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The introduction of hydrogen as a safe energy carrier needs a robust knowledge base, tools for the design and safety assessment of hydrogen technologies built on it, and an internationally harmonized set of standards and regulations. Many of the innovative technologies imply hydrogen at high pressures and/or cryogenic temperatures, with which private users come into contact for the first time in distributed applications. In order to avoid over-conservative, expensive safety solutions, while at the same time demonstrating the usability and safety of hydrogen applications and maintaining acceptance for the technology, safety research must also keep pace with, or better yet anticipate, trends in technological development. Thus, this overview article describes not only the current state of knowledge and technology regarding hydrogen safety, but also its further development.
Die Einführung von Wasserstoff als sicherer Energieträger braucht eine robuste Wissensbasis, darauf aufgebaute Werkzeuge zur Auslegung und Sicherheitsbewertung von Wasserstofftechnologien und ein international harmonisiertes Regelwerk. Viele der innovativen Technologien implizieren Wasserstoff bei hohen Drücken und/oder kryogenen Temperaturen, mit denen in verteilten Anwendungen erstmalig private Nutzer in Kontakt kommen. Um überkonservative, teure Sicherheitslösungen zu vermeiden, gleichzeitig aber die Einsetzbarkeit und Sicherheit von Wasserstoffanwendungen zu demonstrieren und die Akzeptanz für die Technologie aufrecht zu halten, muss auch die Sicherheitsforschung mit den Trends der technologischen Entwicklung Schritt halten, oder sie besser noch antizipieren. So beschreibt dieser Überblicksartikel nicht nur den gegenwärtigen Stand der Kenntnisse und Technik bezüglich Wasserstoffsicherheit, sondern auch ihre Weiterentwicklung.
The silicon based semiconductor structure Si/SiO2/Si3N4/LaF3/Pt can be used as a potentiometric oxygen sensor working at room temperature. A thermal re-activation can be applied to overcome the earlier disadvantage of an increase in response time with continuous use. Using the Pt gate electrode as a resistive heater, very short electrical high-power pulses can be applied. A heating time as short as 300 ns was sufficient for the re-activation of the sensor. This way, only the sensitive thin layer system LaF3/Pt was heated, and the whole sensor was at room temperature immediately after heating. Impedance spectroscopy, X-ray photoelectron spectroscopy (XPS) and quadruple mass spectrometric (QMS)thermogravimetry (TG) were used to investigate the mechanism of deterioration in dynamic sensor behaviour and re-activation. The formation of hydrated carbonate and the desorption of CO2 and H2O have been shown to be the causes.
This paper describes a modified experimental setup for the test apparatus 20-L-Sphere (also known as 20-L Siwek Chamber), that enables the test samples to be kept under inert atmospheric conditions nearly until ignition. This setup was designed to allow the determination of safety characteristics of nano powders under most critical circumstances (e.g. minimisation of the influence of oxidation before the test itself). The aim of this modification was to determine, whether or not the current setup and procedures underestimate the explosion violence and ignitability of nano powders. For this purpose, two different methods, the so called inerting method and the modified method (using a special nozzle called mushroom nozzle) are used. Both methods are described in the paper. The work includes experimental results of micrometer dusts to validate the modified method. Moreover first results of nanometer iron and aluminium dusts are presented, which were kept at inert conditions until shortly before the ignition. The tested nano iron was found to react pyrophoric, as soon as it gets in contact with air, while the tested nano aluminium did not generally show such behaviour. Tests with nano aluminium using the inerting method revealed a higher pressure rise in comparison to the standard test procedure. This could suggest a different extent of passivation. To investigate this effect more closely, further testes with more nano powders are required.
Modified setup of 20-L-sphere for the determination of safety characteristics of nano powders
(2013)
This paper describes a modified experimental setup for the test apparatus 20-L-Sphere (also known as 20-L Siwek Chamber), that enables the test samples to be kept under inert atmospheric conditions nearly until ignition. This setup was designed to allow the determination of safety characteristics of nanopowders under most critical circumstances (e.g. minimisation of the influence of oxidation before the test itself). The aim of this modification was to determine, whether or not the current setup and procedures underestimate the explosion violence and ignitability of nanopowders. The work includes experimental results of micrometer dusts to validate the modified setup. Moreover first results of nanometer iron and Aluminium dusts are presented, which were kept at inert conditions until shortly before the ignition. The tested nano iron was found to react pyrophoric, as soon as it gets in contact with air, while the tested nano Aluminium did not generally show such behaviour.
In practice, occurring explosive dust/air mixtures are usually not homogeneous and in many cases do not spread over the whole enclosure. For the safety measure explosion venting, a smaller venting area might be sufficient as calculated according to venting standards (EN 14491 'Dust Explosion Venting Protective Systems'). The tendency of bulk materials to form dust clouds is not taken into account so far. To optimize the design of explosion protection measures, a new safety characteristic the so-called 'dustiness' (see VDI 2263 part 9 'Determination of Dustiness of Bulk Materials'.) could be useful. Dustiness means the tendency of dust to form dust clouds. There are six dustiness groups (DG) from one to six (one means little tendency to stay airborne, six the opposite). The paper describes first results on the reasons for different dustiness and on dust explosion venting for several dusts of different dustiness. A 75 L vertical tube apparatus for vented dust explosion experiments was created. Pressure, pressure rises and flame speeds were measured to evaluate the course of the dust explosions. In addition the paper includes CFD simulations (ANSYS CFX) about the possibilities to model the dust/air mixtures with the Euler/Lagrange approach. In order to simulate the settling of dust clouds more realistic the particle surface area was adjusted and the particle size distribution was taken into account. Results were compared to experimentally determined terminal velocities.
Determination of measurement uncertainties in adiabatic hot storage experiments for flammable dusts
(2012)
Experimentelle Untersuchungen zum Einfluss von Brandbeschleuniger auf den Verlauf von Raumbränden
(2013)
Observed autoignition events and extinguishing the resulting smouldering fires in an underground storage system of a coal-fired power plant have provided insight into the array of contributing variables, and some experience on quantifying the risk with alternative scenarios of event initiation, progress and potential mitigation. Although the first attempts to quantify the risk suggest high sensitivity to the sequence of action taken after fire alarm, and no similar storage sites really exist, some recommended preventive, corrective and other mitigating activities can be at least partly defined and improved by using the cumulative experience and parallel efforts in other closed or underground storage sites. However, there are also so-called black (or at least grey) swans: unexpected events for which the facility may be poorly prepared for. In the case of the underground storage silos, such an event was experienced when incoming cold coal during a harsh winter season froze the sewer system that normally protects the stored coal from seepage water. With blocked normal bypass, the seepage water found its way to the coal silos and created large clumps of icy coal that blocked the coal conveyors. Although freezing weather is not unusual at high-latitude power plants, the common methods to combat freezing of coal are mainly useful for open storage sites and above-ground transport. Options for mitigation are discussed, as well as the event chain leading to an event that had never previously occurred. The case is discussed from the point of view of options to prepare for rare or unforeseen events.
A new safety characteristic the 'dustiness' according to VDI 2263 part 9 (Verein Deutscher Ingenieure, 2008) is investigated. Dustiness means the tendency of a dust to form clouds. The paper deals with the influence of the dustiness on vented dust explosions. In order to look into the effects of the dustiness on dust cloud formation and explosion properties experiments and simulations in a vertical dust dispersion glass tube apparatus were carried out.
Preliminary explosion experiments showed that the dustiness has an influence on the reduced explosion pressure in a vented 75 L test apparatus. Dusts with comparable pmax and KSt values and different dustiness were tested. Dusts with higher dustiness produced higher overpressures, despite comparable safety characteristics. In order to verify the results for applications in the process industries further tests with different settings are planned as well as industrial scale experiments. Characteristics of the dust such as particle size, density, specific surface area and particle shape, which influence the dispersibility, have been determined experimentally.
The Euler/Lagrange and the Euler/Euler approaches are compared for simulating an exemplary dust/air mixture. Especially sedimentation and the ability of the approaches to simulate the tendency of dust to stay airborne were investigated. The Euler/Lagrange approach is better suited for simulating local dust concentrations, particle size distributions and particle forces. It could be used to point out regions of high dust concentrations in a vessel. With the Euler/Euler method it is possible to achieve fast solutions for one specified diameter, but the simulated dust/air mixtures are always more homogenous than in reality. ANSYS CFX version 13 was used in all simulations.
Determination of measurement uncertainties in adiabatic hot-storage experiments for reactive dusts
(2013)
The formal kinetics of self-ignition of solid bulk materials theoretically can be derived from just one single adiabatic hot-storage test. The question arises how uncertainties in the measurements can be quantified and how these uncertainties affect the results of the subsequent predictions. Adiabatic and isoperibolic hot-storage basket tests were performed for samples of lignite coal, black coal, cork dust, a polymer dust, and wax-coated silicid acid. In the adiabatic experiments, the starting temperature and the temperature control of the oven were varied systematically to study the uncertainty margin of adiabatic tests. The apparent activation energy and the pre-exponential factor of the lumped reaction were derived from the adiabatic tests including average values and standard deviations and compared to isoperibolic experiments performed according to the European standard EN 15188. It could be shown that with a precise temperature control of the adiabatic oven combined with an automated computation of the maximum rate of temperature rise the uncertainty of the apparent activation energy can be limited to less than 10%.
The Fractional Effective Dose model was used to predict the fire smoke toxicity numerically. In this context fire tests were carried out for three different building materials: polyurethane, flame retardant polyurethane and polyvinyl chloride. The fire tests were performed for flaming and smoldering combustion. The aim of the fire tests was to determine the light extinction, the smoke density and the combustion products at varying oxygen concentrations, different temperatures and different irradiance levels. The fire tests were performed in the German DIN-tube and also in the Cone Calorimeter. Stoichiometric coefficients at varying oxygen concentrations and temperatures were determined from measurements. With these stoichiometric coefficients reaction equations were defined and implemented in the Computational Fluid Dynamics (CFD) program, ANSYS CFX. The implemented reaction equations were used to account for different ventilation and temperature conditions in the simulation. The fire and smoke propagation was calculated numerically with CFD in the room corner test geometry. Equations to account for toxicity and light extinction were also implemented and were used to analyse the toxicity and the optical properties of fire smoke with CFD.
Die Nanotechnologie gilt als die Wachstumsbranche der nächsten Jahrzehnte. Nicht zuletzt ist diese Entwicklung der veränderten Eigenschaften der Materialien im Nanometerbereich zuzuschreiben. Das andersgeartete Verhalten solcher Stoffe und die daraus ableitbare Unkenntnis über die Interaktion dieser Materialien mit ihrer Umgebung erfordert eine intensive Auseinandersetzung mit der Thematik zur Risikoabschätzung. Deshalb wurden und werden z.B. die gesundheitlichen Wirkungen von nanoskaligen Materialien auf den menschlichen Organismus bereits in zahlreichen Studien und Forschungsvorhaben untersucht.
Fundierte Erfahrungen und Erkenntnisse über Brand- und Explosionsgefahren bei der Herstellung und Handhabung von nanoskalig hergestellten brennbaren Materialien bzw. von Stoffen mit Partikelgrößen < µlpm liegen hingegen bisher kaum vor. Aufgrund von Erfahrungen mit Stäuben mit Partikelgrößen im Mikrometerbereich ist jedoch bekannt, dass Stoffe mit abnehmender Partikelgröße kritischer einzustufen sind, da beispielsweise ihre Explosionsheftigkeit und Zündempfmdlichkeit zunehmen.
Die Explosionseigenschaften brennbarer Stäube werden durch sicherheitstechnische Kenngrößen beschrieben. Die Bestimmung sicherheitstechnischer Kenngrößen von Nanostäuben - welche die Grundlage für eine Gefährdungsbeurteilung und das Auslegen von Schutzmaßnahmen für Anlagen bilden - erfolgte bislang nur in geringem Umfang. Diese Untersuchungen wurden zudem großteils in Analogie zu den genormten Verfahren für Mikrostäube durchgeführt. Es wurde dabei jedoch nicht überprüft, ob die für Mikrostäube etablierten Prüfverfahren für eine sichere Bewertung des Brenn- und Explosionsverhaltens geeignet sind. Darüber hinaus kann es durch aus den Prüfapparaturen freigesetzten Staub zu einer Gesundheitsgefährdung der Mitarbeiter kommen.
Da bisherige Untersuchungen zum Brand- und Explosionsverhalten von Nanostäuben den Oxidationsgrad der Proben nicht berücksichtigt haben, bestand die Vermutung, dass das Gefahrenpotential von Nanostäuben bislang unterschätzt werden könnte. Deshalb wurde ein modifizierter Prüfaufbau der Prüfapparatur 20-L Kugel entwickelt, um Nanostäube und deren Gefahrenpotential richtig einschätzen und der Kernfrage im Titel dieses Beitrages näher auf den Grund gehen zu können.
Insbesondere metallische Nanostäube wurden bei den ersten Tests zur Bestimmung des Brand- und Explosionsverhaltens untersucht. Bei entsprechenden Stäuben ist zu erwarten, dass sich eine mögliche Oberflächenoxidation bzw. Passivierung besonders stark auf das Explosionsverhalten auswirken könnte. Darüber hinaus ist bekannt, dass metallische Stäube pyrophor reagieren oder sich aufgrund der hohen Scherkräfte bereites beim Eindüsen in die Versuchsapparatur entzünden können. Dies kommt gelegentlich bei Metallstäuben mit Medianwerten von wenigen Mikrometern vor. Da bei nanoskaligen Stäuben theoretisch wesentlich größere Oberflächen auftreten, ist davon auszugehen, dass sich dieses Verhalten bei solchen Stäuben verstärken könnte. Dies wurde von Wu et al. in für nanoskalige Eisen und Titanpartikel nachgewiesen.