorter reaction time, more uniform bed temperature distribution, and 15.33% higher gravimetric exergy-output rate. In addition, the number of optimization iterations had little effect on the optimal results, which could be obtained by implementing only one optimization iteration. The optimization results showed that more ENG should be allocated to the internal layer of the MgH2-ENG compact. The compacts were divided into three layers, and the ENG content of each layer was calculated according to the optimized configuration based on the EDEP. The optimization method proposed in this study can be applied to optimize
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.
Minimum ignition temperature of dust clouds (MITC) was studied experimentally and theoretically in different atmospheres. Three carbonaceous dusts were tested in both air and O2/CO2 atmospheres with CH4 mole fraction from 0 to 2%. Results showed that the ignition risk of the three dusts significantly increases (decrease of MITC by ~100 ℃) with increasing XO2 from 21% to 50%, but significantly decreases replacing N2 in air with CO2. The inhibition effect of CO2 on MITCs could be diminished by increasing XO2 or adding CH4. The addition of small amount of CH4 has different effects on the MITCs of different dust samples, following the opposite order of volatile matter content: anthracite>bituminous coal>starch. Two modified steady-state ignition models, considering the density of mixture gas and dust cloud, XO2 and its diffusivity, were developed to interpret the experimental observations. The analysis revealed that the global heterogeneous ignition model suits well for the hybrid mixtures of anthracite or bituminous coal dusts. In contrast, the proposed global homogeneous ignition model was found to be only valid for the pure starch dust, and the extra CH4 addition could strongly affect the ignition process of starch, particularly in O2/CO2 atmospheres with higher XO2.
Godbert-Greenwald furnace was used to investigate the minimum ignition temperature of dust clouds (MITC) in air with the presence of flammable gas which is lower than its lower explosion limit (LEL). Three flammable gases (CH4, H2 and CO) and three carbonaceous dusts (anthracite coal, bituminous coal and sweet potato starch) were tested. Results showed that all flammable gases have distinct effects on the MITC of the dust samples and volatile matter content of dust plays an important role during the ignition process. Specifically, the MITC of anthracite coal dust decreased from 610 °C to 560 °C, 580 °C and 570 °C with 3% CH4, 3% CO and 2.5% H2, respectively. Moreover, a heterogeneous ignition mechanism model was proposed to verify the equally global ignition characteristic between hybrid anthracite coal-CxHy mixture and bituminous coal. All three gases had an ignorable effect on the MITC of starch dust considering the experimental error. The presence of CO and H2 slightly promoted the ignition of bituminous coal dust, but the addition of CH4 showed a distinct concentration effect on the MITC of bituminous coal: the MITC decreased with 1% CH4 while increased with 2% and 3% CH4.
This negative-effect of flammable gases at such low concentrations on ignition temperature of bituminous coal dusts was found for the first time. Furthermore, the presence of the 2nd flammable gas had a smaller effect on the MITC of dust samples with a higher volatile content, resulted from the competition of heterogeneous and homogeneous ignition mechanisms.
MIKE III apparatus tests were conducted to investigate the minimum ignition energy (MIE) of coal dusts in air and O2/CO2 atmospheres with and without small amount of CH4/H2. The O2 mole fraction (XO2) in the gas mixtures varied from 21% to 50% with the CH4/H2 mole fraction from 0 to 2%. Experimental result showed that MIE of coal dusts significantly decreases even by three orders of magnitude in mJ with increasing XO2 and the addition of CH4/H2. Compared with CH4, H2 had a relatively strong promotion effect on the spark ignition of coal dusts. The inhibiting effect of CO2 was found to be much stronger than N2, but this inhibiting effect of CO2 could be eliminated by 9% increment of XO2. The effect on MIE of coal dusts thus followed by the order: 9% increment of XO2 > CO2 replacing N2 > 2% CH4 or H2 addition. Moreover, two empirical models were used to estimate the MIE of hybrid dust-gas mixture (HMIE), and the results showed that calculated data can well reflect the promoting effect of elevated XO2 and flammable gas addition, and the inhibiting effect of inert gas
Minimum explosion concentration (MEC) of three agriculture dusts and two coal dusts was studied via a 20-L explosion chamber to reveal the role of gaseous inhibitors. Both active method (CO2 diluting air) and passive method (CO2 replacing O2) were used. The TG and DTG thermal analysis tests were conducted to study the pyrolysis and combustion characteristics of dust samples. An alternative explosion criterion based on combustion duration time was used to determine MEC, and compared with the standardized overpressure method. Under 10-kJ ignition condition, as oxygen mole fraction (XO2) decreased from 21% to 10%, MEC of agriculture dusts and coal dusts respectively increased by around 5 times and 2 times. The active inerting method with a lower N2/CO2 ratio was found to have a better suppression effect on the explosion of the five carbonaceous dusts because the blend has a higher specific heat and a lower oxygen diffusion rate.
Experiments were conducted in a semi-confined pipe to investigate the effects of obstacle location and gasoline vapor concentration on gasoline-air fuel explosions. The variations of internal overpressure, external overpressure, flame propagation and flame-overpressure coupling relationship were analyzed. The results showed thatthe internal overpressure histories existed three obvious peaks, and when the obstacle location was set at 0.4 m, the maximum absolute values of overpressure (pmax and pneg), overpressure rise rates ((dp/dt)ave and (dp/dt)max) and the deflagration index (KG) were obtained. Additionally, more than two positive overpressure peaks were observed in the external overpressure histories. The maximum values of external overpressures and overpressure rise rates were obtained at the obstacle location of 0.4 m. For the fuel concentrations of 1.3%,.1.7% and 2.1%, the shortest time to reach pmax appeared at the obstacle location of 0.4 m, 0.2 m and 0.6 m, respectively, while the shortest time to reach (dp/dt)max and the maximum flame propagation speed were obtained for all the fuel concentrations at the obstacle location of 0.2 m. Moreover, a coupling relationship between overpressure and flame propagation was found. lt could be tleduced that the formation of the positive overpressure peak ofthe external overpressure might be directly related to the gas explosion inside the pipe and the flow jet caused by the high-speed flame propagation. rat her than the external explosion (or secondary explosion) out of the pipe. These results improve our understanding on gas explosion dynamics in a semi- confined space.
The Globally Harmonized System of Classification and Labelling of Chemicals (UN-GHS) is being implemented in more and more countries all over the world; the EU has done so with the CLP-Regulation (EU-CLP). Compared to the undeniably important questions on health and environmental hazards, the classification of physical hazards of chemicals often has not been in the focus, although their implementation can be challenging and there are traps and pitfalls to be avoided. The following overview of the classification systematics for physical hazards aims at a principle understanding without detailing all criteria or test methods. Similarities and differences between the classification systems of the UN-GHS and EU-CLP, the transport of dangerous goods and the former EU system are reviewed with regard to the physical hazard classes. Available physical hazard classifications for the transport of dangerous goods and according to the former EU system can be used as available information when classifying according to the GHS. However, the interfaces of these classification systems and their limitations have to be understood well when concluding on GHS/CLP classifications. This applies not only to industry when applying CLP but especially to legislators when adapting legislation that in one way or another refers to the classification of chemicals.
A series of experiments were conducted in a 10L closed and vented tube with L/D = 10.0, and effects of initial fuel volume concentration, inert gas dilutions (diluted by N2 and CO2), inert gas–water mist twin fluid medium dilutions (diluted by N2-H2O twin fluid medium, CO2-H2O twin fluid medium) and end boundary conditions on overpressure transients of hydrocarbon fuel–air mixtures explosion were revealed. Results show that the overpressure-time profiles consistent with the dynamic evolution law of ‘approximately zero-1st overpressure rising stage-2nd overpressure rising stage-descending stage’, and ‘rate of overpressure rise-time’ curves exhibit the characteristics of multi-stages and multi-peaks, such as (dp/dt)(1,max), (dp/dt)(1,min), (dp/dt)(2,max) and (dp/dt)(2,min). Specifically, as the fuel volume concentration increased, both the maximum overpressures (pmax), and the maximum rates of overpressure rise ((dp/dt)(1,max) and (dp/dt)(2,max)) show a variation trend of increasing firstly and then decreasing, while the corresponding times (tmax, θ(1,max) , θ(2,max)) show a total different variation trend. Moreover, when YCH is lower than 1.88%, the value of (dp/dt)(1,max) is greater than (dp/dt)(2,max), while the value of (dp/dt)(1,max) was less than (dp/dt)(2,max), and when YCH was higher than 1.88%. The addition of N2 and CO2 can obviously inhibit the explosion intensity of hydrocarbon fuel, and the inhibition effect of CO2 is better than that of N2. Due to the synergy inhibition effect of the inert gas and ultrafine water mist, all the values of pmax, (dp/dt)(1,max) and (dp/dt)(2,max) diluted by inert gas-ultrafine water mist twin fluid medium were smaller than those diluted by sole inert gases. In addition, there are significant differences in the overpressure-time and the rate of overpressure rise-time profiles between closed and end venting explosions. The values of maximum overpressure and the rates of overpressure rise of the closed explosion were higher than those of the venting explosion, but the minimum rate of overpressure rise is a smaller one.
To reveal and improve our understanding of the ignition behavior and mechanism, G-G furnace experiments of three typical organic dusts were performed to investigate the minimum ignition temperature (MIT) in O2/N2, O2/ Ar and O2/CO2 atmospheres with oxygen mole fraction from 8.4% to 50%. The experimental results were presented in oxygen-lean and oxy-fuel atmospheres to evaluate the ignition sensitivity of dusts in different atmospheres. It was found that CO2 is the strongest in terms of lowing the ignition sensitivity of the three dusts, and the dust explosion risk increases significantly with increasing O2 mole fraction for the three dusts through a logarithmically and significantly reducing MIT. However, for different dusts, inert gases show different suppression effects. In addition, a modified steady-state homogeneous ignition model was proposed and successfully applied to oxygen-lean atmospheres, and in oxy-fuel atmospheres, this model has also been improved to estimate the ignition mechanism. This ignition mechanism model could be used to successfully predict the minimum ignition temperature of high volatile dust under different inert atmospheres controlled by homogeneous ignition, which will provide a reference for the ignition hazard assessment of dust on hot surfaces.
Experiments have been performed to determine the consequences of a storage vessel containing liquified hydrogen (LH2) is engulfed by a fire. The tests were performed at the Test Site Technical Safety of the Bundesanstalt für Materialforschung und –prüfung (BAM) in Germany within a research cooperation between BAM and Gexcon as part of the SH2IFT program. Three tests were performed using double-walled vacuum insulated vessels of 1 m3 volume varying the orientation of the vessel and the effect of the insulation material used (perlite or multi-layer insulation (MLI)). The degree of filling of the vessel was approximately 35 % in each of the tests performed. The fire load was provided by a propane fed burner positioned under the storage vessel and designed to give a homogeneous fire load. In one of the tests a rupture of the storage vessel occurred causing a blast, a fireball and fragments. Apart from measuring these consequences, the conditions in the vessel (e.g. temperatures and pressure) during the heating process were monitored in all three tests. The work described was undertaken as part of the project Safe Hydrogen fuel handling and Use for Efficient Implementation (SH2IFT).
Large-scale experiments have been performed to investigate the possible consequences of realistic amounts of liquified hydrogen (LH2) encountering water. The experiments aimed at simulating an accidental release of LH2 onto water, for instance during the fuelling of a ship. For liquified natural gas (LNG), it has been demonstrated that physical explosions may occur when it is spilled onto water. These phenomena are referred as rapid phase transitions (RPTs). It cannot be excluded that RPTs are also possible in the case of LH2. The tests were performed at the Test Site Technical Safety of the Bundesanstalt für Materialforschung und –prüfung (BAM) in Horstwalde, Germany. The tests were performed in a 10 m x 10 x 1.5 m basin filled with water. LH2 releases of up to about 1 kg/s were established releasing directly from a trailer carrying LH2. The releases occurred from a height of 50 cm above the water surface pointing downwards, 30 cm under the water surface pointing downwards and 30 cm under the water surface pointed along the water surface. All release configurations resulted in a very chaotic LH2-water mixing zone, causing considerable evaporation and resulting in minor over pressures. No RPTs were observed. The main phenomenon to be observed is, however, an ignition of the released gas cloud resulting in significant blast wave overpressures and heat radiation to the surroundings. The ignition occurred in all under-water releases and in about 90 % of the releases above the water surface.
Experiments have been performed to determine the consequences of a storage vessel containing liquified hydrogen (LH2) is engulfed by a fire. The tests were performed at the Test Site Technical Safety of the Bundesanstalt für Materialforschung und –prüfung (BAM) in Germany within a research cooperation between BAM and Gexcon as part of the SH2IFT program. Three tests were performed using double-walled vacuum insulated vessels of 1 m3 volume varying the orientation of the vessel and the effect of the insulation material used (perlite or multi-layer insulation (MLI)). The degree of filling of the vessel was approximately 35 % in each of the tests performed. The fire load was provided by a propane fed burner positioned under the storage vessel and designed to give a homogeneous fire load. In one of the tests a rupture of the storage vessel occurred causing a blast, a fireball and fragments. Apart from measuring these consequences, the conditions in the vessel (e.g. temperatures and pressure) during the heating process were monitored in all three tests. The work described was undertaken as part of the project Safe Hydrogen fuel handling and Use for Efficient Implementation (SH2IFT).
Large-scale experiments have been performed to investigate the possible consequences of realistic amounts of liquified hydrogen (LH2) encountering water. The experiments aimed at simulating an accidental release of LH2 onto water, for instance during the fuelling of a ship. For liquified natural gas (LNG), it has been demonstrated that physical explosions may occur when it is spilled onto water. These phenomena are referred as rapid phase transitions (RPTs). It cannot be excluded that RPTs are also possible in the case of LH2. The tests were performed at the Test Site Technical Safety of the Bundesanstalt für Materialforschung und –prüfung (BAM) in Horstwalde, Germany. The tests were performed in a 10 m x 10 x 1.5 m basin filled with water. LH2 releases of up to about 1 kg/s were established releasing directly from a trailer carrying LH2. The releases occurred from a height of 50 cm above the water surface pointing downwards, 30 cm under the water surface pointing downwards and 30 cm under the water surface pointed along the water surface. All release configurations resulted in a very chaotic LH2-water mixing zone, causing considerable evaporation and resulting in minor over pressures. No RPTs were observed. The main phenomenon to be observed is, however, an ignition of the released gas cloud resulting in significant blast wave overpressures and heat radiation to the surroundings. The ignition occurred in all under-water releases and in about 90 % of the releases above the water surface.
In case of a vehicle fire, an installed LPG (liquefied petroleum gas) tank with a malfunctioning safety device poses severe hazards. To investigate the consequences in case of tank failure, we conducted 16 tests with toroidal shaped LPG vehicle tanks. Three tanks were used for a Hydraulic Burst Test under standard conditions. Another three tanks were equipped with a statutory safety device and were subjected to a gasoline pool fire. The safety device prevented tank failure, as intended. To generate a statistically valid dataset on tank failure, ten tanks without safety devices were exposed to a gasoline pool fire. Five tanks were filled to a level of 20 %; the re-maining five were filled to a level of 100 %. In order to gain information on the heating process, three tem-perature readings at the tank surface, and three nearby flame temperatures were recorded. At distances of l = (7; 9; 11) m to the tank, the overpressure of the shock wave induced by the tank failure and the unsteady tem-peratures were measured. All ten tanks failed within a time of t < 5 min in a BLEVE (boiling liquid expanding vapor explosion). Seven of these resulted directly in a catastrophic failure. The other three resulted in partial failure followed by catastrophic failure. A near field overpressure at a distance of l = 7 m of up to p = 0.27 bar was measured. All ten tests showed massive fragmentation of the tank mantle. In total, 50 fragments were found. These 50 fragments make-up 88.6 % of the original tank mass. Each fragment was georeferenced and weighed. Fragment throwing distances of l > 250 m occurred. For the tanks with a fill level of 20 %, the average number of fragments was twice as high as it was for the tanks that were filled completely.
Compressed natural gas (CNG) is a widely used automotive fuel in a variety of countries. In case of a vehicle fire where the safety device also malfunctions, a failure of the CNG automotive cylinder could occur. Such a cylinder failure is associated with severe hazards for the surrounding environment. Firstly, a comprehensive analysis is given below, summarizing various accidents involving CNG automotive cylinders and their consequences. In an extensive experimental program, 21 CNG automotive cylinders with no safety device were tested. Of the 21, burst tests were carried out on 5 Type III and 5 Type IV cylinders. Furthermore, fire tests with 8 Type III and 3 Type IV cylinders were conducted. Apart from cylinder pressure, inner temperature and cylinder mantle temperature, the periphery consequences, such as nearfield blast pressure and fragmentation are documented. The maximum measured overpressure due to a Type III cylinder failure was p = 0.41 bar. Each traceable fragment was georeferenced. All-in-all, fragment throw distances of d > 300 m could be observed. As one key result, it can be stated that the tested Type IV CNG cylinders showed less critical failure behavior then the Type III cylinders under fire impingement.
The number of cars which use a battery for propulsion, like BEV (battery electric vehicle) or PHEV (plug-in hybrid electric vehicle), is increasing. Following, the probability of these car types being involved in car accidents will increase. In a worst-case accident scenario, the installed batteries could go under thermal runaway (TR). A TR could be initiated by various causes, e.g., high temperatures from outside, mechanical damage of the cells/modules/batteries or internal and external short circuits. During such an event, large amounts of heat and toxic and/or flammable gases are released. This poses a great hazard to people and property in the immediate vicinity. The paper describes a large-scale test series on the lithium-ion battery TR consequences of automobile cells and modules up to E = 6.85 kWh. Near field temperatures of ΔT > 800°C in a distance of l = 2 m were measured. During an overcharge test, fragment throwing distances of l > 30 m were detected. Subsequent gas explosions of the released gases were documented. Hydrogen fluoride (HF) was measured in all tests, from cell to module. The highestmeasured concentration was cHF = 76 ppm, which is significantly higher than the 30-min-level for AEGL 2 (acute exposure guideline level 2). Based on the experimentally determined consequences, concrete measures for the accident analysis are subsequently drawn.
For a comprehensive safety assessment of stationary lithium-ion-battery applications, it is necessary to better understand the consequences of thermal runaway (TR). In this study, experimental tests comprising twelve TR experiments including four single-cell tests, two cell stack tests and six second-life module tests (2.65 kW h and 6.85 kW h) with an NMC-cathode under similar initial conditions were conducted. The temperature (direct at cells/modules and in near field), mass loss, cell/module voltage, and qualitative vent gas composition (Fourier transform infrared (FTIR) and diode laser spectroscopy (DLS) for HF) were measured. The results of the tests showed that the battery TR is accompanied by severe and in some cases violent chemical reactions. In most cases, TR was not accompanied by pregassing of the modules. Jet flames up to a length of 5 m and fragment throwing to distances to more than 30 m were detected. The TR of the tested modules was accompanied by significant mass loss of up to 82%. The maximum HF concentration measured was 76 ppm, whereby the measured HF concentrations in the module tests were not necessarily higher than that in the cell stack tests.
Subsequently, an explosion of the released vent gas occurred in one of the tests, resulting in the intensification of the negative consequences. According to the evaluation of the gas measurements with regard to toxicity base on the “Acute Exposure Guideline Levels” (AEGL), there is some concern with regards to CO, which may be equally as important to consider as the release of HF.
The number of cars which use a battery for propulsion, like BEV (battery electric vehicle) or PHEV (plug-in hybrid electric vehicle), is increasing. Following, the probability of these car types being involved in car accidents will increase. In a worst-case accident scenario, the installed batteries could go under thermal runaway (TR). A TR could be initiated by various causes, e.g., high temperatures from outside, mechanical damage of the cells/modules/batteries or internal and external short circuits. During such an event, large amounts of heat and toxic and/or flammable gases are released. This poses a great hazard to people and property in the immediate vicinity. The paper describes a large-scale test series on the lithium-ion battery TR consequences of automobile cells and modules up to E = 6.85 kWh. Near field temperatures of ΔT > 800°C in a distance of l = 2 m were measured. During an overcharge test, fragment throwing distances of l > 30 m were detected. Subsequent gas explosions of the released gases were documented. Hydrogen fluoride (HF) was measured in all tests, from cell to module. The highest measured concentration was cHF = 76 ppm, which is significantly higher than the 30-min-level for AEGL 2 (acute exposure guideline level 2). Based on the experimentally determined consequences, concrete measures for the accident analysis are subsequently drawn.
Every technical system has a failure rate, including a lithium-ion battery. To minimize the effects in the event of a thermal runaway, it is necessary to know what consequences to expect. In the talk, current results from tests on the thermal runaway behaviour of lithium-ion batteries will be presented and conclusions drawn for the handling of those.
Again and again in case of a fire a bursting of acetylene cylinders occure. In the case of such a cylinder failure, these represent an enormous threat to fire and rescue services. BAM has been dealing for many years with the effects of acetylene cylinder failure. The presentation introduces BAM's experimental work in this area and outlines various options for action to reduce the risk for fire and rescue services. In the beginning BAM as well as the experimental possibilities at the BAM TTS are presented.
Lithium Ion Batteries - Europe and Germany in general and BAM with safety aspects in particular
(2019)
The article introduces the BAM as well as the experimental possibilities at the BAM TTS in the first part. The second part explains general aspects of the electromobility strategy and the research landscape on lithium batteries in Germany and Europe. In the last part of the presentation current investigations on the safety of lithium batteries as well as perspectives planned investigations of the BAM in this area are presented.
The combustion characteristics and explosive hazard of syngas (H2/CO)/air mixtures are affected by its exact composition and equivalence ratios. In this paper, the explosion pressure and spectral radiant intensity of free radicals were quantitatively examined for syngas with different H2 proportions ([H2 in syngas] = 0, 30, 50, 70, 100 vol%) and equivalence ratios (φ = 0.8, 1.0, 1.2, 1.4, 1.6, 2.0, 2.5). The results show that the explosion process of syngas/air mixtures can be separated into the initial slow combustion stage, the violent deflagration stage and the deflagration ending stage. The peaks of explosion pressure, pressure rise rate, OH*spectral intensity and rise rate of spectral intensity first increase and then decrease with increasing the equivalence ratio, and they reduce gradually with the decrease of H2 proportion in syngas. The H2 content in syngas greatly affects the heat release and the concentration of excited state OH*, especially for the syngas/air mixtures with smaller proportion of H2. Additionally, the presence of H2 greatly increases the deflagration index and spectral radiant index of OH* for syngas/air mixtures. The average rise rates of explosion pressure and spectral intensity of free radicals are introduced and the coupling model between them is established based on the first law of thermodynamics and the principle of chain reaction. The established model is furthermore verified by the experimental results. It is indicated that there is a linear relationship between average rise rates of explosion pressure and spectral intensity (OH*). The results can be used to improve the combustion efficiency of syngas and to guide theoretically the prevention, mitigation and control of syngas explosions.
In the presented work, the potential of fiber-optic distributed acoustic sensing (DAS) for detection of small gas pipeline leaks (<1%) is investigated. Helical wrapping of the sensing fiber directly around the pipeline is used to increase the system sensitivity for detection of weak leak-induced vibrations. DAS measurements are supplemented with reference accelerometer data to facilitate analysis and interpretation of recorded vibration signals. The results reveal that a DAS system using direct fiber application approach is capable of detecting pipeline natural vibrations excited by the broadband noise generated by the leaking medium. In the performed experiment, pipeline vibration modes with acceleration magnitudes down to single ug were detected. Simple leak detection approach based on spectral integration of time-averaged DAS signals in frequency domain was proposed. Potential benefits and limitations of the presented monitoring Approach were discussed with respect to its practical applicability. We demonstrated that the approached is potentially capable of detection and localization of gas pipeline leaks with leak rates down to 0.1% of the pipeline flow volume and might be of interest for monitoring of short- and medium-length gas pipelines.
The monitoring of oil and gas pipelines by means of distributed fibre optic sensors is becoming common. The most recent development in the field of fibre optic sensing is the distributed acoustic sensing (DAS), which allows to detect and to localize third party threats to pipelines. For this purpose, fibre optic telecommunication cables located close to the pipelines are usually used. However, DAS carries a far greater potential for continuous condition monitoring of pipelines.
The interdisciplinary research project AGIFAMOR (Ageing Infrastructures – Fibre Optic Monitoring of Pipes) at BAM investigates a new technical approach to extend the application field of DAS towards the detection and localization of acoustic signals that indicate critical alterations and certain damage scenarios originated from within the pipeline or the pipe wall. Therefore, the optical fibre sensors are applied onto the pipe itself and the application procedure towards an optimal acoustic signal transduction is optimized.
A number of laboratory scale experiments were performed focusing on the signal transmission of acoustic signals as well as the detection of damages in the pipe wall by means of DAS. Furthermore, real-scale tests on a pipeline DN100 of 38m length have been carried out at the BAM test site for technical safety (BAM-TTS) to study the detection and localization of leaks and of changing flow profiles due to corrosion or sedimentation processes.
The monitoring of oil and gas pipelines by means of distributed fibre optic sensors is becoming common. The most recent development in the field of fibre optic sensing is the distributed acoustic sensing (DAS), which allows to detect and to localize third party threats to pipelines. For this purpose, fibre optic telecommunication cables located close to the pipelines are usually used. However, DAS carries a far greater potential for continuous condition monitoring of pipelines.
The interdisciplinary research project AGIFAMOR (Ageing Infrastructures – Fibre Optic Monitoring of Pipes) at BAM investigates a new technical approach to extend the application field of DAS towards the detection and localization of acoustic signals that indicate critical alterations and certain damage scenarios originated from within the pipeline or the pipe wall. Therefore, the optical fibre sensors are applied onto the pipe itself and the application procedure towards an optimal acoustic signal transduction is optimized.
A number of laboratory scale experiments were performed focusing on the signal transmission of acoustic signals as well as the detection of damage in the pipe wall by means of DAS. Furthermore, real-scale tests on a pipeline DN100 of 38 m length have been carried out at the BAM test site for technical safety (BAM-TTS) to study the detection and localization of leaks and of changing flow profiles due to corrosion or sedimentation processes.
Safety characteristics are used to keep processes, including flammable gases, vapors, and combustible dusts, safe. In the standards for the determination of safety characteristics of gases and vapors, the induction spark is commonly used. However, classic transformers are hard to obtain, and replacement with new electronic transformers is not explicitly allowed in the standards. This article presents the investigation of five gases that are normally used to calibrate devices for the determination of safety characteristics, the maximum experimental safe gap (MESG), with an electronic transformer, and the values are compared to the ones that are obtained with the standard transformer. Additionally, calorimetric measurements on the net energy of both ignition sources were performed as well as open-circuit voltage measurements. It is concluded that the classic type of transformer can be replaced by the new type obtaining the same results for the MESG and introducing the same amount of energy into the system.
Safety characteristics are widely used in industrial processes to avoid explosive atmospheres (primary explosionprotection) or to mitigate the consequences of an explosion (constructive explosion protection). Several laboratory parameters influence the determined values when performing the test series such as the beginning pressure and the pre-ignition pressure rise, the ignition source, the ignition energy, the burning duration and volume or the concentration of the combustible substance.
In the different standards for the determination of safety characteristics of dusts there is no statement about the scattering or the deviation when parameters are chosen or occur on the borders of their allowed range. Thus, two laboratories might determine values that are hardly comparable for the same given substance.
This article summarizes some of the influential factors that cause a deviation and shows the inherent scattering of dust tests when all other parameters are kept constant. It also provides some advice how to minimize the deviation and the scattering with little effort.
There are several standardized ignition sources in use for the determination of explosion characteristics of gases, vapors and dusts. In the standards the ignition source is stated, but they vary in stating other characteristics like burning duration, energy or burning volume. Since heat is not visible under normal circumstances a Schlieren-Technique was used to make the full heating volume and not just the flames visible.
While an earlier paper of the authors focused on the ignition energy and burning duration of four standardized ignition sources, this paper focuses on the initial igniting volume, the ratio between initial igniting volume and the test-vessel size and other phenomena that were observed with the Schlieren-Technique-.
Several standardized ignition sources are used to determine the safety characteristics of gases, vapours and dusts. Standards indicate the source of ignition but vary in specifying other features such as the burning duration, energy or the volume in which the energy is released. Since heat is not visible under normal conditions, a schlieren technique was used to visualize the entire igniting volume and not just the flames. This article focuses on the igniting volume, compares it among the four standardized ignition sources and displays its relationship to the size of the test vessel. Differences in the ignition behaviour of the ignition sources might lead to the determination of erroneous safety characteristics and with that to the unsafe operation of processes.
For the determination of safety characteristics of gases, vapors and dusts different types of ignition sources are used in international standards and guidelines. The paper presents test results of a comparative calorimetric and visual study between four different types of ignition sources. The ignition procedures were analyzed visually with a high-speed camera and electric recordings. In addition to that, the influence of the electrode-orientation, -distance as well as ignition energy on the reproducibility of the exploding wire igniter was tested.
The exploding wire is already in use for standardized determination of safety characteristics of gases, first tests on the suitability of the exploding wire igniter for dust testing have been carried out but are not standardized yet. Using the exploding wire, the ignition energy can be varied from 2 J to 10 000 J (2 x 5000 J) and thus it could be used for gases, vapors, dusts and hybrid mixtures. Moreover it can be used at high initial pressures and it is the only ignition source with an easily measurable ignition energy release. Furthermore, it does not introduce another chemical reaction into the system.
Finally, a proposal for a standard ignition source for explosion tests on hybrid mixtures is derived from the test results.
For the determination of safety characteristics of gases, vapors and dusts different types of ignition sources are used in international standards and guidelines. Table 1 compares technical relevant ignition sources with their main features. The paper presents test results of a comparative calorimetric and visual study between four different types of ignition sources. The ignition procedures were analyzed visually with a high-speed camera and electric recordings. In addition to that, the influence of the electrode-orientation, -distance as well as ignition energy on the reproducibility of the exploding wire igniter was tested.
The exploding wire is already in use for standardized determination of safety characteristics of gases, first tests on the suitability of the exploding wire igniter for dust testing have been carried out by Scheid et al. Using the exploding wire, the ignition energy can be varied from 2 to 10 000 J (2 x 5 000 J) and thus it could be used for gases, vapors, dusts and hybrid mixtures. Moreover it can be used at high initial pressures and it is the only ignition source with an easily measurable ignition energy release. Furthermore, it does not introduce another chemical reaction into the system.
Finally, a proposal for a standard ignition source for explosion tests on hybrid mixtures is derived from the test results.
The maximum rate of pressure rise (dp/dt)𝑚𝑎𝑥 and the corresponding K-value of hybrid mixtures containing flammable gases and dusts are important for constructive explosion protection measures. Since the safety characteristics of dusts and gases are determined under different conditions, there has been considerable confusion about the influence of flammable gas on the (dp/dt) of dusts and vice versa. While some investigations showed comparably higher values for hybrid mixtures, others stated that the highest value for the gas component alone is the worst case.
The first part of this paper focuses on the confusion around the different statements about (dp/dt)𝑚𝑎𝑥 of hybrid mixtures and where they come from. In the second part of this paper experimental results are presented that illustrate how to clarify the different findings of past research and show what to expect as a real worst-case-value for hybrid mixtures.
While developing a standard for the determination of safety characteristics for hybrid mixtures the authors discovered, that, beside the ignition source, the mixing procedure is the main difference between the single-phase standards for dusts and gases. The preparation of hybrid mixtures containing a flammable gas and a flammable dust in the 20 L-sphere can be realized in different ways. Either the flammable gas is filled only in the sphere or only in the dust container or in both. In previous works, almost always the first method is applied, without giving any information on the accuracy of the gas mixtures. In this work the accuracy of the gas mixtures and the results of the tests applying two methods of mixing were studied. No significant influence of the mixing method itself on the safety characteristics explosion pressure pex and the normalized rate of pressure rise (K-value) was found. Obviously, homogenization of the gas mixtures can be obtained sufficiently by the turbulence that is caused during the injection from the dust container into the explosion chamber within a short time. However, the mixing procedure has a great influence on the accuracy of the gas amount of the mixtures obtained. Without modifying the 20 L-sphere by installing precise pressure sensors, assuring its tightness and performing gas analysis, it must be expected, that the accuracy of the gas mixtures is very low. This has a significant influence on the measured safety characteristics and may lead to unsafe facilities or unnecessary expensive safety measures.
Influence of pre-ignition pressure rise on safety characteristics of dusts and hybrid mixtures
(2021)
For the determination of the safety characteristics of dusts it is necessary to disperse the dust in the oxidating atmosphere (usually air). In the standard procedures for dusts this is realized by a partially evacuated explosion vessel (20L-sphere) in which the dust gets injected from a dust chamber pressurized with air. Shortly after that injection (60 ms) the dust cloud gets ignited under turbulent conditions, that are otherwise seen as almost ambient with 20 ◦C and about 1 bar (abs). While there has been a lot of research about the influence of the ignition delay time and the level of turbulence in the recent years little attention was paid to the pre–ignition pressure rise and the allowed variations in the standards. In the following work we showed that the allowed ranges for the pressures in the different dust standards influence the safety characteristics of dust alone severely.
Even though hybrid mixtures are an emerging risk problem in an interconnected industry there is no standard for the determination of their safety characteristics. In this work it is shown that especially for the preparation of hybrid mixtures of flammable dust and gas the pressures after injection of the dust and the mixing procedure have a large influence on the composition of the tested mixtures and therefore on the safety characteristics.
Considering both effects, wrong concentration of gas and wrong initial pressure, the discrepancy of safety characteristics from different facilities will be too big to applicable. The methods to overcome these weaknesses are also presented.
There is no applicable existing standard for the determination of safety characteristics for hybrid mixtures. While developing a new standard in a joint research project in Germany first results from parameter studies led to a standard procedure that can be adopted by laboratories that are already testing dusts in the so called 20L-sphere with as little additional effort as necessary. In fact, one of the main objectives of this research project was to keep modifications and adjustments from the generally accepted dust testing procedures as easy and minimal as possible so as to limit potential deviations from one laboratory to another.
In this first round robin test on hybrid mixtures ever, with methane as gas component and a specific corn starch as dust sample, the practicality of the whole procedure, the scattering of the results and the deviation between the testing apparatuses is investigated. This paper summarizes the experimental procedure adopted and objectives of the first round-robin phase involving three of the four original German companies, plus volunteering laboratories from Australia, Belgium, Czech Republic, France, Poland and P.R. China. The results will have an impact on the new standard and may lead to robust data for later simulation purposes.
There are several standardized ignition sources in use for the determination of explosion characteristics of gases, vapors and dusts. In the standards the ignition source is stated, but they vary in stating other characteristics like burning duration, energy or burning volume. Since heat is not visible under normal circumstances a Schlieren-Technique was used to make the full heating volume and not just the flames visible. While an earlier paper of the authors focused on the ignition energy and burning duration of four standardized ignition sources, this paper focuses on the initial igniting volume, the ratio between initial igniting volume and the test-vessel size and other phenomena that were observed with the Schlieren-Technique.
In the standards for the determination of safety characteristics of dusts an initial pressure difference of 400 mbar (all: abs) is applied, that increases to 1013 mbar to achieve a homogeneous dust-air mixture. Since the measuring equipment accuracy is given with ± 0,1 bar the initial pressure could range somewhere between 300 and 500 mbar and the pressure increase between 500 and 700 mbar, leading to a testing pressure of 800 to 1200 mbar.
This variation does not only affect the testing pressure but also the concentration of dust and the level of turbulence, leading to wrong values of Pmax, Kst and assigning them to wrong concentrations. When tests for hybrid mixtures are conducted there are more degrees of freedom leading to even higher variations. To overcome these variations a higher accuracy is demanded for hybrid mixture testing. Further, in this presentation four standardized ignition sources are presented.
For the determination of safety characteristics of gases, vapors and dusts different types of ignition sources are used in international standards and guidelines. Table 1 compares technical relevant ignition sources with their main features. The paper presents test results of a comparative calorimetric and visual study between four different types of ignition sources. The ignition procedures were analyzed visually with a high-speed camera and electric recordings. In addition to that, the influence of the electrode-orientation, -distance as well as ignition energy on the reproducibility of the exploding wire igniter was tested.
The exploding wire is already in use for standardized determination of safety characteristics of gases, first tests on the suitability of the exploding wire igniter for dust testing have been carried out by Scheid et al. Using the exploding wire, the ignition energy can be varied from 2 to 10 000 J (2 x 5 000 J) and thus it could be used for gases, vapors, dusts and hybrid mixtures. Moreover it can be used at high initial pressures and it is the only ignition source with an easily measurable ignition energy release. Furthermore, it does not introduce another chemical reaction into the system.
Finally, a proposal for a standard ignition source for explosion tests on hybrid mixtures is derived from the test results.
Safety characteristics like the lower explosion limit, the highest concentration for a given substance mixed with air that does not result in a self-propagating flame, or the maximum explosion pressure, the highest pressure that can be reached after ignition for a given combustible substance mixed with air at any concentration, are widely used in the industry to either prevent an explosion or to mitigate the effects of it. Safety characteristics are not physical constants, are determined experimentally and depend on the chosen experimental parameters such as the ignition energy or turbulence.
For the determination of the safety characteristics lower explosion limit (LEL), limiting oxygen concentration (LOC), maximum explosion pressure (pmax) and maximum rate of pressure rise ((dp/dt)max) of gases and vapors the gas is filled via partial pressures into a test vessel and then ignited under quiescent conditions with a weak (2 J - 20 J) ignition source. For dusts, the same safety characteristics are determined under turbulent conditions to elevate
the dust homogeneously and it is ignited with two chemical igniters with an ignition energy of 1000 J each (LEL and LOC) or 5000 J each (pmax and (dp/dt)max). For the determination of safety characteristics of hybrid mixtures (a mixture containing a combustible dust and a flammable gas) there is no existing standard.
In the last 40 years most of the research on their safety characteristics was performed with dust testing equipment that was modified for the addition of flammable gas. Because of the different mixing procedures of gases and dusts with air and because of different ignition energies and sources that are normally used for the standard tests of gases or dusts, the results were hardly reproducible. Statements about the different safety characteristics were contradictory and left the reader or the person responsible for designing safety measures for a process plant or a facility behind with no clear suggestion about the behavior of hybrid
mixtures.
This thesis is aimed on determining the influence of the different ignition sources and energies on the safety characteristics pmax, (dp/dt)max, lower explosion limit, and limiting oxygen concentration of hybrid mixtures.
Several test series were conducted to characterize different standardized ignition sources, that are already in use for the determination of safety characteristics of single-phase substances (gases, liquids, dusts). The burning duration, the igniting volume and the net energy were investigated.
It was shown, that the chemical igniters and the exploding wire are suitable ignition sources for the determination of safety characteristics of hybrid mixtures in general. Their burning duration was long enough to ignite dusts and quick enough, that the decay of the turbulence or sedimentation of the dusts did not occur. Both ignition sources produced comparable results for the determination of pmax, LEL and (dp/dt)max of dusts when they had the same ignition energy. A reduced ignition energy of the exploding wire and the chemical igniters did not affect the pmax and (dp/dt)max. The LEL changed with lower energies. However, for the determination of the LOC of hybrid mixtures the exploding wires with an overall energy of 2 kJ produced the best results.
The influence of the different mixing procedures that have already been used for hybrid mixtures and the requirements for them were also investigated experimentally for the gas concentration and the determined safety characteristics and compared to each other. It was shown, that the partial pressure method works for mixing hybrid mixtures but the pressures should be measured very accurately and the gas concentration should be validated.
Furthermore, the influence of the turbulence that is inevitable when testing dusts, on the safety characteristics of gases was determined. It was found that the chemical igniters and exploding wires produced comparable results for the determination of pmax, LEL and (dp/dt)max under turbulence. For the LOC only exploding wires with two times 1 kJ worked.
Finally, the safety characteristics of hybrid mixtures were determined with different ignition energies and sources and the data were compared. It was discovered, that the pmax of hybrid mixtures was the same value than the higher determined one of the single substances while (dp/dt)max of hybrid mixtures was about 10 % to 25 % higher than the value of the stoichiometric gas mixture under turbulence. The point was found at the stoichiometric gas concentration with very little amounts of dust.
To prove the key findings of this work and for the establishment of a standardized procedure for the determination of safety characteristics of hybrid mixtures, an international round robin test was conducted with eleven participating facilities in seven countries. The results were comparable within a reasonable range and are presented in this dissertation in an extra chapter.
Based upon the observations in this work a reliable solution for a new standardizable ignition source to determine the safety characteristics of hybrid dust-gas-mixtures is proposed.
Self-sustaining smoldering as a novel disposal approach for food waste with high moisture content
(2021)
This work aims to explore the self-sustaining smoldering treatment (SSST) for the destruction of food waste. The food waste used in this work mainly consists of cereal, vegetable, and meat. To examine the processing procedures and parameters, three experimental groups (raw food waste, food-waste paste and food-waste paste blended with anthracite) and five variables (moisture content, sand size, sand-to-food waste ratio, air flow and food waste-to-coal ratio) were extensively investigated. Results show that raw food waste with 40% moisture content can be disposed by SSST with the mass destruction ratio over 90%. However, the robustness of SSST for raw food waste is constrained by the heterogeneous issue due to a variety of components and sizes of food waste. This issue is addressed through stir pre-processing of raw food waste as food-waste paste. The robustness of SSST for food waste is significantly further enhanced only if a slight mass fraction of anthracite (<20% of raw food waste) is supplemented. This provides an alternative solution for employing SSST for raw food waste with very high moisture content.
The following presentation provides an overview on some of the challenges with metallic materials used as structural materials in the energy sector for the transport and storage of hydrogen. The presentation contains explanations about the methodologies utilized to characterize the susceptibility of these materials for hydrogen.
In the field of explosive reactions, there is a type of explosive effect that lacks a sufficient database and reproducible experiments regarding biomechanics. It concerns the primary explosive effect. It is defined as pure shock wave of the explosion. The physical behavior of the shock wave when interacting with different types of tissue and, in particular, the subsequent transitions of the shock wave, have barely been investigated. The transition of the shock wave into other materials is the focus of the research Therefore, the aim of the investigations is the development of a multidisciplinary method to investigate shock wave behavior in various generic tissue simulants under the most reproducible conditions possible with realistic loads in an experimental test series with short set-up times. An autoclave is used to generate the pressure waves. A simplified torso model consisting of ballistic gelatin is used as a simulant.
In this paper, the influence of protective equipment on the pressure load in the tissue simulant is investigated. For this purpose, consecutive test setups are used. First, the behavior of ballistic gelatin as a tissue simulant is investigated. Then, the simplified torso model is covered with typical combat clothing consisting of four layers.
Afterwards a currently used UHMWPE ballistic protective plate is placed in front of the simplified torso model.
Finally, the combat clothing and the protective plate are examined in combination. Three cast-in pressure sensors are used as measuring devices, as well as an acceleration sensor attached to the protective plate.
The experiments show that the maximum overpressure in a model rotected by combat clothing and the protective plate can be reduced by 95%. However, the propagation speed of the shock wave within the simplified torso model increases from 1535.5 m/s to 2204.5 m/s. This shows that even protective equipment, which is not primarily intended to protect against blast, offers a significant reduction in the pressure load in the protected area. On the one hand it is caused by the media transition from air to PE and the resulting higher reflection of the acceleration of the transmitted wave within the simulant. On the other hand, it is also reduced due to the damping and dispersion caused by the clothing layers.
Blast injuries are among the most common injuries in military operations. Also, in civilian environments, more explosive threats are expected in the future due to emerging conflicts and threats. While the effect of fragments, which is classified as secondary blast injury, could be minimized by police and military personnel’s modern ballistic body protection systems, the effects of shock wave propagation in the body as part of the primary explosion trauma still remain a serious threat needing further research.
The detonation-physical processes of highly dynamic pressure changes within the human body, the reflection-related amplification of shock waves at organ-dermis interfaces, and the consequences of injury mechanisms have become more prominent in international research. Various approaches have been used to investigate these aspects. Animal experiments on free field test sites or shock tube setups combined with a subsequent biological evaluation and numerical simulations provided promising results and allowed the discussion of different biomechanical aspects. However, due to poor reproducibility and a lack of short-term dynamic material properties, most research approaches have significant limitations. Laboratory test setups do not represent real-scale high explosive detonation parameters with regards to pressure characteristics, impulse duration and blockage problems. Measured values are interpreted with partly outdated, selective and not validated limit values for overpressures from field tests with animals. This is due to the lack of a validated and comprehensive data set covering a variation of the crucial parameter. Injury mechanisms and their effects have not yet been sufficiently elucidated for the torso and extremities.
In order to contribute to the research efforts on the primary explosion effects, the German Federal Armed Forces established an interdisciplinary military medical research project in cooperation of the Bundeswehr Hospital Berlin and the German Federal Institute for Materials Research and Testing (BAM). The aim of the planned investigation is the development of a multidisciplinary method to investigate shock wave behavior in various generic tissue simulants under the most reproducible conditions possible with realistic loads in an experimental test series with short set-up times.
Following directly from the information presented at IFBIC 2023 on the research project 'Investigation of intracorporeal shock wave propagation using a simplified torso model and a shock wave generator', the latest results are presented below [1]. In order to contribute to the research efforts on the primary explosion effects, the aim of the investigation is the development of a multidisciplinary method to investigate shock wave behavior in various generic tissue simulants under the most reproducible conditions possible with realistic loads in an experimental series with short set-up times.
To achieve this, an autoclave with a volume of 0.065 m3 is used to generate reproducible pressure waves (Fig. 1). The autoclave will be referred to as Shockwave Generator (SWG). The pressure wave is produced by the detonation of a stoichiometric mixture of acetylene and oxygen under atmospheric conditions. The SWG-outlet is sealed by a rupture disc, which can be adjusted in thickness to vary the initial pressure. Additionally, modifying the composition of the acetylene-oxygen mixture can result in different load cases. The SWG requires approximately 30 minutes of set-up time between trials. The SWG was adjusted to match the characteristics of a real and typical explosive through free-field measurements. The experiments demonstrated that the pressure wave propagates in a hemispherical shape and has sufficient reproducibility.
To represent soft tissue, a basic model made of homogeneous ballistic gelatin is used in a geometrically simplified torso model (STM) (Fig. 2). The STM was enlarged to outer dimensions of 400 x 250 x 240 mm. Viscoelastic behavior of the ballistic gelatin can be assumed due to the collagen structure [2]. The density of the ballistic gelatin, and therefore the sound velocity, can be adjusted by changing the mixing ratio. Simplified simulants, such as hollow and solid material (bone simulant), were embedded in the STM. Additionally, the STM has been tested as a carrier material for biological substances, such as indicator species. The next step is to test the STM as a carrier material for larger organic tissue structures such as lungs or kidneys. The organic tissue samples will undergo histological examination to analyze their structural changes afterwards. The STM is equipped with embedded piezoelectric pressure sensors, an accelerometer and a temperature sensor. Visual documentation is captured using a high-speed camera. This measurement setup allows for the tracking of the coupled pressure wave and its behavior within the model and at the media transitions. Pressure values can be recorded after certain media changes, such as from soft tissue to a solid material (Figure 3).
The following is a review of the optimizations made to the entire experimental setup. The reproducibility of the SWG was increased. This was achieved by extending the evacuation process to the entire feed system of the SWG. Nitrogen residues in the SWG system can thus be avoided. As a result, the double peaks that occur at the first maximum can be avoided, as combustion runs more evenly without the nitrogen residues. In addition, partially varying peak overpressures can be avoided, as the acytelene-oxygen mixture is not too lean due to the elimination of the nitrogen residues. The workflow has been streamlined, resulting in an average set-up time of 25 minutes for the SWG. In the case of the STM, the manufacturing process in particular was optimized by examining and defining the manufacturing process based on scientific publications, which increases the reproducibility of the STM base bodies. As already mentioned in the previous paragraph, the STM was equipped with various additives in order to investigate the transition behavior of the pressure wave.
The following trail serves as an example: A comparison is made between the STM in the basic structure (Fig. 2 l.s.) and with an embedded solid material (bone plate) (Fig. 3 l.s.). An external overpressure of 100 kPa is generated by the SWG at a distance of 1 m, where the STM is placed. For the basic STM structure, the sensor distance is consistently 100 mm. The internal overpressure is visible in Fig. 2 r.s.. A typical ideal pressure curve can be seen. The characteristic points are easily distinguishable from the reflection peaks. In the STM with an embedded solid material, the sensor distance remains consistently at 66.6 mm
In the field of explosive reactions, there is a type of explosive effect that lacks a sufficient database and reproducible experiments regarding biomechanics. It concerns the primary explosive effect. It is defined as pure shock wave of the explosion. The physical behavior of the shock wave when interacting with different types of tissue and, in particular, the subsequent transitions of the shock wave, have barely been investigated. The transition of the shock wave into other materials is the focus of the research Therefore, the aim of the investigations is the development of a multidisciplinary method to investigate shock wave behavior in various generic tissue simulants under the most reproducible conditions possible with realistic loads in an experimental test series with short set-up times. An autoclave is used to generate the pressure waves. A simplified torso model consisting of ballistic gelatin is used as a simulant. In this paper, the influence of protective equipment on the pressure load in the tissue simulant is investigated. For this purpose, consecutive test setups are used. First, the behavior of ballistic gelatin as a tissue simulant is investigated. Then, the simplified torso model is covered with typical combat clothing consisting of four layers. Afterwards a currently used UHMWPE ballistic protective plate is placed in front of the simplified torso model. Finally, the combat clothing and the protective plate are examined in combination. Three cast-in pressure sensors are used as measuring devices, as well as an acceleration sensor attached to the protective plate. The experiments show that the maximum overpressure in a model protected by combat clothing and the protective plate can be reduced by 95%. However, the propagation speed of the shock wave within the simplified torso model increases from 1535.5 m/s to 2204.5 m/s. This shows that even protective equipment, which is not primarily intended to protect against blast, offers a significant reduction in the pressure load in the protected area. On the one hand it is caused by the media transition from air to PE and the resulting higher reflection of the acceleration of the transmitted wave within the simulant. On the other hand, it is also reduced due to the damping and dispersion caused by the clothing layers.
Experimental Setup for the Reproducible Generation of Pressure Waves in Free Field Conditions
(2023)
The injuries caused by the primary blast are still poorly understood, especially in the torso region. To generate sufficiently large data sets, shock tubes are often used. However, these have some limitations, such as blockage, use of the exit jet, widening cross-sections, and scaling problems with respect to compressive strength and test objects. Therefore, it is appropriate to conduct experiments under free-field conditions, but tests with real explosives are often associated with long preparation and setup times as well as high safety requirements.
Therefore, this paper presents an experimental setup for the reproducible generation of blast waves under free-field conditions. This experimental setup aims to provide a test environment for a sufficiently large specimen to investigate the behaviour of the shock wave within the specimen, especially at the media interfaces. As an example of application, the influence of the primary explosive effect on protective equipment or on tissue simulants for the investigation of blast injuries can be mentioned. An autoclave is used as a shock wave generator. It has a volume of 0.065 m3 and is filled with a stoichiometric acetylene-oxygen gas mixture. The setup and turnaround time is approximately 30 minutes. The following factors have been selected as target variables for the optimization of the shock wave generator: reproducibility of the pressure wave, use-case-relevant positive phase duration and peak overpressure, a pressure curve characteristic corresponding to that of a military explosive under undisturbed free field conditions, and short setup times of the experimental setup. For this purpose, the experimental setup is presented in this paper. Several series of measurements are presented, showing the characteristics of the generated pressure wave. For the generated pressure wave, the classical pressure curve characteristics can be clearly recognized. A peak pressure of 92 kPa is reached at a distance of 1 m from the opening, and the first positive pressure phase lasts 1.17 ms. Furthermore, the pressure wave propagates in a hemispherical shape. The typical characteristics of the blast wave generated by the SWG have been demonstrated using the military explosive PETN. It is shown that the actual load case corresponds to about 70 g of PETN.
Experimental Setup for the Reproducible Generation of Pressure Waves in Free Field Conditions
(2023)
The injuries caused by the primary blast are still poorly understood, especially in the torso region. To generate sufficiently large data sets, shock tubes are often used. However, these have some limitations, such as blockage, use of the exit jet, widening cross-sections, and scaling problems with respect to compressive strength and test objects. Therefore, it is appropriate to conduct experiments under free-field conditions, but tests with real explosives are often associated with long preparation and setup times as well as high safety requirements.
Therefore, this paper presents an experimental setup for the reproducible generation of blast waves under free-field conditions. This experimental setup aims to provide a test environment for a sufficiently large specimen to investigate the behaviour of the shock wave within the specimen, especially at the media interfaces. As an example of application, the influence of the primary explosive effect on protective equipment or on tissue simulants for the investigation of blast injuries can be mentioned. An autoclave is used as a shock wave generator. It has a volume of 0.065 m3 and is filled with a stoichiometric acetylene-oxygen gas mixture. The setup and turnaround time is approximately 30 minutes. The following factors have been selected as target variables for the optimization of the shock wave generator: reproducibility of the pressure wave, use-case-relevant positive phase duration and peak overpressure, a pressure curve characteristic corresponding to that of a military explosive under undisturbed free field conditions, and short setup times of the experimental setup. For this purpose, the experimental setup is presented in this paper. Several series of measurements are presented, showing the characteristics of the generated pressure wave. For the generated pressure wave, the classical pressure curve characteristics can be clearly recognized. A peak pressure of 92 kPa is reached at a distance of 1 m from the opening, and the first positive pressure phase lasts 1.17 ms. Furthermore, the pressure wave propagates in a hemispherical shape. The typical characteristics of the blast wave generated by the SWG have been demonstrated using the military explosive PETN. It is shown that the actual load case corresponds to about 70 g of PETN.
The safety characteristics of flammable gases and liquids are required when identifying potentially explosive mixtures and taking appropriate actions concerning explosion protection. Examples are given here of the safe handling and evaluation of hazards during the processing, storage, transport, and disposal of flammable liquids and gases. The CHEMSAFE database is presented as a reliable source of safety characteristic data, and its new open-access version is introduced. CHEMSAFE currently contains assessed properties for about 3000 liquids, gases and mixtures. The lack of a broad experimental foundation in the extensive field of non-atmospheric conditions shows the need for further investigation and standardization. This article summarizes experimental evidence and estimation methods for safety characteristic data under non-atmospheric conditions pointing out current limitations. Suggestions for pre-normative research on safety data under non-atmospheric conditions are given.
The paper provides a summary of safety characteristics of hydrogen and hydrogen fuel gases. The inves-tigations focus on water electrolysis, the feeding of hydrogen into the natural gas grid and the use ofhydrogen for the fermentation process in biogas plants. The safety characteristics of hydrogen such as avery low minimum ignition energy, very large explosion range and high flame velocity with the resultingrapid pressure increase of hydrogen explosions are of particular importance for explosion protection andthey differ strongly from those of natural gas. Explosion ranges of hydrogen-methane-carbon dioxidemixtures have been measured for the use of hydrogen in biomethane production. The paper also showsand discusses explosion ranges of hydrogen and hydrogen-natural gas mixtures. Pressure and tempera-ture dependencies of the explosion limits of mixtures were investigated. Furthermore, pressure rise rates(KGvalues) were measured with regard to constructive explosion protection. The maximum experimen-tal safe gaps were determined for the classification of the mixtures and assignment to explosion groupsaccording to the European ATEX directives. It was found that admixture of 10% hydrogen to natural gashas only a minor influence on the safety characteristics of gas explosions.
Minimum explosion concentrations of coal dusts with CH4/H2/CO below the gas lower explosion limit
(2020)
A 20-L spherical explosion chamber was used to investigate the explosion characteristics of dust clouds in air with the presence of flammable gas which is lower than its lower explosion limit (LEL).
including minimum explosion concentration (MEC) of dust. Explosion pressure (Pex) and explosion pressure rise (dp/dt)ex). Two dust samples (anthracite coal, bituminous coal) and were three flammable gases (CH4, H2 and CO) were tested. Experimental results showed that the explosion of hybrid mixtures occurs when both dust and gas concentrations are lower than the LEL/MEC of the single substances.
Meanwhile. all flammable gases with different volume fractions have distinct effects on the MEC. Pex and (dp/dt)ex of the dust samples.
With the increase of the flammable gas concentration. either the Pex and (dp/dt)ex increase or the MEC decreases for all the hybrid mixtures of both two dust samples. At the same concentration of coal dusts. the addition of CH4 promotes higher explosion risks than the other two flammable gases. The distribution of (dp/dt)ex is quite different with the restricted area defined by empirical formulas.
These results improve our understanding of the explosion behaviour and the explosion risk of hybrid dust-gas mixtures in air.
Industrial fires and explosions initiating from self-ignition of combustible porous dust deposits represent a serious hazard for human beings, environment and industry. Understanding the fundamental basis of combustible dust ignition behaviours at different geometries is of importance to prevent and mitigate the accidental risks. A correlation of self-ignition temperatures (SITs) measured by hot-oven tests and minimum ignition temperatures of dust layers (MITLs) determined by hot-plate tests has been established previously. However, this analogy approach based on Frank-Kamenetzkii model is limited by ignoring the influence of oxygen diffusion. In this work, an improved method is developed by implementing a correction factor for the pre-exponential factor caused by the boundary geometry. This method is testified by comparing with experimental data, previous analogy method and numerical simulation. Results show that our proposed method performs a better predictability of MITLs and simplicity. The improved analogy method indicates that the different boundary geometries of a dust deposit significantly impact the apparent pre-exponential factor, while have an ignorable influence on the activation energy, which is also verified by numerical investigations. Furthermore, the numerical model with the corrected kinetic parameters provides a satisfactory explanation compared with experimental observations regarding to temperature and concentration evolutions of dust layers.
Self-ignition Behaviour of Bulk Materials: How Reliable is the Extrapolation of Laboratory Tests?
(2022)
The self-ignition behaviour of bulks is usually determined with the aid of isoperibolic or adiabatic hot storage tests; the sample volumes here are typically in the range of approx. 100 cm³ to several litres. The extrapolation to technically relevant volumes holds, however, considerable uncertainties. To reduce these uncertainties, a test stand was set up that allows to investigation sample sizes of up to 1000 dm³. These allow the study of selfignition behavior closer to the conditions that prevail in practice. The suitability (or unsuitability) of the established methods (including dangerous goods classification tests) were to be demonstrated and influencing variables that cannot be measured on a laboratory scale were to be determined.
In addition, various analytical methods were used for the determination of reaction kinetic data of solid bulk materials and to predict the self-ignition behaviour of large storages. These are thermal analyses such as differential scanning calorimetry DSC, simultaneous thermal analysis STA as well as microcalorimetry for highprecision measurement of heat flows.
Complete test series using all mentioned test methods will be presented for crosslinked polyvinyl-pyrrolidone (PVP) and conclusions regarding the applicability of the extrapolation methods will be discussed. Hot storage tests up to semi-industrial scale and their combination with various thermoanalytical methods allow a much more precise prediction of the self-ignition behaviour of large bulks. A further promising approach to estimate their heat release rates, and hence, the risk of self-ignition under technical conditions, is the use of microcalorimetric methods.
Self-ignition Behaviour of Bulk Materials: How Reliable is the Extrapolation of Laboratory Tests?
(2022)
The self-ignition behaviour of bulks is usually determined with the aid of isoperibolic or adiabatic hot storage tests; the sample volumes here are typically in the range of approx. 100 cm³ to several litres. The extrapolation to technically relevant volumes holds, however, considerable uncertainties. To reduce these uncertainties, a test stand was set up that allows to investigation sample sizes of up to 1000 dm³. These allow the study of selfignition behavior closer to the conditions that prevail in practice. The suitability (or unsuitability) of the established methods (including dangerous goods classification tests) were to be demonstrated and influencing variables that cannot be measured on a laboratory scale were to be determined.
In addition, various analytical methods were used for the determination of reaction kinetic data of solid bulk materials and to predict the self-ignition behaviour of large storages. These are thermal analyses such as differential scanning calorimetry DSC, simultaneous thermal analysis STA as well as microcalorimetry for highprecision measurement of heat flows.
Complete test series using all mentioned test methods will be presented for crosslinked polyvinyl-pyrrolidone (PVP) and conclusions regarding the applicability of the extrapolation methods will be discussed. Hot storage tests up to semi-industrial scale and their combination with various thermoanalytical methods allow a much more precise prediction of the self-ignition behaviour of large bulks. A further promising approach to estimate their heat release rates, and hence, the risk of self-ignition under technical conditions, is the use of microcalorimetric methods.
CEQAT-DGHS Interlaboratory Test Programme for Chemical Safety - Need of Test Methods Validation -
(2019)
Safety experts, manufacturers, suppliers, importers, employers or consumers must be able to rely on the validity of safety-related test methods and on correct test results and assessments in the laboratory. Via the eChemPortal lots of data from the REACH registration dossiers are available. However, the quality and correctness of the information remains in the responsibility of the data submitter. Unfortunately, we found more or less appropriate information on physicochemical properties and concluded that more quality or adequacy of any data submitted will be needed.
Interlaboratory tests play a decisive role in assessing the reliability of test results. Interlaboratory tests on different test methods have been performed by Bundesanstalt für Materialforschung und –prüfung (BAM) and Physikalisch-Technische Bundesanstalt (PTB) in collaboration with the QuoData GmbH during the last 10 years. Significant differences between the results of the participating laboratories were observed in all interlaboratory tests. The deviations of the test results were not caused only by laboratory faults but also by deficiencies of the test method.
In view of the interlaboratory test results the following conclusions can be drawn:
• To avoid any discrepancy on classification and labelling of chemicals it should become state of the art to use validated test methods and the results accompanied by the measurement uncertainty.
• A need for improvement is demonstrated for all examined test methods. Thus, interlaboratory tests shall initially aim at the development, improvement and validation of the test methods and not on proficiency tests.
• The laboratory management and the practical execution of the tests need to be improved in many laboratories.
• The term "experience of the examiner" must be seen critically: A "long experience with many tests" is not necessarily a guarantee for correct results.
Experimental study on the performance of the standardized test method for detonation flame arresters
(2022)
Flame arresters are autonomous protection systems and are among the constructive explosion protection measures that limit the effects of an explosion.
In this study, the performance of the standardized test method regulated in the DIN EN ISO 16852 standard for in-line flame arresters for stable and unstable detonations, which is mainly designed for atmospheric conditions, is examined. In an interlaboratory comparison, experiments are performed for different pressures before ignition and explosion groups according to the standardized test method. The experimental data is analyzed in detail to further optimize the test method and to thus achieve an improved reproducibility of detonation tests at high pressures, especially regarding the deflagration to detonation transition.
Based on these results, an improved test method for detonation flame arresters will be developed, which will ensure better reproducibility as well as applicability under non-atmospheric conditions.
For hazard assessment purposes, the dispersion of gases in complex urban areas is often a scenario to be considered. However, predicting the dispersion of heavy gases is still a challenge. In Germany, the VDI Guideline 3783, Part 1 and 2 is widely used for gas dispersion modelling. Whilst Part 1 uses a gauss model for calculating the dispersion of light or neutrally buoyant gases, Part 2 uses wind tunnel experiments to evaluate the heavier-than-air gas dispersion in generic built up areas. In practice, with this guideline, it is often not possible to adequately represent the existing obstacle configuration. To overcome this limitation, computational fluid dynamics (CFD) methods could be used. Whilst CFD models can represent obstacles in the dispersion area correctly, actual publications show that there is still further research needed to simulate the atmospheric flow and the heavy gas dispersion. This paper presents a modified k-ε-turbulence model that was developed in OpenFOAM v5.0 (England, London, The OpenFOAM Foundation Ltd Incorporated) to enhance the simulation of the atmospheric wind field and the heavy gas dispersion in built-up areas. Wind tunnel measurements for the dispersion of neutrally buoyant and heavy gases in built-up environments were used to evaluate the model. As a result, requirements for the simulation of the gas dispersion under atmospheric conditions have been identified and the model showed an overall good performance in predicting the experimental values.
CFD simulations of near-ground gas dispersion depend significantly on the accuracy of the wind field. When simulating wind fields with conventional RANS turbulence models, the velocity and turbulence profiles specified as inlet boundary conditions change rapidly in the approach flow region. As a result, when hazardous materials are released, the extent of hazardous areas is calculated based on an approach flow that differs significantly from the boundary conditions defined. To solve this problem, a turbulence model with consistent boundary conditions was developed to ensure a horizontally homogeneous approach flow. Instead of the logarithmic vertical velocity profile, a power law is used to overcome the problem that with the logarithmic profile, negative velocities would be calculated for heights within the roughness length. With this, the problem that the distance of the wall-adjacent cell midpoint has to be higher than the roughness length is solved, so that a high grid resolution can be ensured even in the near-ground region which is required to simulate
gas dispersion. The evaluation of the developed CFD model using the German guideline VDI 3783/9 and wind tunnel experiments with realistic obstacle configurations showed a good agreement between the calculated and the measured values and the ability to achieve a horizontally homogenous approach flow.
The maximum explosion overpressure and the maximum rate of pressure rise, which characterize thedust explosion severity, are commonly measured in apparatuses and under specific conditions defined byinternational standards. However, those standards conditions, designed for micropowders, may not befully adapted to nanoparticles. Investigations were conducted on different nanopowders (nanocellulose,carbon black, aluminum) to illustrate their specific behaviors and highlight the potential inadequacyof the standards. The influence of the sample preparation was explored. Various testing procedureswere compared, focusing on the dust cloud turbulence and homogeneity. Dust dispersion experimentsevidenced the importance of the characterization of the dust cloud after dispersion, due to the frag-mentation of agglomerates, using metrics relevant with nanoparticles reactivity (e.g. surface diameterinstead of volume diameter). Moreover, the overdriving phenomenon (when the experimental resultsbecome dependent of the ignition energy), already identified for micropowders, can be exacerbated fornanoparticles due to their low minimum ignition energy and to the high energy used under standardconditions. It was evidenced that for highly sensitive nanopowders, pre-ignition phenomenon can occur.Finally, during severe explosions and due to a too long opening delay of the ‘fast acting valve’, the flamecan go back to the dust container.
Detonation flame arresters are typically used as protection systems in industrial applications to prevent flame transmission from one section of a plant to another after an incidental ignition. Numerous processes in the chemical and petrochemical industry are taking place under non-atmospheric conditions (e.g., increased pressure and/or temperature) in order to optimize the production capabilities. To verify and examine the suitability of detonation flame arresters, a test method originating from the DIN EN ISO 16852 standard, which is mainly based on findings from experiments under atmospheric conditions, is used. In order to improve the reproducibility of detonation tests at high pressures, especially regarding the deflagration to detonation transition, test methods will be analyzed and improved.
The main objective of this study is to develop an improved test method for detonation flame arresters, which offers a higher reproducibility and moreover, an applicability under non-atmospheric conditions. Therefore, an interlaboratory comparison on the performance of in-line flame arresters for stable and unstable detonations is jointly conducted by the project partners (PTB, BAM, Braunschweiger Flammenfilter GmbH and IBExU GmbH). The experiments are performed according to the test method regulated in the DIN EN ISO 16852 standard for different pressures before ignition and different explosion groups. Potential ambiguities of the standardized test method that might lead to the differing results at the different institutes are identified from the interlaboratory comparison. Based on these results, an improved test method for detonation flame arresters will be developed, which will ensure a greater safety at process plants while handling combustibles.
Comparative study on the performance of the standardized test method for detonation flame arrestors
(2020)
Detonation flame arresters are widely used as protection systems in industrial applications to avoid damage from incidental gas explosions, by preventing the propagation of the ongoing explosion from one section of a plant to another. Numerous processes in the chemical and petrochemical industry are taking place under non-atmospheric conditions (e.g. increased pressure and/or temperature) in order to optimize the production capabilities. The suitability of detonation flame arresters is verified and examined according to the DIN EN ISO 16852 standard, which is only based on findings from experiments under atmospheric conditions. In some instances, differing results are obtained by the different institutes using the current standardized test procedure, especially for instable detonations as well as for detonations at elevated pressures before ignition.
The primary objective of this study is to develop an improved test method for detonation flame arresters, which offers a higher reproducibility and moreover, an applicability under non-atmospheric conditions. For this aim, the project partners (PTB, BAM, Braunschweiger Flammenfilter GmbH and IBExU GmbH) jointly conduct an interlaboratory comparison on the performance of in-line flame arresters for stable and instable detonations. The experiments are performed according to the test method regulated in the DIN EN ISO 16852 standard for different pressures before ignition and for different explosion groups (IIA, IIB, IIC). The interlaboratory comparison points out potential ambiguities of the standardized test procedure that might lead to the differing results at the different institutes. Based on these experimental findings, an improved test method for detonation flame arresters will be developed, which will ensure a greater safety at process plants while handling combustible liquids and gases.
The explosion characteristics of anthracite and bituminous coals in O2/N2 ambience were experimentally studied via a 20-L spherical explosion chamber with various ignition energies of 2, 5 and 10 kJ. A novel method based on combustion duration time was proposed for the first time, with an emphasis on the determination of the limiting oxygen concentration (LOC). The values of LOC determined by the alternative method were almost consistent with those obtained by using the standardized overpressure method, where the LOCs were above 21.6%, 19.8%, and 13.2% for anthracite coal and 11.4%, 9.6%, and 9.0% for bituminous coal when the ignition energy is 2, 5, and 10 kJ, respectively. But the newly proposed method was found to be much less affected by the ignition energy compared with the standardized overpressure method, taking combustion duration time as an explosion criterion thus had a higher efficiency and required fewer experiments. The results also showed that as oxygen concentration decreases from 21.6% to 14.4%, the maximum explosion pressure decreases from 0.4334 MPa to 0.1034 MPa for anthracite coal and from 0.5664 MPa to 0.3981 MPa for bituminous coal, respectively. Moreover, the effect of ignition energy varied with varying volatile matter content and ignition mechanism of coal dusts. The higher the volatile content, the less sensitive it is to the ignition energy. The newly proposed method will provide a reference for the new standard development, hazard analysis, explosion prevention and suppression by involving the use of inert gases of combustible powder industries.
Meta-analysis of heat release and smoke gas emission during thermal runaway of lithium-ion batteries
(2023)
Herein a meta-analysis of 76 experimental research papers from 2000 to 2021 is given about possible effects on the thermal runaway of lithium-ion battery cells. Data on the hazards of gas emissions and released heat are related to each other and differentiated by cell properties such as, cell geometry, cathode type or state of charge. Quantitative information on the total heat release in the range of 2.0–112.0 kJ Wh−1, the peak heat release rate in the range of 0.006–2.8 kW Wh−1and the smoke gas emission were extracted, normalized in terms of cell energy (Wh), combined in a data library and compared graphically. The total amount of gas emitted (3–48 mmol Wh−1) as well as the released amount of carbon monoxide (1–161 mg Wh−1) and hydrogen fluoride (2–197 mg Wh−1) were investigated as a function of the state of charge and cell geometry. The analysis reveals that the measured values are significantly influenced by the types of calorimeters and smoke gas analyzers used as well as by the type of thermal runaway trigger. This meta-analysis can serve as an important basis for any risk assessment of lithium-ion batteries.
The hydrogen tightness of high-pressure hydrogen storage is a Basic criterion for long-term storage. The H2 permeation coefficients of epoxy resin and a glass lacquer were determined to enable the geometric optimization of a glass capillary storage. It was found that the curing conditions have no significant influence on the H2 permeation coefficient of resin.
The H2 permeation coefficient of epoxy resin is only about three orders of Magnitude greater than that of borosilicate glass. This suggests that the initial pressure of 700 bar takes about 2.5 years to be halved in capillary array storage. Therefore, a high-pressure hydrogen storage tank based on glass capillaries is ideally suited for long-term storage in mobile applications.
Leaking methane (CH4) from infrastructures, such as pipelines and landfills, is critical for the environment but can also pose a safety risk. To enable a fast detection and localization of these kind of leaks, we developed a novel robotic platform for aerial remote gas sensing. Spectroscopic measurement methods for remote sensing of selected gases lend themselves for use on mini-copters, which offer a number of advantages for inspection and surveillance over traditional methods. No direct contact with the target gas is needed and thus the influence of the aerial platform on the measured gas plume can be kept to a minimum. This allows to overcome one of the major issues with gas-sensitive mini-copters. On the other hand, remote gas sensors, most prominently Tunable Diode Laser Absorption Spectroscopy (TDLAS) sensors have been too bulky given the payload and energy restrictions of mini-copters. Here, we present the Unmanned Aerial Vehicle for Remote Gas Sensing (UAV-REGAS), which combines a novel lightweight TDLAS sensor with a 3-axis aerial stabilization gimbal for aiming on a versatile hexacopter. The proposed system can be deployed in scenarios that cannot be addressed by currently available robots and thus constitutes a significant step forward for the field of Mobile Robot Olfaction (MRO). It enables tomographic reconstruction of gas plumes and a localization of gas sources. We also present first results showing its performance under realistic conditions.
In this paper, we present an autonomous aerial robot to reconstruct tomographic 2D slices of gas plumes in outdoor environments. Our platform, the so-called Unmanned Aerial Vehicle for Remote Gas Sensing (UAV-REGAS) combines a lightweight Tunable Diode Laser Absorption Spectroscopy (TDLAS) sensor with a 3-axis aerial stabilization gimbal for aiming on a versatile octocopter. The TDLAS sensor provides integral gas concentration measurements but no information regarding the distance traveled by the laser diode's beam or the distribution of the gas along the optical path. We complemented the set-up with a laser rangefinder and apply principles of Computed Tomography (CT) to create a model of the spatial gas distribution from these integral concentration measurements. To allow for a rudimentary ground truth evaluation of the applied gas tomography algorithm, we set up a unique outdoor test environment based on two 3D ultrasonic anemometers and a distributed array of 10 infrared gas transmitters. We present first results showing the 2D plume reconstruction capabilities of the system under realistic conditions.
In this paper, we present an autonomous aerial robot to reconstruct tomographic 2D slices of gas plumes in outdoor environments. Our platform, the so-called Unmanned Aerial Vehicle for Remote Gas Sensing (UAV-REGAS) combines a lightweight Tunable Diode Laser Absorption Spectroscopy (TDLAS) sensor with a 3-axis aerial stabilization gimbal for aiming on a versatile octocopter. The TDLAS sensor provides integral gas concentration measurements but no information regarding the distance traveled by the laser diode's beam or the distribution of the gas along the optical path. We complemented the set-up with a laser rangefinder and apply principles of Computed Tomography (CT) to create a model of the spatial gas distribution from these integral concentration measurements. To allow for a rudimentary ground truth evaluation of the applied gas tomography algorithm, we set up a unique outdoor test environment based on two 3D ultrasonic anemometers and a distributed array of 10 infrared gas transmitters. We present first results showing the 2D plume reconstruction capabilities of the system under realistic conditions.
In this talk, general aspects of the safety and acceptance of hydrogen technologies were presented. How can trust in new technologies be built when past accidents led to myths and fairy tales? The presentation does away with general prejudices and shows that handling hydrogen is neither more unsafe nor safer than handling other fuel gases. The basis for the safe handling of hydrogen is always a risk analysis.
Leaking methane (CH4) from infrastructures, such as pipelines and landfills, is critical for the environment but can also pose a safety risk. To enable a fast detection and localization of These kind of leaks, we developed a novel robotic platform for aerial remote gas sensing - the so-called Unmanned Aerial Vehicle for Remote Gas Sensing (UAV-REGAS).
In this paper, we present an autonomous aerial robot to reconstruct tomographic 2D slices of gas plumes in outdoor environments. Our platform, the so-called Unmanned Aerial Vehicle for Remote Gas Sensing (UAV-REGAS) combines a lightweight Tunable Diode Laser Absorption Spectroscopy (TDLAS) sensor with a 3-axis aerial stabilization gimbal for aiming on a versatile octocopter. The TDLAS sensor provides integral gas concentration measurements but no information regarding the distance traveled by the laser diode's beam or the distribution of the gas along the optical path. We complemented the set-up with a laser rangefinder and apply principles of Computed Tomography (CT) to create a model of the spatial gas distribution from these integral concentration measurements. To allow for a rudimentary ground truth evaluation of the applied gas tomography algorithm, we set up a unique outdoor test environment based on two 3D ultrasonic anemometers and a distributed array of 10 infrared gas transmitters. We present first results showing the 2D plume reconstruction capabilities of the system under realistic conditions.
The flammable hydrogen-blended methane–air and natural gas–air mixtures raise specific safety and environmental issues in the industry and transportation; therefore, their explosion characteristics such as the explosion limits, explosion pressures, and rates of pressure rise have significant importance from a safety point of view. At the same time, the laminar burning velocities are the most useful parameters for practical applications and in basic studies for the validation of reaction mechanisms and modeling turbulent combustion. In the present study, an experimental and numerical study of the effect of hydrogen addition on the laminar burning velocity (LBV) of methane–air and natural gas–air mixtures was conducted, using mixtures with equivalence ratios within 0.90 and 1.30 and various hydrogen fractions rH within 0.0 and 0.5. The experiments were performed in a 14 L spherical vessel with central ignition at ambient initial conditions. The LBVs were calculated from p(t) data, determined in accordance with EN 15967, by using only the early stage of flame propagation. The results show that hydrogen addition determines an increase in LBV for all examined binary flammable mixtures. The LBV variation versus the fraction of added hydrogen, rH, follows a linear trend only at moderate hydrogen fractions. The further increase in rH results in a stronger variation in LBV, as shown by both experimental and computed LBVs. Hydrogen addition significantly changes the thermal diffusivity of flammable CH4–air or NG–air mixtures, the rate of heat release, and the concentration of active radical species in the flame front and contribute, thus, to LBV variation.
The Jack Rabbit II (JR II) chlorine field trials in 2015 and 2016 involved nine 5–20 ton releases of pressurized liquefied chlorine from a tank mounted 1 m above a broad flat desert sand surface. A model comparison study was initiated, where 17 widely-used dense-gas dispersion models were run by scientists in seven countries.
Predictions were submitted following specified formats, using specified emissions and meteorology inputs. To compare with the model predictions, sets of observations were defined for the arc-maximum 1–3 s averaged concentrations (arc max C) and for cloud widths and heights (to 20 ppm and 200 ppm contours) at distances from 0.2 to 11.0 km from the release. The initial focus is on the three field trials (1, 6, and 7) that have the highest observed concentrations and that have detailed emissions information. It is found that these models are able to satisfactorily simulate (generally within a factor of two) the observed arc max C’s and their variation with downwind distance at this flat desert site. At each downwind distance, the scatter in the arc max C predictions covers about 1 ½ orders of magnitude, but the observed arc max C is within the range of the predictions. The median of the cloud width predictions is about 50% larger than the observed value for the three trials. The median of the cloud height predictions is within about 10% of the observed value. For both cloud width and/or height, there are a few models with large (factor of 3 or higher) overpredictions. Of the 17 models, when compared to observations, there is a core group of 5 or 6 with consistently (across all three trials and all distances) less mean error and scatter in their predictions of arc max C and cloud width and height. However, as a group, the 17 models are performing adequately (using the “factor of two” rule of thumb). An important caveat is that, at the JR II desert site, chlorine deposition is minimal. At a site with vegetation and/or organic-rich soil, the effects of removal of chlorine by deposition are expected to be significant.
Competence Centre H2Safety@BAM – Safeguarding the Quality Infrastructure in the Hydrogen Economy
(2022)
Hydrogen is a central component of the energy transition and the European Green Deal for a climate-neutral Europe. To achieve the goals defined for 2050, the EU and the German government have developed a framework for action and are making long-term investments in research, development, and the rapid implementation of innovative hydrogen technologies.
With the Competence Centre "H2Safety@BAM", BAM is creating the safety-related prerequisites for the successful implementation of hydrogen technologies at national as well as European level.
To this end, BAM conducts research, testing and consulting in a holistic and inter-disciplinary manner under one roof – in the Competence Centre H2Safety@BAM. The activities of the competence centre focus on ensuring the safety of infra-structures, plants, and processes as well as innovative hydrogen transport and storage systems based on digital quality testing and the experimental testing of components and systems. It thus creates the prerequisites for the implementation and adaptation of legal framework conditions as well as for standardization. Closely related to this are investigations into the properties and compatibility of metallic materials and polymers as well as friction systems for the safe operation of components, plants, processes, and systems. This interdisciplinary and holistic approach is complemented by the development of gas analytics and suitable sensors, online measurements of gas properties in process control, test scenarios under real conditions as well as impact assessments of accidents and risk assessments and risk management systems derived from them. With its portfolio of tasks and competences, BAM builds trust in the safety and reliability of technical system solutions for hydrogen.
Safety criteria for the transport of hydrogen in permanently mounted composite pressure vessels
(2020)
The recent growth of the net of hydrogen fuelling stations increases the demands to transport compressed hydrogen on road by battery vehicles or tube-trailers, both in composite pressure vessels. As a transport regulation, the ADR is applicable in Europe and adjoined regions, and is used for national transport in the EU. This regulation provides requirements based on the behaviour of each individual pressure vessel, regardless of the pressure of the transported hydrogen and relevant consequences resulting from generally possible worst case scenarios such as sudden rupture. In 2012, the BAM (German Federal Institute for Materials Research and Testing) introduced consequence-dependent requirements and established them in national transport requirements concerning the “UN service life checks” etc. to consider the transported volume and pressure of gases. This results in a requirement that becomes more restrictive as the product of pressure and volume increases. In the studies presented here, the safety measures for hydrogen road transport are identified and reviewed through a number of safety measures from countries including Japan, the USA and China. Subsequently, the failure consequences of using trailer vehicles, the related risk and the chance are evaluated. A benefit-related risk criterion is suggested to add to regulations and to be defined as a safety goal in standards for hydrogen transport vehicles and for mounted pressure vessels. Finally, an idea is given for generating probabilistic safety data and for highly efficient evaluation without a significant increase of effort.
Laboratory test results are of vital importance for correctly classifying and labelling chemicals as “hazardous” as defined in the UN Globally Harmonized System (GHS) / EC CLP Regulation or as “dangerous goods” as defined in the UN Recommendations on the Transport of Dangerous Goods. Interlaboratory tests play a decisive role in assessing the reliability of laboratory test results. Interlaboratory tests performed over the last 10 years have examined different laboratory test methods. After analysing the results of these interlaboratory tests, the following conclusions can be drawn:
1. There is a need for improvement and validation for all laboratory test methods examined.
2. To avoid any discrepancy concerning the classification and labelling of chemicals, the use of validated laboratory test methods should be state of the art, with the results accompanied by the measurement uncertainty and (if applicable) the probability of incorrect classification.
This paper addresses the probability of correct/incorrect classification (for example, as dangerous goods) on the basis of the measurement deviation obtained from interlaboratory tests performed by the Centre for quality assurance for testing of dangerous goods and hazardous substances (CEQAT-DGHS) to validate laboratory test methods. This paper outlines typical results (e.g. so-called “Shark profiles” – the probability of incorrect classification as a function of the true value estimated from interlaboratory test data) as well as general conclusions and steps to be taken to guarantee that laboratory test results are fit for purpose and of high quality.
The publicly available document encapsulates the first version of the Catalogue of Services of the future EC4Safenano Centre (CoS 2019).
The CoS 2019 is structured in 12 Service Categories and 27 Service Topics, for each of the 12 categories considered. This architecture configures a 12 x 27 matrix that allows ordering the potential EC4Safenano offer in 324 types of services/groups of services.
Each type of service/group of services is described, in a simple and friendly way, by means of a specific service sheet: the EC4Safenano - Service Data Sheet (EC4-SDS). These EC4-SDSs allow structuring and summarizing the information of each service, providing the customer with a concise view of characteristics of the service and also the contact details with the service provider.
The CoS 2019 deploys a map of services consisting of a set of 100 EC4-SDSs, covering 7 of the 12 Service Categories and 17 of the 27 Service Topics.
The harmonization of services is visualized as a future necessary step in EC4Safenano, in order to strengthen the offer and provide added value to customers with a growing offer of harmonized services in future versions of the CoS.
The information contained in this document is structured in 3 main sections, as follows:
• Catalogue structure. This section describes in short the main characteristics of the CoS 2019.
• Catalogue content. This section represents the core part of the document and encapsulates the set of 100 SDSs displaying the offer proposed by the CoS 2019.
• Online Catalogue. This section describes the resources implemented by EC4Safenano to facilitate the on-line consultation of the CoS 2019 by customers and other interested parties.
Performance of the standardized testing method for detonation fl ame arresters at increased pressure
(2022)
Detonation flame arresters are typically used as autonomous protection systems in industrial applications to prevent potential hazards associated with flammable and/ or explosive chemicals. To verify and examine the suitability of detonation flame arresters, a testing method originating from the DIN EN ISO 16852 standard is used, which is mainly designed for atmospheric conditions.
In order to optimize the production capabilities, numerous industrial processes are taking place at pressures, temperatures, or oxygen concentrations beyond the ambient range, i.e. at non-atmospheric conditions and information on the performance of the regulated testing method are therefore required when the standard testing protocols are modified with regard to pressure, temperature or oxidizer.
The main objective of this study is to develop an improved testing method for detonation flame arresters, which offers a higher reproducibility and moreover, an applicability under non-atmospheric conditions. Therefore, an interlaboratory comparison on the performance of in-line flame arresters for stable and unstable detonations is jointly conducted by the project partners (PTB, BAM, Braunschweiger Flammenfilter GmbH and IBExU GmbH). The experiments are performed according to the testing method regulated in the DIN EN ISO 16852 standard for different pressures before ignition and different explosion groups. The experimental data is analyzed in detail to further optimize the test method and to thus achieve an improved reproducibility of detonation tests at high pressures, especially regarding the deflagration to detonation transition.
Potential ambiguities of the standardized testing method that might lead to the differing results at the different institutes are identified from the interlaboratory comparison and the test method is modified accordingly. Based on these results, an improved testing method for detonation flame arresters will be developed, which will ensure a greater safety at process plants while handling combustibles.
Tetrafluoroethylene (TFE) is an industrial scale starting material e.g. for polymer production (PTFE, FEP). When ignited the chemically unstable TFE is capable of decomposing in an explosive way. Explosion propagation through pipe systems of production plants have led to damage and fatalities within the last seven decades.
Incident analyses identified compression heat a relevant source of ignition. Chemical plants consist of pipes, vessels, separating valves, strainers and other components. Before restarting the process after maintenance work, different parts of the plant components could be filled with TFE, nitrogen or air at different initial pressures ranging from vacuum or atmospheric to TFE at operating pressure. Valve opening procedures may cause a temperature increase in the gas phase. Compression takes place at polytropic conditions. Heat losses cannot be neglected. The temperature development in the gas depends upon the surface to volume ratio of the enclosure, geometrical influences, the state of gas flow, how fast the valve opens, and the heat capacity of the gas being compressed.
Laboratory scale tests (Meyer, 2009) revealed ignition of TFE/air due to compression heat. Tests in pipes of 28 mm inner diameter, i.e. already industrial scale, were performed by (Kluge et. al., 2016). In the present contribution initial test results from a 63 mm pipe will be compared with existing 28 mm pipe data. A description of the experimental setup as well as an explanation of the hazard diagram will be given.
Furthermore, a method allowing for the identification of hazardous conditions will be discussed.
Tetrafluoroethylene (TFE) is an industrial scale starting material e.g. for polymer production (PTFE, FEP). When ignited the chemically unstable TFE is capable to decompose in an explosive way. Explosion propagation through pipe systems of production plants have led to damage and fatalities within the last 7 decades.
Incident analyses identified compression heat a relevant source of ignition. Chemical plants consist of pipes, vessels, separating valves, strainers and other components. Before restarting the process after maintenance work different parts of the plant components could be filled with TFE, Nitrogen or Air at different initial pressures ranging from vacuum or atmospheric to TFE at operating pressure. Valve opening procedures may cause a temperature increase in the gas phase. Compression takes place at polytropic conditions. Heat losses cannot be neglected. Therefore the temperature development in the gas depends upon the surface-to-volume-ratio of the enclosure, geometrical influences, the state of gas flow, how fast the valve opens and the heat capacity of the gas being compressed.
In the present work initial test results from a 2.5” pipe will be compared with existing 1.1” pipe data. Geometrical effects will be briefly discussed as well as some first results concerning the influence of orifices are reported. Furthermore a method allowing for the identification of hazardous initial conditions is discussed.
This work presents an overview about the explosion behaviour of metallic powders from micron to nanosize.
Aluminium, magnesium, titanium, iron and zinc were considered and their explosion safety parameters were analysed as a function of their mean primary particle size either determined by BET measurements, particle size distribution. To depict the course of explosion behaviour for these metals, extensive literature review has been performed and additional experimental tests were also performed. Generally, decreasing the particle size in a metallic powder leads to a higher explosion severity. It appears that this statement is true till a critical Diameter below which the explosion severity (pmax, dp/dtmax) decreases for all the considered powders. This critical size can be explained by theoretical considerations on the nature of thermal transfer in the flame, namely by analysing the Cassel model. Finally, semi-empirical models were also developed for aluminium to highlight the specific micrometre and nanometre behaviour and the influence of turbulence, particle burning time, Diameter and concentration. The influence of these key parameters needs to be further assessed in a future work in order to better understand the mechanisms involved and to extend the scope to other powdered materials.
The production of materials with dimensions in the nanometre range has continued to increase in recent years. In order to ensure safety when handling these products, the hazard potential of such innovative materials must be known. While several studies have already investigated the effects of explosions (such as maximum explosion pressure and maximum pressure rise) of powders with primary particles in the nanometre range, little is known about the ignition temperatures and flame velocities. Therefore, the minimum ignition temperature (MIT) of metallic nano powders (aluminium, iron, copper and zinc) was determined experimentally in a so called Godbert-Greenwald (GG) oven. Furthermore, the flame velocities were determined in a vertical tube. In order to better classify the test results, the tested samples were characterised in detail and the lower explosion limits of the tested dust samples were determined. Values for the burning velocity of aluminium nano powders are higher compared to values of micrometre powd
ers (from literature). While MIT of nanometre aluminium powders is within the range of micrometre samples, MIT of zinc and copper nano powders is lower than values reported in literature for respective micrometre samples.
The production of materials with dimensions in the nanometre range has continued to increase in recent years. In order to ensure safety when handling these products, the hazard potential of such innovative materials must be known. While several studies have already investigated the effects of explosions (such as maximum explosion pressure and maximum pressure rise) of powders with primary particles in the nanometre range, little is known about the ignition temperatures and flame velocities. Therefore, the minimum ignition temperature (MIT) of metallic nano powders (aluminium, iron, copper and zinc) was determined experimentally in a so called Godbert-Greenwald (GG) oven. Furthermore, the flame velocities were determined in a vertical tube. In order to better classify the test results, the tested samples were characterised in detail and the lower explosion limits of the tested dust samples were determined. Values for the burning velocity of aluminium nano powders are higher compared to values of micrometre powders (from literature). While MIT of nanometre aluminium powders is within the range of micrometre samples, MIT of zinc and copper nano powders is lower than values reported in literature for respective micrometre samples.
Quasi-static dispersion of dusts for the determination of lower explosion limits of hybrid mixtures
(2020)
Knowledge of explosion limiting concentration of explosible materials is necessary for the design of explosion protection measures. Currently employed methods of testing MEC of a dust cloud or LEL of a hybrid mixture are based on arbitrary assumptions and possess technical limitations that often lead to values of MEC/LEL, which are unrealistically low or poorly reproducible.
This contribution presents an improved method for experimental determination of MEC of a combustible dust cloud or LEL of a flammable gas or hybrid mixture. The new set-up operates under laminar conditions and allows a uniform suspension of dust particles in an open top acrylic glass tube. Dust concentration is measured with the help of infrared sensors installed a few centimeters above and below the ignition source.
In order to evaluate the dependence of MEC on flow front velocity, MEC of lycopodium was determined at four flow velocities. The results show that the flow field intensity does not significantly influence the MEC of lycopodium for the flow ranges tested in this work. Moreover, LEL of hybrid mixtures of lycopodium and methane was also tested at flow velocities of 4.7 cm/s, 5.8 cm/s, 7 cm/s and 11 cm/s and compared with the values obtained from other sources. The results suggest that the requirement of high energy pyrotechnical igniter may be relinquished, provided that a truly homogeneous suspension of dust particles could be achieved.
Moreover, the effect of relative amount of dust and gas, on the course of ignition and flame propagation in hybrid mixtures at their LEL, was studied by the help of high speed videos. For hybrid mixtures of carbonaceous dusts (like lycopodium) at their LEL, ignition occurs in the gas phase, however, flame propagation is only possible through a two-way interaction of dust and gas during the course of combustion.
Protection from explosion events requires the determination of key safety parameters like lower explosion limit. maximum Explosion over-pressure. and maximum rate of pressure rise. These Parameters are routinely obtained through standard tests performed typically either in a 20 L -sphere or a 1 m3-container. But several aspects are worth a closer investigation. Firstly, the test apparatus must be able to disperse a fairly uniform dust cloud. However. previous investigations showed that actually the current dispersion System can be improved. Secondly, the influence of humidity on the explosivity is not considered in current standards. lt is just stated that the relative humidity should be checked and noted down.
though some provisions exist in American standards. Thirdly. the ignition delay time is sometimes modified to study the impact of the dust cloud turbulence on flame propagation but is often misunderstood.
Maybe these aspects have not been thoroughly considered for micron powders. However. in the case of nanopowders. the importance of these influencing factors was shown in order to duly evaluate explosion parameters. Experimental evidences confirm these aspects and alternative solutions will be presented.