2.1 Sicherheit von Energieträgern
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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 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.
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.
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.
In this study, experimental determination and modelling investigations for the explosion regions of 1,3-dioxolane/inert gas/N2O and 1,3-dioxolane/inert gas/air mixtures were carried out and compared. The experimental measurements were carried out at 338 K and atmospheric pressure according to EN1839 method T using the inert gases N2, CO2, He and Ar. The results showed that the ratio of the lower explosion limit in N2O (LELN2O) to the lower explosion limit in air (LELair) is 0.52 and the ratio of the maximum oxygen content in air (MOCair) to the limiting oxidizer fraction in nitrous oxide (LOFN2O) is 0.36 ± 0.02 independent of the inert gas. When comparing the inert gas amount at the apex based on the pure oxidizing component, which is O2 in case of air, N2O-containing mixtures need less inert gas to reach the limiting oxidizer quantity whereas the efficiency of inert gases is in the same order. The coefficients of nitrogen equivalency however were found to differ to some extent. The explosion regions of 1,3-dioxolane/inert gas/oxidizer mixtures were modelled using the calculated adiabatic flame temperature profile (CAFTP) method as well as corrected adiabatic flame temperatures. The results indicate good agreement with experimental data for CO2, N2 and Ar- containing mixtures. The noticeable deviations that occur when He is the inert gas are due to the lacking transport data of that mixture.
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.
Die F-Gas-Verordnung der EU gewährt Ausnahmen vom GWPbezogenen Verbot des Inverkehrbringens für stationäre Kühlgeräte für Anwendungen unter -50 °C. Brennbare Alternativen auf der Basis von Methan, Ethan und Ethylen stehen zur Verfügung, sind aber aufgrund ihrer Entzündbarkeit nicht für alle Anwendungen einsetzbar. Distickstoffmonoxid (N2O) mit einem Tripelpunkt bei -92 °C scheint aber eine Alternative zu sein. Die mögliche exotherme Zersetzung von N2O erfordert jedoch zusätzliche Maßnahmen, um solche Systeme sicher betreiben zu können. Am ILK und an der Hochschule Karlsruhe wurden zwei Tieftemperatursysteme mit Gemischen aus N2O und CO2 und verschiedenen Schmierstoffen entwickelt, gebaut und bei Verdampfungstemperaturen bis -80 °C erfolgreich betrieben.
VORSICHT: Reines N2O sowie Mischungen von N2O und CO2 mit Schmiermitteln auf Kohlenwasserstoffbasis können explosionsartig reagieren.
The EU F-Gas Regulation grants exceptions from the GWP-related placing on the market prohibition for stationary refrigeration equipment for applications below -50 °C. Nonetheless, non-flammable refrigerants, which can be used for that temperature range, become increasingly expensive and rare inside the EU due to the phase down of HFCs under the regulation. Flammable alternatives based on methane, ethane and ethylene are available, but are not viable for all applications due to their flammability. Carbon dioxide cannot be used for applications below -50 °C due to CO 2 ’s triple point at -56 °C. Nitrous oxide with a triple point at -92 °C seems to be an alternative. However, possible exothermal decomposition of N 2 O calls for additional measures in order to be able to operate such systems safely. Two low-temperature systems have been developed, built and successfully operated at evaporation temperatures down to - 80 °C with mixtures of N 2 O and CO 2 and different lubricants at ILK and Karlsruhe University of Applied Sciences. The units achieved similar energy efficiency as the standard HFC-equipment used for freeze drying. Possible decomposition of N 2 O could successfully be supressed by various measures.
Die Explosionsbereiche für Dreistoffsysteme aus Brennstoff Inertgas und Luft wurden nach dem Modell der konstanten adiabatischen Flammentemperaturprofile berechnet. Für die Parametrisierung des halbempirischen Modells muss der Explosionsbereich für ein bestimmtes Dreistoffsystem aus Brennstoff, Inertgas und Luft bekannt sein. Dann lassen sich Explosionsbereiche desselben Brennstoffs mit einem beliebigen Inertgas und bei einer beliebigen Temperatur berechnen. Ergänzend zu früheren Arbeiten, in denen die Explosionsbereiche für Brenngase aus der homologen Reihe der Alkane und Alkene berechnet worden sind, wurden nun die Berechnungen für 1-Propanol, Aceton und Difluormethan durchgeführt. Als Inertgase wurden neben Stickstoff und Kohlendioxid auch die Edelgase Argon und Helium berücksichtigt.
Für die Berechnung der Explosionsbereiche in Systemen mit Helium, ist das Modell erweitert worden, so dass auch die Transporteigenschaften (d.h. Wärmeleitfähigkeit, Diffusionskoeffizient) der Komponenten berücksichtigt werden. Weiterhin ist eine Möglichkeit zur praxisnahen Berechnung der Spitze des Explosionsbereichs implementiert worden. Die Ergebnisse zeigen insgesamt, dass die Berechnung der Explosionsbereiche für Alkohole, Ketone und halogenierte Kohlenwasserstoffe mit ähnlicher Genauigkeit wie für Alkane und Alkene möglich ist. Die vorgenommenen Modifikationen sind geeignet, um auch eine Berechnung für Gasgemische mit Helium durchzuführen, dessen starke inertisierende Wirkung im Vergleich zu den Inertgasen
Argon oder Stickstoff vor allem auf den stark unterschiedlichen Transporteigenschaften beruht.